Capacitance reduction

Abstract

A method of processing a substrate, the method comprising: providing a patterned substrate having one or more gaps between features; depositing a sacrificial material over the substrate, wherein the sacrificial material is deposited in at least one of the one or more gaps; etching the sacrificial material to expose a surface of the feature; forming a thin permeable layer over the substrate, wherein the thin permeable layer is deposited on the sacrificial material and on the exposed surfaces of the features; selectively ashing the sacrificial material through the thin permeable layer to leave an air gap previously occupied by the sacrificial material prior to selectively ashing the sacrificial material, with the thin permeable layer suspending over the air gap; and depositing a dielectric material over the thin permeable layer.

Description

[0001] Cross-referencing The PCT application form is filed together with this specification as part of this application. Each application listed in the concurrently filed PCT application form that claims a benefit or priority under this application is incorporated herein by reference in its entirety for all purposes.

[0002] Existing technology Semiconductor manufacturing processes can involve forming metal lines in back-end processing or forming cells in 3D-NAND structures. However, as devices shrink, the pitch decreases and the capacitance increases. Reducing the pitch while maintaining sufficiently low capacitance presents a challenge.

[0003] The background description provided herein is for the purpose of presenting the general context of this disclosure. The work of the currently designated inventors within the scope described in this background section, as well as aspects of the specification that could not be identified as prior art at the time of filing, are neither express nor implied admissions of prior art to this disclosure. Summary of the Invention

[0004] This document provides methods and apparatus for processing semiconductor substrates. One aspect relates to a method for processing a substrate, the method comprising: providing a patterned substrate having one or more gaps between features; depositing a sacrificial material over the substrate, wherein the sacrificial material is deposited in at least one of the one or more gaps; etching the sacrificial material to expose a surface of a feature; forming a thin permeation layer over the substrate such that the thin permeation layer is deposited on the sacrificial material and on the exposed surface of the feature; selectively ashing the sacrificial material through the thin permeation layer to leave an air gap in the area previously occupied by the sacrificial material before selectively ashing the sacrificial material, wherein the thin permeation layer is suspended over the air gap; and depositing a dielectric material over the thin permeation layer.

[0005] In various embodiments, this feature includes a metal. In some embodiments, the metal is one or more of ruthenium, tungsten, and molybdenum. In some embodiments, the metal is covered with a silicon nitride or silicon oxide material.

[0006] In various implementations, this feature includes a dielectric material.

[0007] In various embodiments, the sacrificial material includes amorphous carbon. In various embodiments, the sacrificial material includes an ashingable hard mask.

[0008] In various embodiments, the one or more gaps include large gaps and small gaps, and the sacrificial material is selectively deposited in the small gaps.

[0009] In various embodiments, the thin penetration layer comprises silicon oxide, boron nitride, doped or undoped silicon carbide, silicon nitride, aluminum oxide, aluminum nitride, or a low-k material.

[0010] In various embodiments, the thin penetration layer has a thickness of about 2 nm to about 15 nm.

[0011] In various embodiments, the one or more gaps have a width of about 5 nm to about 25 nm.

[0012] In some embodiments, the dielectric material comprises silicon oxide, SiOCH, fluoro-silicate glass, or boron nitride. In some embodiments, the dielectric material is a tunneling oxide.

[0013] In various embodiments, the method further comprises selectively removing the horizontal regions of the thin penetration layer prior to selectively ashing the sacrificial material. In some embodiments, selectively removing the horizontal regions results in leaving vertical spacers on the sidewalls in the one or more gaps.

[0014] In various embodiments, the air gap is formed in a 3D-NAND structure.

[0015] In various embodiments, the feature is an oxide or nitride layer in an ONON stack.

[0016] In various embodiments, the selective ashing is performed by exposing the substrate to a plasma. In some embodiments, the plasma is generated by igniting hydrogen gas. In some embodiments, the plasma is generated by igniting oxygen gas.

[0017] Another aspect relates to a 3D-NAND cell comprising: alternating silicon oxide and word line layers; a metal oxide layer; a blocking oxide material; a charge trapping material adjacent to the blocking oxide material and in contact with one or more metal oxide layers; an air gap in the metal oxide layer between the blocking oxide material and the charge trapping material in adjacent word lines; a tunneling oxide layer; and a channel layer.

[0018] Another aspect relates to a method for processing a substrate, the method comprising: providing a patterned substrate having a metal-containing feature, a gap between the metal-containing feature, and a dielectric capping material on the metal-containing feature at or near the gap opening, wherein the metal-containing feature has a metal-containing surface and the dielectric capping material has an exposed dielectric surface; selectively depositing an inhibitor material on the metal-containing surface relative to the exposed dielectric surface to occlude the metal-containing surface and leave the dielectric surface unoccluded; forming a catalytic layer on the substrate over the dielectric surface unoccluded; and exposing the catalytic layer to a reactant to convert the catalytic layer to a dielectric material having a thickness sufficient to close the gap at the gap opening and leave an air gap between the metal-containing features.

[0019] In various embodiments, the metal-containing feature comprises ruthenium, tungsten, molybdenum, or a combination thereof.

[0020] In various embodiments, the inhibitor material comprises a self-assembled monolayer.

[0021] In various embodiments, the catalytic layer comprises aluminum oxide.

[0022] In various embodiments, the reactant comprises a silanol.

[0023] In various embodiments, the reactant comprises an aminosilane precursor and a hydrazine having the chemical structure: , wherein R3, R4, R5, and R6 are each hydrogen or an alkyl group.

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

[0025] FIG. 1A is a process flow diagram depicting operations performed in accordance with certain disclosed embodiments.

[0026] FIG. 1B is a process flow diagram depicting operations performed in accordance with certain disclosed embodiments.

[0027] FIGS. 2A-2G are schematic illustrations of a substrate in a patterning scheme in accordance with certain disclosed embodiments.

[0028] FIGS. 3A-3F are schematic illustrations of a substrate in a patterning scheme in accordance with certain disclosed embodiments.

[0029] FIGS. 3G-3K are schematic illustrations of a substrate in a patterning scheme in accordance with certain disclosed embodiments.

[0030] FIGS. 4A-4E are schematic illustrations of a substrate in a patterning scheme in accordance with certain disclosed embodiments.

[0031] FIGS. 4F and 4G are side views of a schematic illustration of a substrate drawn for 3D-NAND.

[0032] FIGS. 5A-5L are schematic illustrations of a substrate in a patterning scheme according to certain disclosed embodiments.

[0033] FIGS. 6, 7, and 8 are schematic illustrations of example processing chambers and tools that perform certain disclosed embodiments.

[0034] FIG. 9 is a graph depicting mass loss of ashable hardmask through a thin oxide capping layer exposed to hydrogen plasma treatment.

[0035] FIG. 10 is a graph depicting mass loss of silicon oxide exposed to hydrogen plasma treatment.

[0036] FIG. 11 is a TEM image of an air gap in a substrate.

[0037] FIG. 12 is a graph depicting mass loss of ashable hardmask through a 4 nm silicon oxide exposed to hydrogen plasma treatment and hydrogen and oxygen plasma treatment. DETAILED DESCRIPTION

[0038] In the following description, numerous specific details are set forth to provide a thorough understanding of the implementations. The disclosed implementations can be practiced without the specific details, or with variations upon these details, in some instances. In other instances, well-known processing operations have not been described in detail in order not to unnecessarily obscure the disclosed implementations.

[0039] Semiconductor processing can involve forming metal lines that are separated by dielectric material therebetween. As devices shrink, the metal spacing shrinks, which can result in an increase in RC delay, which can impact the speed of integrated circuits. For example, in some cases, as the spacing decreases, the resistivity of the metal can be higher, and to compensate for the increased resistance, the capacitance can be decreased. However, the increased capacitance can also increase the power consumption of the interconnect. These tradeoffs can be considered in the manufacturing optimization of semiconductor processing. In some cases, to mitigate the increase in RC delay, it can be desirable to lower the dielectric constant of the dielectric between the metal lines. While there are methods of depositing low-k gap fill dielectric materials, they can not sufficiently lower the dielectric constant between the metal lines when the metal lines are in close proximity to each other. Furthermore, low-k gap fill materials can be difficult to integrate into device structures, particularly when more aggressive processing operations are used, such as operations involving high temperatures or challenging chemistries. Exemplary low-k materials can have a dielectric constant of less than about 4.2.

[0040] Techniques to form air gaps in dielectric material have drawbacks. For example, non- conformal dielectric deposition, such as plasma enhanced chemical vapor deposition (PECVD), can be performed whereby the closure of the air gap is above the top of the metal line surface. This can result in the air gap opening downstream, such as during a chemical mechanical planarization (CMP) process or during self-aligned via formation. In another example, partial air gap formation can be performed to adjust process conditions during atomic layer deposition (ALD) reactions between feature tops and bottoms. In this process, a thin dielectric layer is deposited on the metal line sidewalls, which results in a reduced air gap volume and higher parasitic capacitance compared to full air gap formation (no sidewall deposition). Forming air gaps in 3D-NAND channel hole structures is challenging due to the very high aspect ratio and the need to have a substantially uniform structure throughout the hole.

[0041] Methods of forming air gaps in dielectric material between patterned lines are provided herein. In some applications, the lines are made of metal. In some applications, the lines are made of dielectric. In some applications, there will be little or no dielectric material on the sidewalls of the patterned lines. The methods and apparatus are suitable for a variety of applications, including but not limited to subtractive metal etch processes for forming cells in 3D NAND and forming air gaps between metal lines in back end of line (BEOL) processing. Certain disclosed embodiments can also be used in front end of line (FEOL) logic and DRAM applications. For example, air gaps can be used between word lines in 3D NAND structures. Certain disclosed embodiments can also be used in PCRAM applications. In various embodiments, the air gaps are formed by filling the gap between metal lines with a sacrificial material, which can be a carbon-containing material such as an ashable hard mask, and forming a thin permeable film over the sacrificial material, and ashing the sacrificial material through the thin permeable film. The ashing can be performed thermally or by using a plasma. The sacrificial material can be any material that can be selectively formed into a gaseous state relative to the permeable layer, such as but not limited to carbon-containing materials, boron nitride, boron oxide (B2O3), and tin oxide. Certain disclosed embodiments use an ashable hard mask (AHM) as the sacrificial material. The chemical composition of the AHM is such that it can be removed after it has served its purpose by a technique known as "ashing," "plasma ashing," or "dry stripping." One example of an AHM is an amorphous carbon layer or film. The AHM is generally composed of carbon and hydrogen, and optionally trace amounts of one or more dopants such as nitrogen, fluorine, boron, and silicon. The bonding structure of the AHM can be sp 2 (graphitic) or sp 3 (diamond-like) or a combination of both, depending on the deposition conditions.

[0042] Certain disclosed embodiments can be performed in a single tool or multiple tools (e.g., two or more tools). Certain disclosed embodiments also have the advantage of utilizing a bottom-up fill to form the AHM, which reduces and / or eliminates the formation of seams and / or voids in the recessed structure. This provides a solid foundation for the subsequent formation of a thin dielectric layer thereover. Certain disclosed embodiments also allow for fine control of the deposition thickness of the AHM, and the deposition thickness of the AHM can be adjusted across the critical dimension range on the wafer. Ashing to remove the AHM also produces volatile byproducts at any temperature, which thus reduces the risk of leaving behind undesirable residues. Ashing can also simultaneously densify the overlying thin dielectric layer, thus enabling sufficient quality of the film to be achieved for integration and device performance even if a higher permeable layer is used to remove the AHM. Additionally, ashing in a reducing environment can prevent and / or eliminate oxidation of underlying metals, resulting in reduced resistance of metal lines. Certain disclosed embodiments can be combined with a variety of techniques for depositing dielectric layers, including deposition techniques that can achieve superconformality, address overhang and void issues, and avoid metal oxidation.

[0043] In some embodiments, a thin liner can be deposited prior to deposition of the AHM. This can help reduce metal oxidation so that the metal sidewalls are not oxidized during AHM ashing or later dielectric material deposition or other subsequent processing. In some embodiments, the liner is capable of passivating surfaces in the gap, which can reduce leakage and address reliability issues. The liner can also increase capacitance. Example liner materials include, but are not limited to, any one or more of the following materials: silicon and carbon containing materials having the formula SiCX (where X can be O, N, ON, or can be omitted), aluminum oxide (AI2O3), SiN, BN, and graphene.

[0044] FIG. 1A is a process flow diagram depicting operations that can be performed in accordance with certain disclosed embodiments. At operation 102, a substrate is provided to a processing chamber. In various embodiments, the substrate is a semiconductor substrate. The substrate can be a silicon wafer, such as a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, including wafers having one or more layers of material (e.g., dielectric, conductive, or semiconductive material) deposited thereon. The substrate can include dielectric material thereon, and optionally metal material. In some embodiments, metal lines are located in the dielectric material and are separated by the dielectric material between the metal lines. In some embodiments, a placeholder material is present at locations where metal lines will be subsequently deposited. Examples of materials that can be located on the substrate include dielectric materials such as oxides (e.g., SiO2) and nitrides (e.g., SiN and TiN), polysilicon (Poly-Si), and metals such as aluminum (Al), copper (Cu), and tungsten (W).

[0045] A substrate can be patterned. The pattern can include positive and negative features. In some embodiments, the negative features can have an aspect ratio of at least about 1 : 1, at least about 2: 1, at least about 4: 1, at least about 6: 1, at least about 10: 1, or higher. The features can also have a dimension near the opening, such as an opening diameter or line width. A via, trench, or other recessed feature can be referred to as an un-filled feature or feature.

[0046] A substrate pattern can include gaps, which can be the same as or similar to the vias, trenches, or other recessed features described above. The gaps on a substrate can be different sizes. For example, in some embodiments, the size of a gap can be measured by the shortest distance between sidewalls on either side of the gap, or referred to herein as the gap width. A small gap can have a gap width from sidewall to sidewall of less than about 50 nm, or less than about 30 nm, such as from about 10 nm to about 30 nm, or from about 15 nm to about 25 nm. A large gap can have a gap width as measured from sidewall to sidewall of up to about 100 nm.

[0047] In some embodiments, a substrate includes a plurality of features. In some embodiments, a substrate includes horizontal features, such as in a 3D-NAND structure.

[0048] In operation 104, the first dielectric layer on the substrate can be optionally etched back to expose surfaces of the features. In some embodiments, the first dielectric layer is etched using a fluorine-containing chemistry. In some embodiments, the first dielectric layer is etched using a thermal process. In some embodiments, the first dielectric layer is etched using a plasma process. In some embodiments, the first dielectric layer is etched by adjusting process conditions. Operation 104 does not completely etch the first dielectric layer. Rather, it is etched sufficiently to expose surfaces of the features, such as surfaces of metal lines. Further examples will be described below. After operation 104, the substrate has a structure including metal features with gaps between the metal features. In various embodiments, a capping material can be over the metal features.

[0049] Although not shown, a liner can be deposited prior to operation 106. The liner can be a layer of silicon and carbon containing material having the formula SiCX, where X can be O, N, ON, or can be omitted, aluminum oxide (AI2O), SiN, BN, and graphene. In some embodiments, the liner can be between the capping material and the metal material.

[0050] In operation 106, the gap is filled with a sacrificial material, such as a carbon-containing material or a gap-fill AHM material. While AHMs are not the only type of sacrificial material that can be used, for the purposes of discussion, certain embodiments described herein will refer to AHMs for the sacrificial material, but one skilled in the art will understand that other sacrificial materials can be used. The AHM is deposited on the layer by plasma-enhanced chemical vapor deposition (PECVD). The PECVD process involves generating a plasma in a deposition chamber. In some embodiments, a dual radio frequency (RF) plasma source including a high frequency (HF) power and a low frequency (LF) power can be used. In some processes, one or more AHM layers are deposited.

[0051] To form the AHM, the substrate can be exposed to a process gas including a hydrocarbon precursor. In some embodiments, the hydrocarbon precursor can be a precursor defined by the formula C x H y where X is an integer between 2 and 10, and Y is an integer between 2 and 24. Examples include methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), butane (C4H 10 ), cyclohexane (C6H 12 ), benzene (C6H6), and toluene (C7H8). In some embodiments, the AHM is doped with a dopant, such as nitrogen, oxygen, boron, sulfur, and combinations thereof.

[0052] In some embodiments, two or more hydrocarbon precursors can be introduced. In addition to the hydrocarbon precursors, a carrier gas can be used to dilute the precursor gas flow. The carrier gas can be any appropriate carrier gas, including helium (He), argon (Ar), nitrogen (N2), hydrogen (H2), or combinations of any of these.

[0053] The total pressure in the deposition chamber can range between about 1 and about 20 Torr. In some embodiments, the pressure is between about 5 Torr and about 10 Torr. In some embodiments, the hydrocarbon precursor is introduced at a low partial pressure, for example, between about 0.01 Torr and about 4 Torr, as discussed in U.S. Patent Nos. 7,981,777 and 7,981,810, which are incorporated by reference herein. In certain embodiments, the partial pressure is equal to or less than about 0.2 Torr.

[0054] The precursor gas flow rate depends on the particular deposition chamber and substrate. An example flow rate for four 300 mm substrates is between about 200 seem and about 4,000 seem of acetylene, between about 1,000 seem and about 20,000 seem of hydrogen, and between about 1,000 seem and about 20,000 seem of helium.

[0055] The flow rates and RF powers disclosed herein are for a four-station tool configured for 300 mm wafers. The power levels and flow rates are generally linearly proportional to the number of stations and substrate area. The flow rates and powers can be expressed on a per area basis, for example, 2500 W can also be expressed as 0.884 W / cm 2 In some embodiments, the AHM is deposited on the substrate by a PECVD process that ignites a plasma by using a dual RF plasma source that includes a low frequency (LF) component and a high frequency (HF) component. In some embodiments, the methods of the embodiments use LF RF power to generate high energy ion bombardment. Low frequency RF power refers to RF power having a frequency between about 100 kHz and about 2 MHz. In some embodiments, the pulse frequency can be limited by the operating capability of the LF generator. In some embodiments, the LF RF power has an RF power with a frequency of about 400 kHz (e.g., 430 kHz). During deposition, in some embodiments, the LF power ranges between about 0.001 W / cm 2 and about 1.25 W / cm 2 The substrate surface area is expressed in cm 2 In some embodiments, the LF power ranges between about 0 and about 1.25 W / cm 2 High frequency RF power refers to RF power having a frequency between about 2 MHz and about 60 MHz. In some embodiments, the HF RF power has an RF power with a frequency of about 13.56 MHz. During deposition, in some embodiments, the HF power per substrate area ranges between about 0.001 W / cm 2 and about 0.5 W / cm 2 In some embodiments, the HF power per substrate area ranges between about 0.5 W / cm 2 and 1.25 W / cm 2

[0056] The methods described herein can be used for any appropriate process temperature, with an example range being about 50 °C to about 550 °C.

[0057] During optional operation 106, material can optionally be formed selectively on the sidewalls of the overburden material above the metal material. Examples are discussed further below with reference to FIGS. 2A-2G, 3A-3F, 3G-3K, and 5A-5L. The material in the substrate around the top of the metal lines (as shown in FIGS. 2A-2G) will form a recessed shape that can facilitate air gap formation with the closure of the air gap located lower in the feature depth than air gaps formed by non-conformal film deposition (e.g., chemical vapor deposition (CVD)).

[0058] ​In operation 108, a thin permeable layer is deposited. In some embodiments, the thin permeable layer is deposited by plasma enhanced atomic layer deposition (PEALD). In some embodiments, the thin dielectric layer is deposited by CVD, ALD, or any other deposition technique sufficient to deeply bury the air gap between the metal material. The thin permeable layer is a dielectric material. In some embodiments, the permeable layer can be silicon oxide. The permeable layer can be boron nitride, doped or undoped silicon carbide, silicon nitride, aluminum oxide, aluminum nitride, any low-k material (flowable or otherwise), or other suitable material with sufficient permeability to pass through it for ashing or selectively removing the sacrificial layer.

[0059] In one example, the following conditions are an example of conditions suitable for depositing a silicon oxide conformal layer by a PEALD process: the temperature can be between about 50 °C and 400 °C, for example about 50 °C; the pressure can be between about 0.5 Torr and about 10 Torr, for example about 2-3 Torr; the RF power can be between about 100 W and 3000 W for four 300 mm wafers to avoid damaging the substrate. Process gases that can be used include silicon amide (e.g., BTBAS - bis-tert-butylaminosilane, BDEAS (bis-diethyl-aminosilane), or DIPAS (diisopropylaminosilane)) as the silicon source, and oxygen or dinitrogen monoxide as the oxygen source can be used, and / or hydrogen gas, which can be used alone or in combination, and diluted with an inert carrier gas (e.g., argon or nitrogen). Additional example silicon sources are described in the Definitions and Precursors section herein. Process gas flow rates can be as follows: for (liquid) silicon precursor (BTBAS, BDEAS, DIPAS) between about 1 and 3 seem, for example about 2.5 seem of BTBAS; for oxygen precursor (O2, N2O) between about 5000 seem and 10,000 seem, for example 5000 seem of N2O; for carrier gas (Ar or N2) between about 0 to 10,000, for example about 5000 Ar.

[0060] In operation 110, the sacrificial layer is selectively removed through the thin permeable layer, leaving air gaps in place where the ashable hard mask was selectively removed before. This can be an ashing operation performed in a reducing environment. During this operation, the thin permeable layer remains on the substrate; in some cases, it remains as a bridge-like layer over the air gaps and is attached to the thin dielectric layer on the feature sidewalls. The selective removal of the AHM sacrificial layer can be performed by exposing the substrate to a plasma, such as a hydrogen (H2) plasma or an oxygen (O2) plasma or a combination thereof. The ashing can be performed by a dry etch that is rich in oxygen. Typically, oxygen is introduced into the chamber under vacuum and RF power creates oxygen radicals in the plasma to react with the AHM and oxidize it to water (H2O), carbon monoxide (CO), and carbon dioxide (CO2). The result is air gaps left in place where the sacrificial layer previously occupied.

[0061] Exemplary non-limiting suitable process parameters for AHM deposition and ashing are presented in the table below. Table 1 provides general ranges of process parameters suitable for carrying out embodiments that can be used in implementations of the disclosed embodiments.

[0062] Table 1. General process parameters for gap fill AHM layer deposition In operation 112, a dielectric material (e.g., a silicon-containing layer) is conformally deposited over the thin permeable layer. Air gaps remain between the features and are buried under the dielectric material. In various embodiments, the silicon-containing layer is a silicon oxide material. This operation can be performed to produce a thicker silicon oxide film over the substrate. In some embodiments, in addition to or in place of the dielectric material, a lower-k material (e.g., SiOCH, FSG, and BN) can be deposited in operation 112.

[0063] Certain disclosed embodiments relate to forming air gaps between metal lines in BEOL, which are patterned using subtractive metal etching and covered by dielectric layers. The air gaps can be formed by selective deposition using a suppressor that inhibits the metal surface. A single layer of aluminum oxide can be deposited on non-suppressed surfaces, which can be dielectric surfaces. Silanol precursors can react with the aluminum oxide to form a self-limiting layer of silicon oxide, thus selectively forming silicon oxide on the dielectric surfaces relative to the metal surfaces. This can be integrated to allow air gaps to be formed by suppressing deposition on the sidewalls of the gaps between features. FIG. IB is a process flow diagram of operations that can be performed in accordance with certain disclosed embodiments. In operation 102, a substrate is provided to a processing chamber; this can be the same as operation 102 in FIG. 1A. The substrate can include features, such as metal-containing features having metal-containing surfaces. In some cases, the metal-containing features can be metal lines. The metal can be a transition metal. The features are separated by gaps therebetween. The features are capped by a capping material that is a dielectric material. The gaps can have sidewalls that include metal-containing surfaces and dielectric-containing surfaces at or near the gap openings.

[0064] In operation 124, a suppressor material is selectively deposited on the metal-containing surfaces relative to the dielectric-containing surfaces. The suppressor material blocks the metal-containing surfaces so that material cannot be deposited thereon, or can have little material deposited thereon in subsequent operations. Exemplary suppressor materials include self-assembled monolayer (SAM) materials (which can include sulfur-containing heads and carbon chain tails), sulfur-containing materials, aniline-containing materials, aromatic materials, and the like. Without being bound by any particular theory, it is believed that the suppressor includes a molecular structure that is capable of weak π-like bonding interactions with the transition metal on the surface.

[0065] In operation 126, a catalytic material is deposited on the exposed dielectric-containing surfaces. In various embodiments, the catalytic material is aluminum oxide. Because the suppressor material remains on the metal-containing surfaces, the catalytic material is only adsorbed to the other exposed surfaces, which can be dielectric surfaces. In various embodiments, the catalytic material is thus selectively deposited on the exposed surfaces of the capping material, including the capping material at or near the gap openings.

[0066] In operation 128, a reactant is introduced to react with the catalytic material, converting the catalytic material to a dielectric material. In various embodiments, the reactant is a silanol. The silanol can be used to selectively react with the aluminum oxide to form silicon oxide on the surface of the dielectric material. In various embodiments, the deposition of this dielectric material is self-limiting.

[0067] In some embodiments, operation 128 can involve performing one or more atomic layer deposition cycles. For example, operation 126 can involve selectively forming an aluminum-containing portion on the surface to form a catalytic material, and operation 128 can involve exposing the substrate to an aminosilane precursor (a silicon source) without igniting a plasma, and exposing the substrate to hydrazine to form a silicon-containing dielectric material. Hydrazine has the chemical structure: where R3, R4, R5, and R6are each hydrogen or an alkyl group.

[0068] In operation 130, operation 128 can be repeated until the gap is closed at or near the gap opening. That is, the reactants can be introduced for a sufficient duration to react with the catalytic material and form a dielectric material of a thickness sufficient to close the gap. In some embodiments, the catalytic material can be deposited again, followed by exposure to additional reactants to continue deposition of the dielectric material. In some embodiments, it can not be necessary to deposit additional catalytic material to deposit a dielectric material sufficient to close the gap opening. Since the catalytic material is only adsorbed on the dielectric surface, the reactants only react with the catalytic material and not on the metal-containing surface that is closed by the suppressant material.

[0069] In optional operation 132, the inhibitor material is selectively removed, which can be performed by ashing it through the dielectric layer. In some embodiments, the dielectric layer is permeable and has characteristics and properties similar to the permeable layer described above with respect to operation 108 of FIG. 1A. Certain disclosed embodiments can be integrated with one or more of the following processes for forming air gaps: (1) deposition of a non-conformal dielectric material (the closure of the air gap can be above the top surface of the metal line, which will result in the air gap opening downstream during a CMP process or in a self-aligned via formation); (2) full air gap formation, which uses a degradable polymer as a sacrificial gap fill material (a thermal process can be applied to decompose the polymer and convert it to a gas, which is removed through the permeable layer (a thin capping layer can be deposited on the substrate, which results in potential problems in larger gaps); and (3) partial air gap formation (during silicon carbide deposition using a remote radical-based plasma, process conditions can be adjusted to have a difference between the ALD reaction at the top of the feature and at the bottom (a thin dielectric layer is deposited on the metal line sidewalls, which results in a reduced air gap volume and higher parasitic capacitance compared to full air gap (no sidewall deposition)). Certain disclosed embodiments have the advantage of being able to selectively deposit dielectric on the dielectric by preventing deposition on the metal. Most inhibitors can not be compatible with other deposition techniques used to form silicon oxide films, or can not provide sufficient duration of inhibition. Another advantage is to reduce process variability. Other methods for forming air gaps can be dependent on the trench profile, which is very challenging to keep constant at small pitch. Certain disclosed embodiments are less dependent on the structure profile and thus more robust. Certain disclosed embodiments also involve fewer process operations than certain other processes that involve a sacrificial layer, which makes the overall process faster and thus improves throughput.

[0070] FIGS. 2A-2G are schematic illustrations of example substrates undergoing various operations performed in accordance with certain disclosed embodiments. FIG. 2A shows a substrate 200 having a silicon oxide layer 201, a feature 203 with a capping material 205, and a gap 299 between the features 203. In one example, the feature 203 is a ruthenium metal line. In one example, the capping material 205 is a silicon nitride material. Although ruthenium is described herein, other suitable metals include, but are not limited to, tungsten or molybdenum.

[0071] FIG. 2B shows deposition of an AHM 207 into the gap 299 of the substrate 200 as a sacrificial layer.

[0072] FIG. 2C shows the substrate 200 after etching back the AHM 207 to form an etched AHM 217, thus exposing the surface of the feature 203 with the capping material 205.

[0073] Figure 2D shows thin silicon oxide 209 (penetrating layer) is conformally deposited over the features such that it contacts both the etched AHM 217 and the cap material 205 of the features 203.

[0074] In this example, Figure 2E shows selective etching of the thin silicon oxide 209 to remove the horizontal regions of the thin silicon oxide 209, leaving behind a spacer 219 on the gap sidewalls. This also exposes the surface 205s of the cap material 205. The etched AHM 217 remains in the gap. The gap between the features has a recessed profile.

[0075] In Figure 2F, the etched AHM 217 is selectively removed.

[0076] In Figure 2G, additional silicon oxide is deposited to form a dielectric material 229, leaving behind an air gap 237 between the features 203. The recessed profile helps to form the air gap 237 when the dielectric material is deposited, and the gap is closed when the dielectric material is deposited on the silicon oxide 209. This deposition can be performed using a non-conformal deposition technique such as CVD.

[0077] Figures 3A-3F are schematic illustrations of an exemplary substrate undergoing various operations performed in accordance with certain disclosed embodiments.

[0078] Figure 3A shows a substrate having a silicon oxide layer 301 with spaced apart ruthenium features 303, some of which can have a distance dl spacing that can be about 18 nm to about 26 nm. In some embodiments, an adhesion layer (not shown) can be present between the silicon oxide layer 301 and the ruthenium (or other metal) features 303. The adhesion layer can be a titanium nitride layer or a tantalum nitride layer. The ruthenium features 303 can also be covered with a silicon nitride cap 305, and have a barrier layer 304 between the ruthenium features 303. The depth of the negative features formed by such a structure depends on the depth of the ruthenium features 303, which can have a height hi of about 30 nm to about 60 nm, and on the thickness of the silicon nitride cap 305, which can have a depth h2 of about 15 nm.

[0079] In Figure 3B, an AHM sacrificial layer 307 is deposited at a low temperature of about 200 °C to about 350 °C using a gap fill technique.

[0080] In Figure 3C, the AHM sacrificial layer 307 is etched back using a hydrogen plasma to form an etched back AHM sacrificial layer 317. The etch back is controlled with the time of exposure to the hydrogen plasma. While a plasma is described in some embodiments, a plasma can not be necessary and a thermal means can be used to selectively remove the AHM sacrificial layer.

[0081] In Figure 3D, a silicon oxide penetration layer 309 is deposited by PEALD at temperatures up to about 300 °C. The silicon oxide penetration layer 309 can be conformal. The silicon oxide penetration layer 309 contacts the silicon nitride cap 305 and the ruthenium features 303 as well as the exposed etch back AHM sacrificial layer 317. The silicon oxide penetration layer 309 can have a thickness of about 2 nm to about 15 nm.

[0082] In Figure 3E, the etch back AHM sacrificial layer 317 is selectively ashed through the silicon oxide penetration layer 309 using a selective removal chemistry, such as hydrogen and / or oxygen plasma. In some embodiments with higher critical dimensions between features, there can be a risk of film collapse of the silicon oxide penetration layer 309 between features. The etch back AHM sacrificial layer 317 is ashed to leave air gaps 337 in small gaps and air gaps 327 in large gaps.

[0083] In Figure 3F, a silicon oxide 319 is conformally deposited over the substrate, leaving the air gaps 337 in small gaps and the air gaps 327 in large gaps.

[0084] Figures 3A and 3G-3J show exemplary substrate schematics undergoing various operations performed in accordance with certain disclosed embodiments.

[0085] Figure 3A can be the same as previously described above in Figure 3A.

[0086] In Figure 3G, an AHM sacrificial layer 347 is deposited in a gap fill manner only on small negative features or gaps, or in small gaps.

[0087] In Figure 3H, the etch back AHM sacrificial layer 347 is etched back to form an etch back AHM sacrificial layer 357 in small gaps.

[0088] In Figure 3I, a silicon oxide penetration layer 329 is deposited by PEALD at temperatures up to about 300 °C to a thickness of about 1.5 nm to about 2 nm. Because the AHM sacrificial layer 347 is not deposited in large gaps, the silicon oxide penetration layer 329 is deposited on the bottom of the large gaps.

[0089] In Figure 3J, the etch back AHM sacrificial layer 357 is selectively ashed through the silicon oxide penetration layer 329 using a hydrogen plasma, leaving air gaps 347 where the etch back AHM sacrificial layer 357 previously occupied. Because the silicon oxide penetration layer 329 in the large gaps remains on the bottom of these features, there is little risk of film collapse.

[0090] In Figure 3K, a silicon oxide 339 is deposited over the substrate; the silicon oxide 339 is deposited in the large gaps and over the small gaps, leaving the air gaps 347 in the small gaps.

[0091] FIGS. 4A-4E are schematic illustrations of an exemplary substrate undergoing various operations performed in accordance with certain disclosed embodiments. Since metal-containing surfaces can be on the sidewalls of the gap, the sidewalls of the gap are partially enclosed.

[0092] FIG. 4A shows a substrate having a silicon oxide layer 401 with spaced apart ruthenium features 403. The ruthenium features 403 are covered by a barrier layer 404 and a silicon nitride cap 405. Although ruthenium is provided as an example, it is understood that the features can have any transition metal.

[0093] In FIG. 4B, inhibitor material 450 is selectively deposited on the exposed surfaces of the ruthenium features 403. The inhibitor material 450 is a material that is selectively deposited on metal surfaces relative to dielectric materials.

[0094] In FIG. 3C, catalytic material 406 is deposited on the exposed surfaces of the cap layer 405. The catalytic material 406 is selectively deposited on the exposed surfaces (e.g., dielectric surfaces) of the cap layer 405 and not on metal surfaces, due to the inhibitor material 450 blocking the catalytic material 406 from depositing on the metal surfaces. The catalytic material 406 can be aluminum oxide or an aluminum-containing material. The catalytic material 406 is adsorbed onto the surfaces of the dielectric cap layer 405.

[0095] In FIG. 4D, a reactant is introduced to react with the catalytic material 406 as an activation material to form a dielectric material 409, such as silicon oxide. The reaction between the reactant and the catalytic material 406 can be self-limiting. In some embodiments, the reaction between the reactant and the catalytic material 406 forms an aluminum-containing moiety. The reactant selectively reacts with the catalytic material 406 to convert the catalytic material 406 to the dielectric material 409, such as silicon oxide. In some embodiments, as the thickness of the dielectric material 409 increases, additional layers of catalytic material 406 can be deposited, thus reacting with more reactant to deposit more dielectric material 409; such operations can be repeated in a loop if desired.

[0096] Certain disclosed embodiments can also be suitable for applications in 3D-NAND structures. Adding more layers or tiers in 3D-NAND structures can significantly increase the aspect ratio (AR), which presents great challenges for etching and deposition. Scaling the cell size in the Z direction can reduce the AR.

[0097] Reducing the vertical cell increases the electrical interaction between adjacent cells (as in 2D-NAND), resulting in stored charge flow and electrical coupling between adjacent word lines. FIG. 4F shows an example 3D-NAND cell in an integration scheme. The cell includes alternating layers of silicon oxide 492 and word lines 481, and blocking oxide 483, charge trapping layer (CTL) 484, tunnel oxide layer 485, and channel 486. FIG. 4G shows an example 3D-NAND cell that includes air gaps 487 separating the CTL 404 and the blocking oxide 483. The charge trapping layer can include a charge trapping material such as silicon nitride.

[0098] FIGS. 5A-5L include schematic diagrams of example substrates undergoing various operations performed in accordance with certain disclosed embodiments. FIG. 5A includes a substrate having alternating layers of silicon oxide 501 and silicon nitride 502, which can be a mold after opening of the channel holes. In FIG. 5B, the silicon oxide 501 is isotropically etched in an oxide recess operation. In FIG. 5C, a conformal deposition of a contrast material 510 is performed. In FIG. 5D, the contrast material 510 is isotropically etched back to form an etched contrast material 511. In FIG. 5E, the silicon nitride 502 is etched back to expose sidewall regions of the etched contrast material 511. In FIG. 5F, a blocking oxide 503 is deposited on the exposed silicon nitride 502 between the silicon oxide 501 layers. In FIG. 5G, a CTL 504 is deposited and the substrate is etched back. The contrast material 511 is resistant to the silicon nitride 502 etch back and the silicon oxide etch back. In FIG. 5H, the contrast material 511 is selectively etched back. The etch back in FIG. 5H is selective with respect to the silicon nitride and silicon oxide. In FIG. 5I, a silicon oxide conformal layer 509 is deposited by ALD to prevent the air gaps from being filled again with word line material after the silicon nitride 502 is later removed. The silicon oxide conformal layer 509 can also serve as part of the tunnel oxide. In FIG. 5J, an AHM lateral gap filler 507 is deposited and then etched back. In FIG. 5K, additional silicon oxide 505 is deposited by ALD to a thickness of about 2 nm to about 3 nm, forming a second portion of the tunnel oxide. In FIG. 5L, the AHM lateral gap filler 507 is selectively removed by ashing through the silicon oxide layers to form air gaps 527. In some embodiments, the ashing can be performed using hydrogen gas and / or an oxygen-containing gas, and / or a mixture of an oxygen-containing gas and a hydrogen-containing gas, and / or a plasma thereof. In some embodiments, the ashing is performed thermally. In some embodiments, a treatment of the silicon oxide (e.g., by annealing) can be performed to improve the quality of the tunnel oxide.

[0099] In certain disclosed embodiments, ashing of the AHM or carbon-containing material can be performed by a hydrogen plasma or an oxygen plasma or another plasma that selectively removes the carbon-containing material from beneath or through the silicon oxide layer without damaging or removing the silicon oxide layer. Ashing can be performed at a low temperature, such as about 200 °C or less. In some embodiments, low temperature ashing can reduce damage to the substrate.

[0100] Certain disclosed embodiments can be integrated in other processes and tools, such as those for tools with UV light. For example, the sacrificial material can be selectively removed by using a UV stimulated volatilization reaction, or by utilizing a reactive chemistry process (e.g., by activating O2 into O3 and / or NH3 into H), or by using a three-step process whereby the UV converts the material deposited in the gap into a material that is then easily ashable. In embodiments utilizing a reactive chemistry process, in some embodiments, it can be performed in a plasmaless process. This can be advantageous in that it does not densify the penetration layer and / or is easier to remove the sacrificial layer. In another example, certain disclosed embodiments can be integrated with a process involving a remote plasma. For example, the material can be deposited by ALD and by incorporating a capacitively coupled plasma in a chamber with a remote plasma generator, the integration scheme can also include densifying the oxide at a temperature of about 400 °C. In another example, the ashing can be performed by a pulsed plasma. In some embodiments, the deposition of the gap fill material can also be performed by using a remote plasma, which can also be integrated in a single tool, a single temperature chamber, which is also used to deposit the penetration layer (which can be silicon oxide), which can be performed by ALD.

[0101] Apparatus A flow-over vapor (FOV) delivery system can be used to deliver liquid phase process chemicals (e.g., inhibitors, precursors, sources, reactants, and other gases described herein) into a process chamber. However, liquid chemicals can have a relatively low vapor pressure. Deposition of such chemicals can be relatively slow due to the low vapor pressure. Further, inhibitor vapor can condense into a liquid phase on surfaces within the delivery system.

[0102] FIG. 6 illustrates a schematic diagram of an exemplary process tool 600 configured to deposit an inhibitor having a low vapor pressure onto a substrate. The process tool 600 is configured as a CVD tool. The process tool 600 includes a process chamber 602 and a substrate support 604 within the process chamber. The substrate support 604 is configured to support a substrate 606 disposed within the process chamber 602. The substrate support 604 can include a pedestal, a chuck, and / or any other appropriate structure.

[0103] The processing chamber 602 further includes a substrate heater 608 configured to heat a substrate disposed on the substrate support 604. In other examples, the substrate heater can be located elsewhere within the processing chamber 602, or can be omitted.

[0104] The processing tool 600 further includes a process gas outlet 610. In some examples, the process gas outlet 610 can include a nozzle, a showerhead, or other means for introducing a gas into the processing chamber 602. The substrate support 604 can be raised and lowered to adjust the spacing between the substrate 606 and the process gas outlet 610. In some examples, the process gas outlet 610 can include a heater.

[0105] The processing tool 600 also includes an ampoule 620 configured to contain a liquid phase process chemical including a vapor pressure. The ampoule 620 is further configured to supply a flow of chemical vapor from the ampoule through a FOV. In some examples, the chemical includes an inhibitor configured to selectively deposit onto a metal surface and inhibit oxide film growth. When the ampoule 620 contains a volume of liquid inhibitor, a gas phase inhibitor occupies at least a portion of the ampoule. In other examples, the ampoule 620 can contain a liquid phase process chemical other than an inhibitor.

[0106] The ampoule 620 includes a FOV gas inlet 622 for flowing a carrier gas from a carrier gas source 623 into the ampoule 620. Exemplary carrier gases include N2, Ar, He, Ne, or Kr. The FOV gas inlet 622 includes a mass flow controller 624 for controlling the flow of carrier gas. In some examples where the carrier gas source 623 includes nitrogen, the mass flow controller 624 is configured as a nitrogen mass flow controller. In other examples, the mass flow controller 624 is configured for controlling the flow of a different carrier gas.

[0107] The ampoule 620 further includes a FOV gas outlet 626 for flowing gas out of the ampoule 620. As the carrier gas flows through the ampoule 620, the carrier gas flows over the surface of the liquid inhibitor and directs the inhibitor gas through the FOV gas outlet 626. Thus, the carrier gas flows through the FOV gas outlet 626 along with the inhibitor.

[0108] The ampoule 620 further includes a bulk fill port 628 to refill the ampoule with inhibitor from an inhibitor bulk source 630. In other examples, the ampoule can be refilled using different methods, such as by replacing a removable inhibitor reservoir. Further, examples can be included that use a liquid phase process chemical other than an inhibitor, a liquid phase process chemical bulk source other than an inhibitor.

[0109] The processing tool 600 further includes an ampoule heater 634 for heating the ampoule 620. The ampoule heater 634 can include any suitable configuration of one or more heating elements. In some examples, the ampoule heater 634 can include a plurality of heating elements configured to apply heat to different locations on the ampoule 620. As an example, the ampoule heater 634 can include one or more of a cartridge heater, a ribbon heater, a jacket heater, a molded heater, or a heating coil. In some examples, the ampoule heater 634 includes a heater disposed beneath the ampoule 620 and one or more heaters disposed around the sides of the ampoule 620. In other examples, the ampoule heater 634 can include any other suitable configuration.

[0110] As noted above, the liquid-phase inhibitor can have a low vapor pressure. The vapor pressure of the inhibitor can increase with temperature. As an example, the inhibitor can have a vapor pressure of < 10 Torr at 60 °C, < 15 Torr at 80 °C, < 25 Torr at 100 °C, and < 50 Torr at 120 °C. Other liquid-phase process chemicals, including other inhibitors, can have vapor pressures outside of these ranges. By heating the ampoule 620, the ampoule heater 634 increases the vapor pressure of the inhibitor. This allows the processing tool 600 to deliver more inhibitor in the carrier gas stream.

[0111] The processing tool 600 further includes a plurality of heated gas lines. More specifically, in this example, the processing tool 600 includes a heated gas line 640A, a heated divert gas line 640B, and a heated hold vacuum line 640C. The heated gas lines 640A, 640B, 640C are heated by gas line heaters 642A, 642B, 642C, respectively. The gas line heaters 642A, 642B, 642C are shown schematically as dashed lines. The gas line heaters 642A, 642B, 642C can each include any suitable configuration of one or more heating elements. As an example, the gas line heaters 642A, 642B, 642C can each include one or more of a jacket heater, a ribbon heater, or a molded heater. The gas line heaters 642A, 642B, 642C can be controlled to heat the heated gas line 640A, the heated divert gas line 640B, and the heated hold vacuum line 640C to any suitable temperature or temperatures, respectively. The use of the gas line heaters 642A, 642B, 642C helps to prevent condensation of the vapor-phase inhibitor on surfaces within the heated gas line 640A, the heated divert gas line 640B, and the heated hold vacuum line 640C.

[0112] Heated gas line 640A is connected to FOV gas outlet 626. During operation, gas from FOV gas outlet 626 flows through heated gas line 640A to processing chamber 602. Gas line heater 642A is configured to heat heated gas line 640A. As described above, by flowing gas through one or more heated gas lines, processing tool 600 can help avoid condensation of inhibitors within the heated gas lines.

[0113] Processing tool 600 further includes a diverter valve system 644 disposed along heated gas line 640A. Heated diverter gas line 640B is connected to diverter valve system 644 and leads to exhaust system 646. Gas line heater 642B is configured to heat heated diverter gas line 640B. Exhaust system 646 is configured to receive gas flowing from processing chamber 602 and / or one or more heated gas lines. In some examples, exhaust system 646 is configured to actively remove gas from processing chamber 602 and / or apply a partial vacuum. Exhaust system 646 can include any suitable hardware, including one or more pumps.

[0114] Diverter valve system 644 can be controlled to divert gas flow away from processing chamber 602 and through heated diverter gas line 640B to exhaust system 646. Diverter valve system 644 includes a first valve 644A and a second valve 644B. When gas is to be diverted to exhaust system 646, diverter valve system 644 can be controlled to close first valve 644A and open second valve 644B without trapping gas. In this way, diverter valve system 644 can help avoid condensation of inhibitors within the gas lines or valves.

[0115] Heated evacuation line 640C is configured to remove gas from ampoule 620 to exhaust system 646. Removing carrier gas and inhibitor vapor from ampoule 620 can facilitate maintenance of ampoule 620. Gas line heater 642C is configured to heat heated evacuation line 640C. As described above, exhaust system 646 can be configured to apply a partial vacuum to facilitate removal of gas from ampoule 620 and / or heated gas lines.

[0116] Processing tool 600 further includes a gas box 648 containing one or more sources of gas. In other examples, the gas box can be separate from processing tool 600. Processing tool 600 further includes a valve 650 to control the flow of one or more gases from gas box 648 into processing chamber 602. Gas box 648 can include a source of one or more gases. In some examples, gas box 648 includes one or more inert gases used as carrier gases.

[0117] The processing tool 600 further includes a remote plasma system 652 configured to form a remote plasma to clean the processing chamber 602. Radicals formed in the plasma can be introduced into the processing chamber 602 through the process gas outlet 610. The radicals can help clean the processing chamber 602 by reacting with deposited material on surfaces within the processing chamber 602. The remote plasma system 652 can also be used to provide radicals for processing of a substrate.

[0118] The processing tool 600 further includes a main power source 654 for supplying power to components of the processing tool 600, such as pumps, sensors, the substrate heater 608, the exhaust system 646, and the valves 644A, 644B, 650. The processing tool 600 further includes an auxiliary power source 656 for supplying power to the gas line heaters 642A, 642B, 642C. In some examples, the gas line heaters can be powered by the main power source 654 and the auxiliary power source 656 can be omitted.

[0119] The processing tool 600 further includes a controller 660 for controlling operation of the processing tool 600. The controller 660 is configured to control various functions of the processing tool 600, such as operating the substrate heater 608 to heat to a desired temperature.

[0120] The controller 660 is configured to control the mass flow controller 624 to flow carrier gas into the ampoule 620 at a desired flow rate. In some examples, the controller 660 is configured to control the mass flow controller 624 to flow nitrogen into the ampoule 620 at a flow rate in a range of 6000 to 7500 standard cubic centimeters per minute (seem). The carrier gas carries the suppressant out of the ampoule 620 through the FOV gas outlet 626. In some examples, the nitrogen flow is controlled so that the suppressant flow through the FOV gas outlet 626 is in a range of 20 seem to 500 seem. In other examples, any other appropriate flow rate can be used. The flow rate can depend on the suppressant vapor pressure and / or the ampoule temperature.

[0121] The controller 660 is further configured to control components of the ampoule 620. In some examples, the controller 660 is configured to receive a signal from the ampoule 620 indicative of a suppressant level in the ampoule 620. In some examples, the controller 660 is configured to output the level information to a display (not shown in FIG. 6). In some examples, the controller 660 is configured to control a main fill system to fill the ampoule 620 with suppressant. For example, the controller 660 can control one or more pumps to pump suppressant from a main source of suppressant 630 into the ampoule 620 through a main fill port 628. In other examples, the suppressant can be added to the ampoule 620 manually. In some examples, the controller 660 is configured to control the ampoule 620 to fill with suppressant based on a level below a threshold.

[0122] The controller 660 is further configured to control the ampoule heater 634 to heat to a desired temperature. In some examples, the ampoule heater can be controlled to heat the suppressant or other liquid phase process chemical to a temperature in the range of 60 to 130 °C. In more specific examples, the ampoule heater can be heated to a temperature in the range of 80 to 100 °C. In other examples, temperatures outside of these ranges can be used. In examples of the suppression process, the temperature to which the ampoule heater is heated depends on the particular suppressant contained in the ampoule and the vapor pressure required.

[0123] The controller 660 is further configured to control the gas line heaters 642A, 642B, 642C to heat the heated gas line 640A, heated divert gas line 640B, heated hold vacuum line 640C, respectively, to a desired temperature. In some examples where the chemical in the ampoule is a suppressant, the controller 660 can control one or more of the gas line heaters to heat to a temperature in the range of 600 to 630 °C. Further, in some examples, the gas line heaters 642A, 642B, 642C can heat the respective heated gas line 640A, heated divert gas line 640B, heated hold vacuum line 640C to a temperature higher than the temperature of the ampoule heater.

[0124] The controller 660 is further configured to operate the divert valve system 644 to direct the suppressant to the process chamber 602 or to the exhaust system 646. The controller 660 is further configured to operate the exhaust system 646. The controller 660 is also configured to operate the valve 650 and the exhaust system 646 to purge the process chamber 602 by flowing inert gas into the process chamber 602 and evacuating the process chamber 602. The controller 660 can also be configured to operate other components of the process tool 600 not shown here. The controller 660 can include any suitable computing system, examples of which are described below with reference to the system controller 750 of FIG. 7 and the system controller 850 of FIG. 8.

[0125] In some implementations, the controller 660 is part of a system, which can be part of the above-described examples. Such systems can include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronics for controlling the operation of the semiconductor processing equipment before, during, and after processing of a semiconductor wafer or substrate. The electronics can be referred to as the “controller,” which can control various components or subcomponents of one or more systems. Depending on the process requirements and / or system types, the controller 660 can be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., of 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 transfer into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0126] Broadly speaking, the controller 660 can 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 can 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 can be instructions communicated to the controller 660 in the form of various individual settings (or programs) of the various parameters defined for processing a particular wafer or group of wafers. The

[0127] In some implementations, the controller 660 can 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 660 can 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 can 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, change parameters of current processing, set processing steps to follow a current process, or start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which can include a local network or the Internet. The remote computer can include a user interface that enables a user to input or

[0128] An exemplary system can include, but is not limited to, 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

[0129] As noted above, depending on the process step or steps to be performed by the tool, the controller 660 can 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.

[0130] As noted above, one or more processing stations can be included in a multi-station processing tool. FIG. 7 depicts an exemplary processing apparatus according to the disclosed embodiments. The tool 700 includes a first processing chamber 702 and a second processing chamber 704. The first processing chamber 702 includes a plurality of processing stations, i.e., four stations 780A-D, each of which can process a wafer. The first processing chamber 702 is configured to perform plasma processing operations on the wafers. The second processing chamber 404 is configured to perform deposition on the wafers and can be considered a deposition chamber. The second processing chamber 704 also includes a plurality of processing stations, i.e., four stations 782A-D, each of which can process a wafer. The first and second processing chambers 702 and 704 can be considered multi-station processing chambers.

[0131] The tool 700 also includes a wafer transport unit configured to transport one or more wafers within the tool 700. Additional features of the tool 700 will be discussed in greater detail below, and various features are discussed herein as part of the technology. In the depicted icon, the wafer transport unit includes a first robot unit 708 in a first wafer transport module 710 and a second robot unit 712 in a second wafer transport module 714, which can be considered an equipment front end module (EFEM) configured to receive a container of wafers, such as a front opening unified pod (FOUP) 716. The first robot unit 708 is configured to transport wafers between the first processing chamber 702 and the second processing chamber 704 and between the second robot unit 712. The second robot unit 712 is configured to transport wafers between the FOUP and the first robot unit 708. After processing a wafer in the first processing chamber 702, the wafer transport unit is able to transport the wafer from the first processing chamber 702 to the second processing chamber 704, where one or more layers of encapsulation material can be deposited on the wafer(s).

[0132] Similar to the above, the first wafer transport module 710 can be a vacuum transfer module (VTM). A gas lock 720, also referred to as a load lock or transfer module, as shown, can be individually optimized to perform various manufacturing processes. The tool 700 also includes a FOUP 716 configured to reduce the pressure of the tool 700 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and to maintain the tool 700 at that pressure. This includes maintaining the first and second processing chambers 702 and 704 and the first wafer transport module 710 at the vacuum or low pressure. The second wafer transport module 714 can be at a different pressure, e.g., atmospheric pressure. The wafers are thus maintained at the vacuum or low pressure as they are transported throughout the tool 700. For example, as the wafers are transferred from the first processing chamber 702 to the first wafer transport module 710 and the second processing chamber 704, the wafers are maintained at the vacuum or low pressure and are not exposed to atmospheric pressure.

[0133] In other examples, the substrate is placed in one of the plurality of FOUPs 718 and the second robot arm unit 712 or front end robot transports the substrate from the FOUP 718 to an aligner, which allows the substrate to be properly centered before it is etched or deposited on or otherwise processed. After alignment, the substrate is moved by the second robot arm unit 712 into the airlock 720. Because the airlock module has the ability to match the environment between the ATM and the VTM, the substrate can be moved between the two pressure environments without damage. From the airlock 720, the substrate is moved by the first robot arm unit 708 through the first wafer transport module 710 or VTM 710 and into the first processing chamber 702. To accomplish this substrate movement, the first robot arm unit 708 uses end effectors on each of its arms.

[0134] FIG. 7 also depicts an embodiment of a system controller 729 for controlling process conditions and hardware states of the tool 700. The system controller 729 can include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). The processors can include CPUs or computers, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0135] As described above, one or more processing stations can be included in a multi-station processing tool. FIG. 8 shows a schematic diagram of an embodiment of a multi-station processing tool 800 having an in-station load lock 802 and an out-station load lock 804, one or both of which can include a remote plasma source. A robot 806 at atmospheric pressure is configured to move a substrate or wafer from a cassette loaded through a cassette boat 808 via an atmospheric port 810 to the in-station load lock 802. The robot 806 places the substrate on a pedestal 812 in the in-station load lock 802, the atmospheric port 810 is closed, and the load lock is pumped down. In the case where the in-station load lock 802 includes a remote plasma source, the substrate can be exposed to a remote plasma treatment in the load lock before being introduced into a processing chamber 814. In addition, the substrate can also be heated in the in-station load lock 802 to, for example, remove moisture and adsorbed gases. Next, a chamber transfer port 816 to the processing chamber 814 is opened, and another robot (not shown) places the substrate into the reactor, on a pedestal of a first station shown in the reactor, for processing. Although the embodiment depicted in FIG. 8 includes load locks, it should be understood that in certain embodiments, direct access of the substrate into the processing stations can be provided. In various embodiments, a soak gas is introduced into the station when the robot 806 places the substrate on the pedestal 812.

[0136] The depicted processing chamber 814 includes four processing stations, numbered from 1 to 4 in the embodiment shown in FIG. 8. Each station has a heated pedestal (shown at 818 for station 1) and gas line inlets. It should be understood that each processing station can have a different or multiple purposes in some embodiments. For example, in some embodiments, a processing station can switch between ALD and PEALD process modes. Additionally or alternatively, in some embodiments, the processing chamber 814 can include one or more pairs of matched ALD processing stations and plasma-enhanced ALD processing stations. While the depicted processing chamber 814 includes four stations, it should be understood that processing chambers according to the present disclosure can have any suitable number of stations. For example, in some embodiments, a processing chamber can have five or more stations, while in other embodiments, a processing chamber can have three or fewer stations.

[0137] FIG. 8 depicts one embodiment of a wafer handling system 890 for transporting substrates within the processing chamber 814. In some embodiments, the wafer handling system 890 can transport substrates between various processing stations and / or between processing stations and load locks. It should be understood that any suitable wafer handling system can be used. Non-limiting examples include a wafer transfer belt and a wafer handling robot. FIG. 8 also depicts an embodiment of a system controller 850 for controlling process conditions and hardware states of the processing tool 800. The system controller 850 can include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processors 852 can include CPUs or computers, analog and / or digital input / output connections, stepper motor control boards, etc. In certain embodiments, the system controller 850 includes machine-readable instructions for performing operations described above, e.g., with respect to FIGS. 2, 3, and 4.

[0138] In some embodiments, a system controller 850 controls the activities of the processing tool 800. The system controller 850 executes system control software 858 stored in mass storage device 854, loaded into memory device 856, and executed on processor 852. Alternatively, the control logic can be hard coded in the controller 850. Special purpose integrated circuits, programmable logic devices (e.g., field programmable gate arrays or FPGAs), and / or the like can be used for these purposes. In the following discussion, wherever “software” or “code” is used, functionally equivalent hard coded logic can be used in its place. The system control software 858 can include instructions for controlling the timing, gas mixtures, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, substrate temperature, target power levels, RF power levels, substrate pedestal, chuck, and / or susceptor positions, and other parameters of the particular process being performed by the processing tool 800. The system control software 858 can be configured in any suitable manner. For example, various processing tool component subroutines or control objects can be written to control the operation of the processing tool components for performing various processing tool processes. The system control software 858 can be coded in any suitable computer readable programming language.

[0139] Experiment Experiment 1 Substrates with 2 nm silicon oxide, 4 nm silicon oxide, and 7 nm silicon oxide on a 35 nm ashable hard mask material were exposed to various process conditions - hydrogen plasma exposure for 10 seconds, hydrogen plasma exposure for 20 seconds, hydrogen plasma exposure for 30 seconds, hydrogen plasma exposure for 60 seconds, and hydrogen plasma exposure for 120 seconds. The AHM mass loss was evaluated to check the potential of H2 plasma to remove AHM through thin silicon oxide films. The results are shown in FIG. 9. Overall, the bare AHM (e.g., no silicon oxide layer) showed almost 100% mass loss after 20 seconds of hydrogen plasma exposure. Longer deposition times appeared to reduce the mass loss, which can be due to re-deposition. The total AHM was removed after 30 seconds of hydrogen plasma treatment. When the silicon oxide film thickness was 4 nm, the amount of AHM removal was significantly reduced, with only about 23% mass loss after 120 seconds of hydrogen plasma treatment. The results for 7 nm silicon oxide appeared to be due to the degradation of the oxide layer.

[0140] Experiment 2 Substrates with 2 nm silicon oxide, 4 nm silicon oxide, and 7 nm silicon oxide were exposed to various process conditions - hydrogen plasma exposure for 30 seconds, and hydrogen plasma exposure for 60 seconds. The silicon oxide mass loss was evaluated to determine if conformal silicon oxide films would deteriorate if AHM ashing was performed through it. The results show that there is little mass loss after hydrogen plasma treatment, indicating an overall trend that the silicon oxide layer can remain on the substrate and AHM can be successfully ashed through the silicon oxide layer without damaging the silicon oxide layer, particularly in, for example, 2 nm embodiments, as the corresponding AHM mass loss in Figure 9 exhibits almost 100% mass loss, while the silicon oxide mass loss in Figure 10 is about 2% or less.

[0141] Experiment 3 A gap fill AHM material was filled in the gaps between features on a substrate and a penetration layer was deposited thereon. The gap fill AHM was selectively ashed through the penetration layer, leaving an air gap between the features. A dielectric silicon oxide was deposited thereon and the air gap was still preserved. Figure 11 shows a TEM image of a substrate with metal features 1103 with an air gap 1127 therebetween and silicon oxide 1139 deposited thereon.

[0142] Experiment 4 A gap fill AHM material was deposited on a substrate. The gap fill AHM was selectively ashed through a 4 nm silicon oxide penetration layer by plasma using various process conditions. Figure 12 shows a plot of the amount of AHM loss depending on pressure, temperature, and exposure time. These results show that selective etching using a plasma generated with O2 and H2 at low pressure and at a temperature of about 400°C can achieve high etch amounts. At low pressure and 400°C with only H2 flow, 30 seconds of exposure resulted in 10% AHM mass loss, 60 seconds of exposure resulted in 16% AHM mass loss, and 120 seconds of exposure resulted in 23% AHM mass loss. At low pressure and 200°C with only H2 flow, 30 seconds of exposure resulted in 3% AHM mass loss, 60 seconds of exposure resulted in 4% AHM mass loss, and 120 seconds of exposure resulted in 5% AHM mass loss. At high pressure and 400°C with only H2 flow, 30 seconds of exposure resulted in 11% AHM mass loss, 60 seconds of exposure resulted in 16% AHM mass loss, and 120 seconds of exposure resulted in 26% AHM mass loss. At low pressure and 400°C with a mixture of O2 and H2, 30 seconds of exposure resulted in 31% AHM mass loss, 60 seconds of exposure resulted in 63% AHM mass loss, and 120 seconds of exposure resulted in 87% AHM mass loss.

[0143] Definitions and precursors Definitions The term "ampoule" generally refers to a container used to contain chemical substances. An ampoule may be at least partially filled with liquid chemical substances, such that the remainder of the ampoule contains gaseous chemical substances.

[0144] The term "ampoule heater" can generally refer to a heater used to heat liquid contained in an ampoule.

[0145] The term "primary filling port" generally refers to the inlet of an ampoule used to refill it with liquid chemicals.

[0146] The term "carrier gas" can generally refer to the gas used to transport chemical vapors in a steam process. Suitable carrier gases include inert gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and krypton (Kr).

[0147] The term "chemical vapor deposition" (CVD) can generally refer to a method of depositing a film on a substrate by flowing one or more chemical substances through the substrate under conditions that allow chemical substances to form a film on the substrate.

[0148] The term "film" can generally refer to a layer of material deposited on a substrate.

[0149] The term “flow-through vapor” (FOV) can generally refer to the flow of a carrier gas over the surface of a liquid chemical substance to guide and transport chemical vapors as the carrier gas flows.

[0150] The term "vapor gas inlet" generally refers to the port on an ampoule used to allow carrier gas to flow into the ampoule.

[0151] The term "vapor outlet" generally refers to the port on an ampoule used to allow carrier gas and vapor to flow out of the ampoule.

[0152] The term "heated gas line" can generally refer to a conduit in a chemical vapor deposition tool that is heated by one or more heaters and used to deliver gaseous chemicals.

[0153] The term "inhibitor" can generally refer to a treatment chemical that is physically or chemically adsorbed onto the material forming the surface of a substrate and prevents film growth on the substrate surface or reduces its growth rate (compared to a substrate surface containing material without an inhibitor).

[0154] The term "liquid level sensor" can generally refer to a sensor configured to detect the liquid level inside an ampoule. Exemplary liquid level sensors include discrete liquid level sensors and continuous liquid level sensors. A discrete liquid level sensor can generally refer to a sensor configured to sense the presence of liquid at one or more fixed levels. A continuous liquid level sensor can generally refer to a sensor configured to detect the liquid level over a continuous range of levels.

[0155] The term "low vapor pressure" in relation to a chemical can generally mean a vapor pressure of less than 10 Torr at a temperature of 60 °C.

[0156] The term "processing chamber" can generally mean an enclosure in which chemical and / or physical processing is performed on a substrate.

[0157] The term "process gas outlet" can generally mean a structure for injecting a gas phase process chemical into a processing chamber of a processing tool. In various examples, a process gas outlet can include a nozzle or a showerhead. Exemplary process chemicals include film precursors, reactants, and inert gases.

[0158] The term "processing tool" can generally mean a machine that includes a processing chamber and other hardware configured to enable processing to be performed in the processing chamber.

[0159] The term "substrate" can generally mean any object on which a film can be deposited.

[0160] The term "substrate heater" can generally mean a heater in a processing chamber configured to heat a substrate. A substrate heater can be integrated with a substrate support, or can be located elsewhere in a processing chamber.

[0161] The term "substrate support" can generally mean any structure for supporting a substrate in a processing chamber. Examples include pedestals, electrostatic chuck pedestals, and showerhead pedestals for backside deposition processes.

[0162] The term "acyl" or "alkanoyl" as used interchangeably herein means a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms in linear, branched, cyclic configurations, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen, attached to a parent molecular group by a carbonyl group as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, an acyl or alkanoyl group is -C(O)-R, where R is hydrogen, aliphatic, or aromatic as defined herein.

[0163] "Alkanoyloxy" means an alkanoyl group as defined herein attached to a parent molecular group through an oxy group as defined herein. This group is exemplified by acetyloxy (-OAc or -OC(O)Me). In some embodiments, an alkanoyloxy group is -OC(O)-R, where R is hydrogen, aliphatic, or aromatic as defined herein.

[0164] "Aliphatic" means a group of at least one carbon atom until 50 carbon atoms (C 1-50Hydrocarbon groups, such as those with 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 The aliphatic group comprises an alkane (or alkyl), an alkene (or alkenyl), an alkyne (or alkynyl), in its cyclic form, and further comprises straight-chain and branched arrangements, as well as all stereo and positional isomers. The aliphatic group is unsubstituted or substituted with functional groups, such as those described herein. For example, the aliphatic group may be substituted with one or more substituents (such as those described herein for alkyl groups).

[0165] "Aliphatic-carbonyl" means an aliphatic group coupled to or potentially coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or converted to a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0166] "Aliphatic-carbonyloxy" means an aliphatic group coupled to or potentially coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or converted to a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0167] "Aliphatic-oxy" means an aliphatic group coupled to or potentially coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or converted to an oxygen group (-C(O)-). In some embodiments, the aliphatic-oxy ​​is -OR, where R is an optionally substituted aliphatic group as defined herein.

[0168] “Aliphatic-oxycarbonyl” means an aliphatic group coupled to or potentially coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or converted to an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted aliphatic group as defined herein.

[0169] “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” respectively mean, as defined herein, an alkyl, alkenyl, or alkynyl group coupled or potentially coupled (or linked) to a parent molecule group by an aryl group as defined herein. Alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted with one or more substituents, as described herein with respect to alkyl and / or aryl groups. An exemplary unsubstituted alkyl-aryl group has 7 to 16 carbons (C60-C60). 7-16 Alkyl-aryl), and those having alkyl groups with 1 to 6 carbons and aryl groups with 4 to 18 carbons (i.e., C10, C20, C30, C40, C50, C6 ... 1-6 Alkyl-C 4-18 Aryl). Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbons (C). 7-16 Alkenyl-aryl), and those having 2 to 6 carbons in an alkenyl group and 4 to 18 carbons in an aryl group (i.e., C). 2-6 alkenyl-C 4-18 Aryl). Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbons (C). 7-16 (alkynyl-aryl), and those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C... 2-6 alkynyl-C 4-18 Aryl). In some embodiments, alkyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkynyl as defined herein.

[0170] "Alkenyl" refers to a group having at least two to 50 carbon atoms (C20-C50). 2-50 (For example, two to 25 carbon atoms (C) 2-25 ), or two to ten carbon atoms (C 2-10 The alkenyl group comprises an unsaturated monovalent hydrocarbon with at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon is derived from a carbon atom of a parent alkene by removing a hydrogen atom. The alkenyl group can be branched, linear, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyl groups comprise optionally substituted C atoms having one or more double bonds. 2-24Alkyl. Alkenyl can be monovalent or polyvalent (e.g., divalent), which is formed by removal of one or more hydrogens to form an appropriate linkage to a parent molecular group or an appropriate linkage between a parent molecular group and another substituent. Alkenyl can also be substituted or unsubstituted. For example, alkenyl can be substituted with one or more substituents, as described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0171] "Alkoxy" means -OR, wherein R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, t-butyloxy, sec-butyloxy, n-pentyloxy, trihaloalkoxy, such as trifluoromethoxy, and the like. Alkoxy can be substituted or unsubstituted. For example, alkoxy can be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkoxy.

[0172] "Alkoxyalkyl" means an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbon (C 2-12 alkoxyalkyl groups, as well as those having an alkyl group with 1 to 6 carbons and an alkoxy group with 1 to 6 carbons (i.e., C 1-6 alkoxy-C 1-6 alkyl groups). In some embodiments, alkoxyalkyl is -L-O-R, wherein L and R are each independently alkyl, as defined herein.

[0173] "Alkoxycarbonyl" means -C(O)-OR, wherein R is an optionally substituted aliphatic group, as described herein. In particular embodiments, alkoxycarbonyl is -C(O)-OAk, wherein Ak is alkyl, as defined herein. Alkoxycarbonyl can be substituted or unsubstituted. For example, alkoxycarbonyl can be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkoxycarbonyl.

[0174] “Alkyl” means a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C 1-50 (eg, 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be derived from the removal of one hydrogen atom from one carbon atom of a parent compound (eg, an alkane). The alkyl group can be branched, straight-chain, or cyclic (eg, cycloalkyl). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), t-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), t-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (eg, divalent), which is formed by the removal of one or more hydrogens to form an appropriate linkage to a parent molecule group or between a parent molecule group and another substituent. For example, the alkyl group can be substituted with one, two, three, or (in the case of alkyl groups having two or more carbons) four substituents, independently selected from the group consisting of: (1) C 1-6 alkoxy (eg, -O-R, wherein R is C 1-6 alkyl); (2) C 1-6 alkylsulfinyl (eg, -S(O)-R, wherein R is C 1-6 alkyl); (3) C 1-6 alkylsulfonyl (eg, -SO2-R, wherein R is C 1-6 alkyl); (4) amino (eg, -NR 1 R 2 , wherein each of R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2(5) aryl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryl acyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 (12) Cycloalkyl; (13) Halogen; (14) Heterocyclic group (e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein); (15) Heterocyclic oxy group (e.g., -OR, where R is a heterocyclic group as defined herein); (16) Heterocyclic acyl group (e.g., -C(O)-R, where R is a heterocyclic group as defined herein); (17) Hydroxyl group (e.g., -OH); N - Protected amino group; (18) Nitro group (e.g., -NO2); (19) Oxyl group (e.g., =O); (20) C 1-6 (21) Thioalkyl (e.g., -SR, where R is an alkyl group); (22) Thiol group (e.g., -SH); (23) -CO2R 1 , where R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (23)-C(O)NR 1 R 2 , where R 1 With R 2 Each of the following is independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 Aryl and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (24)-SO2R 1 , where R 1 Choose from the following groups: (a) C 1-6 Alkyl, (b) C 4-18 Aryl and (c) C 4-18 -Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18aryl) ; (25) -SO2NR 1 R 2 wherein R 1 each of R 2 and R 1-6 is independently selected from the group consisting of (a) hydrogen, (b) C 4-18 alkyl, (c) C 4-18 aryl, and (d) C 1-6 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 4-18 alkyl and R is C 1 aryl) ; and (26) -NR 2 R 1 wherein R 2 each of R 1-6 and R 2-6 is independently selected from the group consisting of (a) hydrogen, (b) N -protecting group, (c) C 2-6 alkyl, (d) C 4-18 alkenyl, (e) C 4-18 alkynyl, (f) C 1-6 aryl, (g) C 1-6 aryl-C 4-18 alkyl (e.g., -L-R, wherein L is C 3-8 alkyl and R is C 3-8 cycloalkyl, and (i) C 1-6 cycloalkyl-C 1-6 alkyl (e.g., -L-R, wherein L is C 3-8 alkyl and R is C 1-3 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl or 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 halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkyl.

[0175] “Alkylene,” “alkenylene,” or “alkynylene” means, respectively, a polyvalent (e.g., divalent) version of an alkyl, alkenyl, or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, the alkylene group is C 1-3 , C1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkylene. In other embodiments, the alkylene is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 alkenylene or alkynylene. The alkylene, alkenylene, or alkynylene can be branched or unbranched. The alkylene, alkenylene, or alkynylene can also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene can be substituted with one or more substituent groups, as described herein for alkyl.

[0176] “Alkylsulfinyl” means an alkyl group as defined herein connected to the parent molecular group through a -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl is C 1-6 or C 1-12 alkylsulfinyl. In other embodiments, an alkylsulfinyl is -S(O)-R, wherein R is an alkyl group as defined herein.

[0177] “Alkylsulfinylalkyl” means an alkyl group as defined herein substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl is C 2-12 or C 2-24 alkylsulfinylalkyl (e.g., C 1-6 alkylsulfinyl-C 1-6 alkyl or C 1-12 alkylsulfinyl-C 1-12 alkyl). In other embodiments, an alkylsulfinylalkyl is -L-S(O)-R, wherein L and R are each independently an alkyl group as defined herein.

[0178] “Alkylsulfonyl” means an alkyl group as defined herein connected to the parent molecular group through a -SO2- group. In some embodiments, an unsubstituted alkylsulfonyl is C 1-6 or C 1-12alkylsulfonylalkyl" means an alkyl group as defined herein that is substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl is a C 1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0179] "Alkylsulfonylalkyl" means an alkyl group as defined herein that is substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl is a C 2-12 or C 2-24 alkylsulfonylalkyl (e.g., C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, an alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0180] "Alkynyl" means an unsaturated monovalent hydrocarbon radical of at least two carbon atoms to 50 carbon atoms (C 2-50 ) (e.g., two to 25 carbon atoms (C 2-25 ), or two to ten carbon atoms (C 2-10 ) and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from the removal of one hydrogen atom from one carbon atom of a parent alkyne. Alkynyl groups can be branched, straight chained, or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include, for example, optionally substituted C 2-24 alkyl. Alkynyl groups can be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or polyvalent (e.g., divalent), by removal of one or more hydrogens to form an appropriate linkage to a parent molecular group or between a parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl groups.

[0181] "Environmental temperature" means a temperature ranging from 16 °C to 26 °C, such as a temperature ranging from 19 °C to 25 °C or from 20 °C to 25 °C.

[0182] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 wherein R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or wherein R 1 and R 2together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein.

[0183] "Amino" means -NR 1 R 2 , wherein R 1 and R 2 each independently is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof, as defined herein; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein. In particular embodiments, R 1 and R 2 each independently is 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 siloxy. In particular embodiments, R 1 and R 2 together with the nitrogen atom to which each is attached can form an optionally substituted heterocyclyl group.

[0184] "Aminoalkyl" means an alkyl group as defined herein substituted with an amino group as defined herein. In some embodiments, the aminoalkyl is -L-NR 1 R 2 , wherein L is an alkyl group as defined herein, and R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl is -L-C(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 each independently is selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein; and R 3 and R 4 each independently is H or alkyl as defined herein.

[0185] "Aminooxy" means an oxy group as defined herein, which is substituted with an amino group as defined herein. In some embodiments, the aminooxy group is -0-NR 1 R 2 wherein R 1 and R 2 each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted siloxy, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein. In particular embodiments, R 1 and R 2 each independently is 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 siloxy.

[0186] "Aromatic" means a cyclic, conjugated group or moiety of 5 to 15 ring atoms (unless otherwise specified) with a single ring (e.g., phenyl) or multiple fused rings, at least one of which is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous and delocalized pi-electron system. Typically, the number of out-of-plane pi-electrons corresponds to the Huckel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. The aromatic group is unsubstituted or substituted with, for example, functional groups as described herein. For example, the aromatic group can be substituted with one or more substituent groups as described herein for alkyl and / or aryl groups.

[0187] "Aromatic-carbonyl" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0188] "Aromatic-carbonyloxy" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the aromatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0189] "Aromatic-oxy" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, the aromatic-oxy is -O-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0190] "Aromatic-oxycarbonyl" means an aromatic group coupled or couplable to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted aromatic group, as defined herein.

[0191] "Aryl" means an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C 5-15 ) (e.g., five to ten carbon atoms (C 5-10 )), having a single ring or multiple condensed rings, which condensed rings can or can not be aromatic, provided that the point of attachment to the remainder of a compound disclosed herein is through an atom of the aromatic carbocyclic group. An aryl group can be substituted with one or more groups other than hydrogen (e.g., aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof). Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group comprising an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Also included within the term aryl is the term non-heteroaryl, which is defined as a group comprising an aromatic group and no heteroatoms. An aryl group can be substituted or unsubstituted. An aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 alkanoyl (e.g., -C(O)-R, wherein R is C 1-6 alkyl); (2) C 1-6 alkyl; (3) C 1-6 alkoxy (e.g., -O-R, wherein R is C 1-6 alkyl); (4) C 1-6Alkoxy-C 1-6 Alkyl (e.g., -L-O-R, where L and R are each independently C 1-6 Alkyl) ; (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 Alkyl) ; (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -L-S(O)-R, where L and R are each independently C 1-6 Alkyl) ; (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 Alkyl) ; (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 Alkyl) ; (9) Aryl; (10) Amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein) ; (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 , or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or C 1-6 alkyl; R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein; R 3 and R 4 are each independently H or C 1-6 alkyl) ; (12) Heteroaryl; (13) C 4-18 Aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6alkyl and R is C 4-18 aryl); (14) aroyl (e.g., -C(O)-R, where R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldo (e.g., -C(O)H); (19) aldo-C 1-6 alkyl (e.g., -L-C(O)H, where L is C 1-6 alkyl); (20) C 3-8 cycloalkyl; (21) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl); (22) halogen; (23) C 1-6 haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or C 1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and R 1 and R 2 each independently is H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, e.g., a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, where R is heterocyclyl as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein); (27) hydroxyl (-OH); (28) C 1-6 hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or alkyl; and R 1 and R 2 each independently is H or C 1-6 alkyl as defined herein); (29) nitro; (30) C 1-6 nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R1 )-R 2 , wherein L 1 is C 1-6 alkyl; L 2 is a covalent bond or alkyl; and R 1 is H or C 2 alkyl; each R 1-6 is independently H or C 1-6 alkyl; (31) N -protected amino; (32) N -protected amino-C 1-6 alkyl; (33) oxo (e.g., =0); (34) C 1-6 thioalkyl (e.g., -S-R, wherein R is C 1-6 alkyl); (35) thio-C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-S-R, wherein L and R are each independently C r alkyl); (36) -(CH2) 1 CO2R 1 , wherein r is an integer from 0 to 4, and R 1-6 is selected from the group consisting of: (a) hydrogen, (b) C 4-18 alkyl, (c) C 4-18 aryl, and (d) C 1-6 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 4-18 alkyl and R is C r aryl); (37) -(CH2) 1 CONR 2 R 1 , wherein r is an integer from 0 to 4, and wherein R 2 and R 1-6 are each independently selected from the group consisting of: (a) hydrogen, (b) C 4-18 alkyl, (c) C 4-18 aryl, and (d) C 1-6 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 4-18 alkyl and R is C r aryl); (38) -(CH2) 1 SO2R 1 , wherein r is an integer from 0 to 4, and wherein R 1-6 is selected from the group consisting of: (a) C 4-18 alkyl, (b) C 4-18 aryl, and (c) C 1-6alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (39) -(CH2) r SO2NR 1 R 2 where r is an integer from 0 to 4 and where R 1 and R 2 each independently is selected from the group consisting of: (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (40) -(CH2) r NR 1 R 2 where r is an integer from 0 to 4 and where R 1 and R 2 each independently is selected from the group consisting of: (a) hydrogen, (b) N -protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), where in one embodiment no two radicals are bound to the nitrogen atom through a carbonyl or sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, where n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, where n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, where R is aryl); (45) cycloalkyloxy (e.g., -O-R, where R is cycloalkyl); (46) cycloalkylalkyloxy (e.g., -O-L-R, where L is alkyl and R is cycloalkyl); and (47) arylalkyloxy (e.g., -O-L-R, where L is alkyl and R is aryl). In a particular embodiment, unsubstituted aryl is C4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 aryl.

[0192] “Aryl-alkyl,”“aryl-alkenyl,” and“aryl-alkynyl” mean an aryl group, as defined herein, coupled or couplable (or attached) to a parent molecular group through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl can be substituted or unsubstituted. For example, the aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl can be substituted with one or more substituent groups, as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbons (C 7-16 aryl-alkyl), as well as those having an aryl group with 4 to 18 carbons and an alkyl group with 1 to 6 carbons (i.e., C 4-18 aryl-C 1-6 alkyl). Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbons (C 7-16 aryl-alkenyl), as well as those having an aryl group with 4 to 18 carbons and an alkenyl group with 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkenyl). Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbons (C 7-16 aryl-alkynyl), as well as those having an aryl group with 4 to 18 carbons and an alkynyl group with 2 to 6 carbons (i.e., C 4-18 aryl-C 2-6 alkynyl). In some embodiments, aryl-alkyl is -L-R, where L is an alkyl or alkylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, aryl-alkenyl is -L-R, where L is an alkenyl or alkenylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, aryl-alkynyl is -L-R, where L is an alkynyl or alkynylene group, as defined herein, and R is an aryl group, as defined herein.

[0193] “Arylene” means a polyvalent (e.g., divalent) version of an aryl group, as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, arylene is C 4-18C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 Or C 6-10 Aryl groups. Aryl groups can be branched or unbranched. Aryl groups can also be substituted or unsubstituted. For example, aryl groups can be substituted with one or more substituents, as described herein with respect to aryl groups.

[0194] "Arylalkoxy" means an aryl-alkyl group as defined herein that is attached to a parent molecule group by an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group as defined herein and R is an aryl group as defined herein.

[0195] "Aryloxy" refers to -OR, where R is an aryl group that is optionally substituted as described herein. In some embodiments, the unsubstituted aryloxy group is C. 4-18 Or C 6-18 Aryloxy group. In other embodiments, R is an aryl group optionally substituted with an alkyl, alkanoyl, amino, hydroxyl, or similar group.

[0196] "Aryloxycarbonyl" refers to an aryloxy group, as defined herein, that is attached to a parent molecule group via a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C10. 5-19 Aryloxycarbonyl. In other embodiments, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group as defined herein.

[0197] "Arylyl" refers to an aryl group that is attached to a parent molecule group via a carbonyl group. In some embodiments, the unsubstituted aryl group is C10. 7-11 Aromatic acyl or C 5-19 Aromatic acyl group. In other embodiments, the aromatic acyl group is -C(O)-R, where R is an aryl group as defined herein.

[0198] "Aryloyloxy" refers to an aryloyl group, as defined herein, that is attached to a parent molecule group via an oxygen group. In some embodiments, the unsubstituted aryloyloxy group is C0. 5-19 Aromatic oxy group. In other embodiments, the aromatic oxy group is -OC(O)-R, where R is an aryl group as defined herein.

[0199] “Azido” refers to the -N3 group.

[0200] "Aryloxy" means an ary! group, as defined herein, appended to the parent molecular group through an oxygen atom. In some embodiments, the aryl group is phenyl. In some embodiments, the aryl group is naphthyl.

[0201] "Azo" means a -N=N- group.

[0202] "Carbamoyl" means an amino group, as defined herein, appended to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, the carbamoyl group is -C(O)NR 1 R 2 wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, as defined herein, or any combination thereof; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein.

[0203] "Carbamoyloxy" means a carbamoyl group, as defined herein, appended to the parent molecular group through an oxy group, as defined herein. In some embodiments, the carbamoyloxy group is -OC(O)NR 1 R 2 wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, as defined herein, or any combination thereof; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein.

[0204] "Carbonimidoyl" means a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted arylalkyl, optionally substituted siloxy, as defined herein, or any combination thereof.

[0205] "Carbonyl" means a -C(O)- group, which can also be represented as >C=0.

[0206] "Carboxyl" means a -CO2H group or a salt thereof.

[0207] "Catalyst" means a compound that is present in small amounts relative to the reactants and is capable of catalyzing a synthetic reaction, as would be readily understood by one of ordinary skill in the art. In some embodiments, a catalyst can comprise a transition metal coordination complex.

[0208] "Cyanato" means a -OCN group.

[0209] "Cyano" means a -CN group.

[0210] "Cycloaliphatic" means a cyclic aliphatic group, as defined herein.

[0211] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, a cycloalkoxy group is -O-R, wherein R is a cycloalkyl group, as defined herein.

[0212] "Cycloalkylalkoxy" means -O-L-R, wherein L is an alkyl or alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0213] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbons (unless otherwise specified), for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1. heptyl] and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group can be substituted with one or more groups, including those described herein for alkyl groups. Additionally, a cycloalkyl group can include one or more double and / or triple bonds.

[0214] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group, as defined herein.

[0215] "Disilanyl" means a group containing a Si-Si bond. In some embodiments, a disilanyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 - or -SiR S1 R S2 -SiR S3 R S4 - group, wherein RS1 S2 S3 S4 S5 each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0216] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0217] "Electron-donating group" means a functional group capable of donating at least a portion of its electron density to a ring to which it is directly attached, e.g., through resonance.

[0218] "Electron-withdrawing group" means a functional group capable of accepting electron density from a ring to which it is directly attached, e.g., through inductive electron withdrawal.

[0219] "Halo" means F, CI, Br, or I.

[0220] "Haloaliphatic" means an aliphatic group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced with a halogen atom (e.g., fluorine, bromine, chlorine, or iodine).

[0221] "Haloalkyl" means an alkyl group as defined herein in which one or more hydrogen atoms (e.g., 1 to 10 hydrogen atoms) are independently replaced with a halogen atom (e.g., fluorine, bromine, chlorine, or iodine). In an independent embodiment, a haloalkyl can be a -C4group, where each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, a haloalkyl is -L-X, where L is an alkyl group as defined herein and X is fluorine, bromine, chlorine, or iodine. In other embodiments, a haloalkyl is -L-C(X)(R 1 2 where L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine, or iodine; and R 1 2 each R is independently H or an alkyl group as defined herein.

[0222] ​​​​​​"Heteroaliphatic" means an aliphatic group as defined herein containing at least one heteroatom up to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 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. The heteroaliphatic group can be unsubstituted or substituted, for example, with a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substituent groups, such as those described herein for alkyl groups.

[0223] "Heteroaliphatic" means an aliphatic group as defined herein containing at least one heteroatom up to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 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. The heteroaliphatic group can be unsubstituted or substituted, for example, with a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substituent groups, such as those described herein for alkyl groups.

[0224] "Heteroaliphatic-carbonyl" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0225] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0226] "Heteroaliphatic-oxy" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, the heteroaliphatic-oxy is -O-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0227] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group coupled or couplable to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaliphatic group, as defined herein.

[0228] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" mean alkyl, alkenyl, or alkynyl groups, respectively, as defined herein, containing at least one heteroatom, up to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0229] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" mean the polyvalent (e.g., divalent) versions of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0230] "Heteroaromatic" means an aromatic group as defined herein containing at least one heteroatom, up to 20 heteroatoms (e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. The heteroaromatic group is unsubstituted or substituted with, for example, functional groups described herein. For example, the heteroaromatic group can be substituted with one or more substituent groups as described herein for alkyl and / or aryl groups.

[0231] "Heteroaromatic-carbonyl" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the heteroaromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0232] "Heteroaromatic-carbonyloxy" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0233] "Heteroaromatic-oxy" means a heteroaromatic group coupled to or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, the heteroaromatic-oxy is -O-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0234] “Heteroaromatic-oxycarbonyl” means a heteroaromatic group coupled or couplable to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the heteroaromatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaromatic group, as defined herein.

[0235] “Heteroaryl” means an aryl group comprising at least one heteroatom up to six heteroatoms (e.g., one to four heteroatoms), which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, wherein the condensed rings can or can not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. The heteroaryl group can be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. An exemplary heteroaryl group includes a subset of heterocyclyl groups as defined herein that are aromatic, i.e., that contain 4n+2 pi electrons within a single or multiple ring system.

[0236] “Heteroarylene” means a polyvalent (e.g., divalent) version of a heteroaryl group as described herein.

[0237] “Heteroatom” means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particularly disclosed embodiments, a heteroatom does not include a halogen atom, e.g., when valence restrictions do not permit.

[0238] "Heterocyclyl" means a 5-, 6-, or 7-membered ring (unless otherwise specified) containing one, two, three, or four heteroatoms (e.g., independently selected from nitrogen, oxygen, phosphorus, sulfur, or halogen). A 5-membered ring has zero to two double bonds, while a 6-membered ring and a 7-membered ring have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings are fused with one, two, or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring (e.g., indolyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, benzofuranyl, benzothiophenyl, and the like). Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, 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.

[0239] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein.

[0240] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein.

[0241] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein. 1 "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein. 2 R 3 wherein R 1 , R 2 and R 3Each is independently selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof; or wherein R 1 With R 2 Combination or R 2 With R 3 The combination of these, along with the nitrogen atoms to which they are attached, can form heterocyclic groups as defined herein. In some embodiments, R 1 R 2 With R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In a particular embodiment, R 2 With R 3 Together with the nitrogen atoms to which they are attached, they form optionally substituted heterocyclic groups.

[0242] “Hydroxyl” means -OH.

[0243] "Hydroxyalkyl" means an alkyl group as defined herein that is substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group is attached to a single carbon atom of the alkyl group. Examples include hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, the hydroxyalkyl group is -L-OH, where L is an alkyl group as defined herein. In other embodiments, the hydroxyalkyl group is -LC(OH)(R 1 )-R 2 Where L is a covalent bond or alkyl group as defined herein, and R 1 With R 2 Each is independently H or alkyl as defined herein.

[0244] "Imidoyl" refers to a group that includes an imine carbonyl group. In some embodiments, the imine acyl group is C(NR) 1 )R 2 , where R 1 With R 2 Each group is independently selected from hydrogen as defined herein, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof. In other embodiments, the imine acyl group is -C(NR) 1 H, C(NR) 1 )RAk , or C(NR N1 )R Ar , wherein R 1 is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, or optionally substituted siloxy as defined herein; R Ak is optionally substituted alkyl or optionally substituted aliphatic; R Ar is optionally substituted aryl or optionally substituted aromatic.

[0245] "Imino" means an -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In particular embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0246] "Isocyanato" means an -NCO group.

[0247] "Isocyano" means an -NC group.

[0248] "Ketone" means -C(O)R or a compound comprising such a group, wherein R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. Examples of ketones can include R 1 C(O)R, wherein R and R 1 are each independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0249] "Nitro" means an -NO2 group.

[0250] "Nitroalkyl" means an alkyl group as defined herein substituted with one to three nitro groups. In some embodiments, the nitroalkyl is -L-NO2, wherein L is an alkyl group as defined herein. In other embodiments, the nitroalkyl is -L-C(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2each independently H or alkyl as defined herein.

[0251] “Oxo” means an =0 group.

[0252] “Oxy” means -O-.

[0253] “Perfluoroalkyl” means an alkyl group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, a perfluoroalkyl group is -(CF2)n-CF3, where n is an integer from 0 to 10. n CF3, where n is an integer from 0 to 10.

[0254] “Perfluoroalkoxy” means an alkoxy group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. In some embodiments, a perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0255] “Salt” means an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes a cationic or anionic compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, nontoxic salts are described in Berge S. M. et al., “Pharmaceutical salts,” J. Pharm. Sci. 66:1-19 (1977), which is incorporated herein by reference in its entirety. In some embodiments, a salt is a pharmaceutically acceptable salt. J. Pharm. Sci.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. Salts can be prepared in situ during the final isolation and purification of the compounds of the disclosure, or separately by reacting the free base group with a suitable organic acid (thus giving an anionic salt) or by reacting the free acid group with a suitable metal or organic salt (thus giving 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, malate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmoate, pamoate, phosphate, phosphate, phthalate, p-toluenesulfonate, salicylate, succinate, sulfate, tartrate, tannate, tartrate, teoclate, and tosylate. Representative cationic salts include ammonium, calcium, choline, diethylamine, diethanolamine, lithium, magnesium, potassium, sodium, and zinc.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, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metals, e.g., aluminum, bismuth, iron, and zinc; and nontoxic ammonium, quaternary ammonium, and amino cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium,Iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium). Optionally substituted furanium, Optionally substituted thiophenium, Optionally substituted imidazolium, Optionally substituted pyrazolium, Optionally substituted isothiazolium, Optionally substituted triazolium, Optionally substituted tetrazolium, Optionally substituted furazanium, Optionally substituted pyridinium, Optionally substituted pyrimidinium, Optionally substituted pyrazine Pyrazinium, optionally substituted triazinium, optionally substituted tetraazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, any Selectively substituted piperazinium, selectively substituted piperidinium, selectively substituted morpholinium, selectively substituted azepanium, selectively substituted azepinium, selectively substituted indolium, selectively substituted isoindolium, selectively substituted indolizinium, selectively substituted indazolium, and selectively substituted benzimidazolium.optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium.

[0256] "Silyl" means a -SiR 1 R 2 R 3 or -SiR 1 R 2 group. In some embodiments, R 1 , R 2 , and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, R 1 , R 2 , and R 3 are each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is Si(R) a (OR) b (NR2) c where each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each > 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.

[0257] "Silyloxy" means -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 where R 1 , R 2 , and R 3each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, R 1 , R 2 , and R 3 each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the siloxy group is -0-Si(R) a (OR) b (NR2) c where each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each > 0; 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.

[0258] "Sulfinyl" means an -S(O)- group.

[0259] "Sulfo" means an -S(O)2OH group.

[0260] "Sulfonyl" or "sulfonate" means an -S(O)2- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0261] "Thioalkyl" means an alkyl group as defined herein attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 thioalkyl groups. In some embodiments, a thioalkyl group is -S-R, where R is an alkyl group as defined herein.

[0262] "Thiol" means an -SH group.

[0263] Those skilled in the art will appreciate that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with five different groups, and the like). Such impermissible substitution patterns will be readily apparent to those skilled in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted, unless otherwise indicated therein.

[0264] As used herein, the term "about" means + / - 10% of any specified value. When used herein, the term is used to modify any specified numerical value, range of values, or end point of one or more ranges.

[0265] As used herein, "top," "bottom," "upper," "lower," "over," "under" are used to provide relative relationships between structures. The use of these words does not indicate or require that a particular structure must be at a particular location in the device.

[0266] Other features and advantages of the present application will be more apparent from the following embodiments and claims.

[0267] Silicon-containing source In various embodiments, the silicon-containing source is a silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In particular embodiments, the silicon-containing source includes a halosilane source. In particular embodiments, the silicon-containing source includes an aminosilane source.

[0268] Aminosilanes include at least one nitrogen atom bonded to a silicon atom, but can also contain hydrogen, oxygen, halogen, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetraaminosilanes (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted mono-, di-, tri-, and tetraaminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2, BTBAS), tert-butyl silylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. A further example of an aminosilane is trisilylamine (N(SiH3)3). In one example, the silicon-containing source is DIPAS. In another example, the silicon-containing source is BTBAS.

[0269] The silicon-containing source can include one or more optionally substituted amines, thus providing non-limiting aminosilanes. In one embodiment, the source has the formula (Rʹ) 4-x Si(NRʹʹ2) xwherein: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic- carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which can be optionally substituted; and each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which can be optionally substituted; or optionally wherein two R'" can be taken together with the nitrogen atom to which each is attached to form an optionally substituted heterocyclyl group.

[0270] In another embodiment, the source has the formula (R"2N) x (R') 3-x Si−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, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which can be optionally substituted; and each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which can be optionally substituted; or optionally wherein two R'" can be taken together with the nitrogen atom to which each is attached to form an optionally substituted heterocyclyl group.

[0271] In certain embodiments, L is an optionally substituted imino, e.g., -NR-, where R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl, e.g., -SiR2-, where each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic.

[0272] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0; and / or L comprises 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, oxyl (-0-), imino, or silyl.

[0273] In certain embodiments, at least one R' or R'" is not H. The source can have any useful combination of R' groups attached to one or more silicon atoms and amine groups (NR'"2).

[0274] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxyl (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-oxyl-silyl (e.g., alkoxy silyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), siloxy (e.g., -O-SiR3), aliphatic-oxyl-siloxy (e.g., alkoxy siloxy or -O-Si(R) a (OR) b ), aminosiloxy (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 form, together with the nitrogen atom to which each is attached, 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.

[0275] In other embodiments, R' is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted siloxy. In some embodiments, R' is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R' is SiR'3, SiR3, Si(R') a (OR) b , Si(R) a (OR) b , Si(R' ) a (NR2) b , Si(R) a (NR2) b , Si(R' ) a (OR) b (NR2) c , Si(R) a (OR) b (NR2) c , OSiR'3, OSiR3, OSi(R' ) a (OR) b , OSi(R) a (OR) b , -OSi(R' ) a (NR2) b , -O-Si(R) a (NR2) b , OSi(R' ) a (OR) b (NR2) c , or OSi(R) a (OR) b (NR2) cwhere each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which can 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 is > 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.

[0276] The source can include at least one R' group attached to the silicon atom. In one embodiment, the source has the formula (R')(H) 3-x Si(NR"2) x where R' and R''can be any described herein, and where x is 1, 2, or 3. In another embodiment, the source has the formula (R')(H)2Si(NR"2), where R' and R''can be any described herein. In one embodiment, the source has the formula (R')(H)Si(NR"2)2, where R' and R''can be any described herein. In another embodiment, the source has the formula (R')2(H)Si(NR"2), where R' and R''can be any described herein. In yet another embodiment, the source has the formula (R')2Si(NR"2)2, where R' and R''can be any described herein. In one embodiment, the source has the formula (R')3Si(NR"2), where R' and R''can be any described herein.

[0277] The source can have no R' groups attached to the silicon atom. In one embodiment, the source has the formula (H) 4-x Si(NR"2) x where each R''can independently be any described herein, and where x is 1, 2, 3, or 4. In another embodiment, the source has the formula Si(NR"2) x where each R''can independently be any described herein. In particular embodiments, each R''is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0278] The source can include one or more hydrogen atoms attached to the silicon atom. In one embodiment, the source has the formula (H)3Si(NR"2) or (H)2Si(NR"2)2 or (H)Si(NR"2)3, where each R''can independently be any described herein. In particular embodiments, each R''is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which can be optionally substituted.

[0279] The source can include a heterocyclyl group having a nitrogen atom. In one embodiment, the source has the formula H3SiHet, where Het is an optionally substituted heterocyclyl group including at least one nitrogen atom. In particular embodiments, the source has the formula where the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein, such as substitution of an alkyl group), where n is 1, 2, 3, 4, or 5. In one embodiment, the source has the formula R'3SiHet, where Het is an optionally substituted heterocyclyl group including at least one nitrogen atom, and each R' can be independently any of those described herein. In particular embodiments, the source has the formula where the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein, such as substitution of an alkyl group); each R' can be independently any of those described herein; and where n is 1, 2, 3, 4, or 5.

[0280] In some examples, the source can have two or more silicon atoms, where the source can include a Si-Si bond. In a particular embodiment, the source has the formula (R"2N) x (R') 3x Si−Si(R') 3x (NR"2) x where R' and R''can be any of those described herein. In one embodiment, the source has the formula (R"2N)(R')2Si−Si(R')2(NR"2), where R' and R''can be any of those described herein. In another embodiment, the source has the formula (R"2N)2(R')Si−Si(R')(NR"2)2, where R' and R''can be any of those described herein. In yet another embodiment, the source has the formula (R"2N)3Si−Si(NR"2)3, where each R''can be independently any of those described herein.

[0281] The source can include different groups attached to the silicon atoms. In one example, the source has the formula (R"2N) x (R') 3-x Si−SiH3, where R' and R''can be any of those described herein.

[0282] A linker can exist between the two silicon atoms. In one example, the source has the formula (R"2N) x (R') 3-x Si−NR−Si(R') 3-x (NR"2) xwhere R' and R" can be any described herein, and where R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another example, the source has the formula (R"2N) x (H) 3-x Si-NR-Si(H) 3-x (NR"2) x where R, R', and R" can be any described herein.

[0283] The source can include a combination of R' groups with a linker having a heteroatom. In one example, the source has the formula (R')3Si-NR-Si(R')3, where R and R' can be any described herein. In another example, the source has the formula (R')3Si-L-Si(R')3, where L and R' can be any described herein. In particular embodiments, L is oxy (-0-), optionally substituted imino (e.g., -NR-), or optionally substituted silyl (e.g., SiR2).

[0284] The source can include any useful combination of R' and NR"2groups in combination with two silicon atoms. In one example, the source has the formula (R"2N)(R')2Si-L-Si(R')2(NR"2) x where L, R', and R" can be any described herein.

[0285] The source can include a heterocyclic group that includes silicon and nitrogen atoms. In one embodiment, The source has the formula where R' and R" can be any described herein, and where n is 1, 2, 3, or 4.

[0286] In another embodiment, the source has the formula where R' and R" can be any described herein, and where n is 1, 2, 3, or 4. In yet another embodiment, the source has the formula where each R" can independently be any described herein; and where n is 1, 2, 3, or 4. In another embodiment, the source has the formula where R' and R" can be any described herein, and where n is 1, 2, 3, or 4. In yet another embodiment, the source has the formula where R" can independently be any described herein; and where n is 1, 2, 3, or 4.

[0287] In any of the sources herein, two R" can form an optionally substituted heterocyclic group along with the nitrogen atom to which each is attached.

[0288] The source can include any of the following, for example, (R Ak )Si(NH2)(NR Ak 2)2, (R Ak )Si(NR Ak 2)3, (R Ak )2Si(NHR Ak 2), (R Ak )(H)Si(NHR Ak )2, (R Ak )3Si(NR Ak 2), (R Ak )3Si(NHR Ak ), H2Si(NHR Ak 2), (R Ak )(H)Si(NR Ak 2)2, HSi(NH2)(NR Ak 2)2, HSi(NR Ak 2)3, Si(NR Ak 2)4, (R')(H)Si(NR"2)2, (R')2Si(NR Ak 2)2, (R')2Si(N[SiH3]2)2, (R')2Si(N[SiR"3]2)2, or (R')3Si(NHR Ak ). In some embodiments, each R' and R'" can be independently any of those described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In particular embodiments, R Ak is methyl (Me), ethyl (Et), n-propyl (nPr), i-propyl (iPr), n-butyl (nBu), s-butyl (sBu), i-butyl (iBu), t-butyl (tBu), and the like.

[0289] Non-limiting examples of the source include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]); dimethylaminodimethylsilane (SiMe2H[NMe2]); dimethylaminotrimethylsilane (SiMe3[NMe2]); dimethylamino-diethylsilane (SiHEt2[NMe2]); dimethylamino-triethylsilane (SiEt3[NMe2]); ethylmethylaminodimethylsilane (SiHMe2[NMeEt]); ethylmethylaminotrimethylsilane (SiMe3[NMeEt]); ethylmethylamino-diethylsilane (SiHEt2[NMeEt]); ethylmethylamino-triethylsilane (SiEt3[NMeEt]); diethylaminomethylsilane (SiH2Me[NEt2]); diethylaminoethylsilane (SiH2Et[NEt2]); ethylaminotrimethylsilane (SiMe3[NHEt]); diethylaminodimethylsilane (SiHMe2[NEt2]); diethylamino-diethylsilane (SiHEt2[NEt2]); diethylaminotrimethylsilane (SiMe3[NEt2]); diethylamino-triethylsilane (SiEt3[NEt2]); isopropylaminodimethylsilane (SiHMe2[NHiPr]); isopropylaminotrimethylsilane (SiMe3[NHiPr]); isopropylamino-diethylsilane (SiHEt2[NHiPr]); isopropylamino-triethylsilane (SiEt3[NHiPr]); diisopropylaminotrimethylsilane (SiMe3[NiPr2]); diisopropylaminosilane (SiH3[NiPr2], C6H 17diisopropylaminosilane (SiH3[NiPr2]); diisopropylaminodimethylsilane (SiHMe2[NiPr2]); diisopropylaminoethylsilane (SiHEt2[NiPr2]); diisopropylaminotriethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]); t-butylaminodimethylsilane (SiHMe2[NHtBu]); t-butylaminotrimethylsilane (SiMe3[NHtBu]); t-butylaminodiethylsilane (SiHEt2[NHtBu]); t-butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl); N-propylisopropylaminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N ethylcyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N- isopropylcyclohexylaminosilane (SiH3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], where Cy is cyclohexyl); pyrrolyltrime- thylsilane (SiMe3[NHPy], where Py is pyrrolyl); pyrrolinyltrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolinyl); piperidinyltrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], where Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], where Im is imidazolyl); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino)methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2); bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2); bis(diethylamino)silane (SiH2[NEt2]2, C8H 22bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(isopropylamino)dimethylsilane (SiMe2[NHiPr]2); bis(isopropylamino)diethylsilane (SiEt2[NHiPr]2); bis(isopropylamino)methylvinylsilane (SiMeVi[NHiPr]2); bis(diisopropylamino)silane (SiH2[NiPr2]2); bis(diisopropylamino)dimethylsilane (SiMe2[NiPr2]2); bis(diisopropylamino)diethylsilane (SiEt2[NiPr2]2); bis(diisopropylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec-butylamino)methylsilane (SiHMe[NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2or BTBAS); bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2); bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); bis(l-imidazolyl)dimethylsilane (SiMe2[Im]2, where Im is an imidazolyl group); tris(dimethylamino)silane (SiH[NMe2]3or 3DMAS); tris(dimethylamino)phenylsilane (SiPh[NMe2]3); tris(dimethylamino)methylsilane (SiMe[NMe2]3); tris(dimethylamino)ethylsilane (SiEt[NMe2]3); tris(ethylmethylamino)silane (SiH[NEtMe]3); tris(diethylamino)silane (SiH[NEt2]3); tris(isopropylamino)silane (SiH[NHiPr]3, C9H 25tris(dimethylamino)silyl amide (Si[NMe2]3[NH2]); tetra(dimethylamino)silane (Si[NMe2]4); tetra(ethylmethylamino)silane (Si[NEtMe]4); tetra(diethylamino)silane (Si[NEt2]4); 1,2-diethyl-tetra(diethylamino)disilane ([Et2N]2EtSi-SiEt[NEt2]2); 1,2-dimethyl-tetra(dimethylamino)disilane ([Me2N]2MeSi-SiMe[NMe2]2); 1,2-dimethyl-tetra(diethylamino)disilane ([Et2N]2MeSi-SiMe[NEt2]2); hexa(methylamino)disilane ([MeHN]3Si-Si[NHMe]3); hexa(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3); hexa(dimethylamino)disilazane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), and the like.

[0290] In some embodiments, the silane source is a halosilane source. A halosilane source is defined as a source having at least one halogen atom and at least one silicon atom. Halogens include chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane source includes a structure of Formula (I): Si(X)4, wherein at least one X includes a halogen atom.

[0291] For example, the halosilane is tetrachlorosilane or silicon tetrachloride (SiCl4). Another example of the chemical formula of the halosilane is Si n X y H z wherein X is a halogen, H is hydrogen; n is an integer greater than or equal to 1 and equal to the number of Si atoms in the molecule; in some embodiments, y is about 1 to about 4, and z is 4-y. Other examples include, but are not limited to, SiHCl3, SiH2Cl2, and SiH3Cl.

[0292] Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes, and fluorosilanes. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane (DCS), monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, hexyl dimethylchlorosilane, hexachlorodisilane (HCDS), and the like.

[0293] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is a source of organosilicon.

[0294] In some embodiments, the halosilane source (e.g., in Formula (I)) has at least one optionally substituted C 1-2 haloalkyl. Non-limiting haloaliphatic groups include -CX y H 3-y wherein y is 1, 2, or 3, wherein each X is independently a halogen (F, CI, Br, or I); -CX z H 2-z CX y H 3-y wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, wherein each X is independently a halogen (F, CI, Br, or I), wherein at least one of z or y is not 0; or -CH2CX y H 3-y wherein y is 1, 2, or 3, wherein each X is independently a halogen (F, CI, Br, or I). Other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2CI), dichloromethyl (-CHC12), trichloromethyl (-CCI3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCI), fluoriodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2CI), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCI2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI), and the like. In particular embodiments, C 1-2 haloalkyl includes beta-haloethyl groups. Still other haloaliphatic groups include C 1-4 haloalkyl, C 2-4 haloalkenyl, and C 2-4 haloalkynyl.

[0295] Conclusion The implementations disclosed herein describe the deposition of material on a substrate (e.g., a wafer, substrate, or other workpiece). Workpieces can have various shapes, sizes, and materials. In this application, the terms "semiconductor wafer," "wafer," "substrate," "wafer substrate," and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will understand that the term "partially fabricated integrated circuit" can refer to a silicon wafer during any of the many stages of integrated circuit manufacturing thereon. Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, 300 mm, or 450 mm. Unless otherwise stated, the processing details described herein (e.g., flow rates, power levels, etc.) relate to processing a 300 mm diameter substrate or a processing chamber configured to process a 300 mm diameter substrate and may be scaled appropriately for substrates or chambers of other sizes. Besides semiconductor wafers, other workpieces that can be used in the implementations disclosed herein include a variety of articles of manufacture, such as printed circuit boards and the like. This process and apparatus can be used in the manufacture of semiconductor devices, displays, LEDs, solar panels, and the like.

[0296] Although the foregoing embodiments have been described in considerable detail for the purpose of clarity, it will be apparent that certain changes and modifications can be made within the scope of the appended claims. It should be noted that many alternative processes, systems, and apparatuses exist for implementing these embodiments. Therefore, these embodiments are to be considered illustrative rather than restrictive, and are not limited to the details given herein.

Claims

1. A method for processing a substrate, the method comprising: providing a patterned substrate having one or more gaps between features; depositing a sacrificial material over the substrate, wherein the sacrificial material is deposited in at least one of the one or more gaps; etching the sacrificial material to expose surfaces of the features; forming a penetration layer over the substrate, wherein the thin penetration layer is deposited on the sacrificial material and on the exposed surfaces of the features; selectively ashing the sacrificial material through the thin penetration layer to leave an air gap where the sacrificial material was previously occupying prior to selective ashing of the sacrificial material, wherein the thin penetration layer is suspended over the air gap; and depositing a dielectric material over the thin penetration layer.

2. The method of claim 1, wherein the features comprise metal.

3. The method of claim 1, wherein the features comprise dielectric material.

4. The method of claim 1, wherein the sacrificial material comprises amorphous carbon.

5. The method of claim 1, wherein the sacrificial material comprises an ashable hard mask.

6. The method of claim 1, wherein the one or more gaps comprise large gaps and small gaps, and wherein the sacrificial material is selectively deposited in small gaps.

7. The method of claim 1, wherein the thin penetration layer comprises silicon oxide.

8. A 3D-NAND cell comprising: alternating silicon oxide and word line layers; a metal oxide layer; a blocking oxide material; a charge trapping material adjacent to the blocking oxide material and in contact with one or more metal oxide layers; an air gap in the metal oxide layer between the blocking oxide material and the charge trapping material in adjacent word lines; a tunneling oxide layer; and a channel layer.

9. A method for processing a substrate, the method comprising: providing a patterned substrate having metal-containing features, gaps between the metal-containing features, and a dielectric capping material on the metal-containing features at or near the gap openings, wherein the metal-containing features have metal-containing surfaces and the dielectric capping material has exposed dielectric surfaces; selectively depositing an inhibitor material on the metal-containing surfaces relative to the exposed dielectric surfaces to close the metal-containing surfaces and leave un-closed dielectric surfaces; forming a catalytic layer over the substrate on the un-closed dielectric surfaces; and exposing the catalytic layer to a reactant to convert the catalytic layer to a dielectric material having a thickness sufficient to close the gaps at the gap openings and leave air gaps between the metal-containing features.

10. The method of claim 9, wherein the metal-containing features comprise ruthenium, tungsten, or molybdenum. ​

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