Low-temperature molybdenum deposition assisted by silicon-containing reactants

Abstract

A molybdenum-containing film is deposited on a semiconductor substrate at a relatively low temperature between about 100°C and about 500°C, such as between about 200°C and about 450°C. For example, molybdenum metal can be deposited at this temperature on a substrate having exposed metal and exposed dielectric in a substantially non-selective manner. In one implementation, a substrate having a recessed feature is provided, where the recessed feature has exposed dielectric on the sidewalls and exposed metal on the bottom. The substrate is exposed to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reagent, thereby reducing the molybdenum-containing precursor to form a molybdenum-containing layer comprising metallic molybdenum. The use of a silicon-containing reactant leads to reduced selectivity of molybdenum deposition over metal / over dielectric.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) A PCT application form is being filed contemporaneously herewith as a part of this application. Each application to which this application claims benefit or priority, as identified in the contemporaneously filed PCT application form, is hereby incorporated by reference in its entirety for all purposes.

[0002] The present invention relates to methods of semiconductor device manufacturing. In particular, embodiments of the present invention relate to depositing molybdenum-containing films in semiconductor processing. [Background technology]

[0003] In semiconductor device fabrication, deposition and etching techniques are used to form patterns of material, such as to form metal lines embedded in a dielectric layer. Some patterning schemes require conformal deposition of material, where the deposited layer should follow the contours of protruding and / or recessed features above the surface of the substrate. Atomic layer deposition (ALD) is often the preferred method of forming conformal layers on a substrate, as it relies on the adsorption of one or more reactants (precursors) on the surface of the substrate and the subsequent chemical conversion of the absorbed layer to the desired metal. Because ALD uses sequential reactions that occur on the surface of the substrate, separated in time and typically limited by the amount of absorbed reactant, the method can provide thin conformal layers with excellent step coverage.

[0004] Chemical vapor deposition (CVD) is another deposition technique that is widely used in semiconductor processing. In CVD, the reaction occurs within the volume of the processing chamber and is not limited by the amount of reactant adsorbed on the surface. As a result, films deposited by CVD are often less conformal than those deposited by ALD. CVD is typically used in applications where step coverage is not as important.

[0005] ALD and CVD may use plasma to drive the reaction of deposition precursors to form the desired film. Processes that utilize plasma are known as plasma enhanced ALD (PEALD) and plasma enhanced CVD (PECVD). Processes that do not use plasma are called thermal ALD and thermal CVD.

[0006] Although ALD and CVD are most commonly used to deposit silicon-containing films, such as silicon oxide, silicon nitride, and silicon carbide, these methods are also suitable for depositing some metals.

[0007] The background statement provided herein is intended to generally provide a context for the present disclosure. To the extent described in this Background section, the works of the inventors named herein, as well as aspects of the statement that may not otherwise be considered prior art at the time of submission, are not admitted, expressly or impliedly, as prior art to the present disclosure. Summary of the Invention

[0008] A method is provided for depositing molybdenum metal via reduction of a molybdenum-containing precursor at a relatively low temperature between about 100° C. and about 500° C. The method utilizes a silicon-containing reactant to improve the reduction of the molybdenum-containing precursor and / or to adjust the selectivity of the molybdenum deposition. In some embodiments, the method is used to deposit molybdenum metal on a semiconductor substrate that includes different exposed materials (e.g., exposed metal and exposed dielectric). For example, a molybdenum-containing layer may be deposited substantially non-selectively in a recessed feature having exposed dielectric material on the sidewalls and exposed metal at the bottom. The provided molybdenum deposition method can be used, for example, in gap-fill applications. The provided method is particularly useful for depositing molybdenum-containing layers, but can also be used to deposit other metals with vaporizable precursors, such as cobalt, ruthenium, and tungsten.

[0009] In one aspect, a method of forming a molybdenum-containing layer on a semiconductor substrate is provided. The method involves: (a) providing a semiconductor substrate having recessed features to a process chamber; and (b) exposing the semiconductor substrate to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to reduce the molybdenum-containing precursor to form a molybdenum-containing layer on the semiconductor substrate, the molybdenum-containing layer comprising a layer of molybdenum metal. In some embodiments, the formed molybdenum-containing layer further comprises a layer comprising a sublayer of molybdenum silicide.

[0010] In some embodiments, the molybdenum-containing precursor is MoX n Y m wherein X is a chalcogen, Y is a halogen, n is 0, 1, or 2, and m is 2, 3, 4, 5, or 6.

[0011] Examples of suitable molybdenum-containing precursors are MoCl5, Mo2Cl 10 , MoO2Cl2, MoOCl4, or any combination thereof.

[0012] In some embodiments, the silicon-containing reactant is Si x R y where x is 1 to 4, y is 4 to 18, and each R is independently selected from the group consisting of H, halogen, and alkyl. Examples of suitable silicon-containing reactants include silane, chlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, trichlorodisilane, dichlorodisilane, chlorodisilane, disilane, or any combination thereof.

[0013] In one implementation, the reducing agent is hydrogen (H2), and exposing the semiconductor substrate to the molybdenum-containing precursor, the reducing agent, and the silicon-containing reactant includes (i) contacting the semiconductor substrate with the silicon-containing reactant for a period of time without delivering a molybdenum-containing precursor to the processing chamber, and (ii) contacting the semiconductor substrate with the molybdenum-containing precursor and H2 after (i). In some embodiments, the semiconductor substrate is contacted with the molybdenum-containing precursor without simultaneously delivering hydrogen to the processing chamber. In other embodiments, the semiconductor substrate is contacted with the molybdenum-containing precursor and hydrogen simultaneously. In some embodiments, the deposition method includes repeating steps (i) and (ii). In some embodiments, step (ii) includes sequentially contacting the semiconductor substrate with the molybdenum-containing precursor and hydrogen, and repeating the sequentially contacting with the molybdenum-containing precursor and hydrogen. In some embodiments, the method further includes (iii) contacting the semiconductor substrate with the silicon-containing reactant after step (ii).

[0014] In some implementations, the reducing agent is hydrogen (H2), and exposing the semiconductor substrate to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant includes contacting the semiconductor substrate with hydrogen, a molybdenum-containing precursor, and a silicon-containing reactant simultaneously.

[0015] In some implementations, the reducing agent is hydrogen (H), and exposing the semiconductor substrate to the molybdenum-containing precursor, the reducing agent, and the silicon-containing reactant includes (i) contacting the semiconductor substrate with hydrogen and the silicon-containing reactant simultaneously, and (iii) contacting the semiconductor substrate with the molybdenum-containing precursor without simultaneously delivering the silicon-containing reactant to the processing chamber.

[0016] In some implementations, the reducing agent is hydrogen (H2), and exposing the semiconductor substrate to the molybdenum-containing precursor, the reducing agent, and the silicon-containing reactant includes (i) contacting the semiconductor substrate with the molybdenum-containing precursor and the silicon-containing reactant simultaneously, and (ii) contacting the semiconductor substrate with hydrogen without delivering the silicon-containing reactant to the process chamber.

[0017] In some embodiments, a recessed feature provided on a semiconductor substrate includes a silicon-containing dielectric exposed on sidewalls of the recessed feature and a metal (e.g., tungsten or cobalt) exposed on a bottom of the recessed feature, and a molybdenum-containing layer is deposited both on the bottom of the recessed feature and on the sidewalls of the recessed feature with a selectivity (bottom to sidewall) of about 1.3:1 or less. In some embodiments, the method includes completely filling the recessed feature with a molybdenum-containing layer, the molybdenum-containing layer comprising a molybdenum metal layer.

[0018] In some embodiments, the methods provided herein are integrated with photolithography processing. For example, the methods may include applying a photoresist to a semiconductor substrate, exposing the photoresist to light, patterning the photoresist to transfer the pattern to the semiconductor substrate, and selectively removing the photoresist from the semiconductor substrate. For example, such photolithography patterning may be used to form recessed features on the substrate prior to depositing a molybdenum-containing material.

[0019] In another aspect, an apparatus for processing a semiconductor substrate is provided, the apparatus including: (a) a process chamber having a substrate holder for holding a semiconductor substrate and one or more inlets for introducing reactants into the process chamber; and (b) a controller with program instructions for performing any of the methods provided herein. For example, the program instructions may include instructions for contacting the semiconductor substrate with a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to form a layer of molybdenum-containing material, the semiconductor substrate having a recessed feature thereon. For example, in some embodiments, the program instructions may be configured to (i) contact the semiconductor substrate with the silicon-containing reactant without simultaneously delivering a molybdenum-containing precursor to the process chamber; and (ii) after (i), contact the semiconductor substrate with a molybdenum-containing precursor and hydrogen. In some embodiments, the program instructions include instructions configured to (i) simultaneously contact the semiconductor substrate with hydrogen and a silicon-containing reactant without delivering a molybdenum-containing precursor to the processing chamber, and (ii) contact the semiconductor substrate with a molybdenum-containing precursor without simultaneously delivering a silicon-containing reactant to the processing chamber. In some embodiments, the program instructions include instructions configured to (i) simultaneously contact the semiconductor substrate with a molybdenum-containing precursor and a silicon-containing reactant without simultaneously delivering hydrogen to the processing chamber, and (ii) contact the semiconductor substrate with hydrogen without simultaneously delivering a silicon-containing reactant to the processing chamber.

[0020] In another aspect, a computer machine readable medium is provided that includes code for effecting any of the steps of the methods provided herein. For example, the code may be provided for contacting a semiconductor substrate having recessed features with a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to form a layer of molybdenum-containing material on the semiconductor substrate.

[0021] In another aspect, there is provided a system including an apparatus as described herein and a stepper.

[0022] In another aspect, a method for forming a metal-containing layer (e.g., a layer containing molybdenum, tungsten, cobalt, or ruthenium) on a semiconductor substrate is provided. In some embodiments, the method includes: (a) providing a semiconductor substrate having recessed features to a process chamber; and (b) exposing the semiconductor substrate to a metal precursor (e.g., a molybdenum precursor, a tungsten precursor, a cobalt precursor, or a ruthenium precursor), a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to reduce the metal precursor and form a metal-containing layer on the semiconductor substrate, the metal-containing layer comprising a layer of a metal (e.g., molybdenum, tungsten, cobalt, or ruthenium) in a zero oxidation state. In some embodiments, the metal-containing layer further comprises a layer of a metal silicide (e.g., molybdenum silicide, tungsten silicide, cobalt silicide, or ruthenium silicide).

[0023] These and other aspects of implementations of the subject matter described herein are illustrated in the accompanying drawings and the description that follows. [Brief description of the drawings]

[0024] [Figure 1A] 1 illustrates a schematic cross-sectional view of a substrate during molybdenum-containing film deposition according to embodiments provided herein. [Figure 1B] 1 illustrates a schematic cross-sectional view of a substrate during molybdenum-containing film deposition according to embodiments provided herein. [Figure 1C] 1 illustrates a schematic cross-sectional view of a substrate during molybdenum-containing film deposition according to embodiments provided herein.

[0025] [Figure 2A] 1 is a process flow diagram of a method of forming a molybdenum-containing film according to embodiments provided herein.

[0026] [Figure 2B] 1 is a process flow diagram of a method of forming a molybdenum-containing film according to embodiments provided herein.

[0027] [Figure 2C] 1 is a process flow diagram of a method of forming a molybdenum-containing film according to embodiments provided herein.

[0028] [Figure 2D] 1 is a process flow diagram of a method of forming a molybdenum-containing film according to embodiments provided herein.

[0029] [Diagram 3] 1 is a process flow diagram of a method of forming a molybdenum-containing film according to embodiments provided herein.

[0030] [Figure 4] Provided are examples of ligands that can be used in the molybdenum precursors according to embodiments provided herein.

[0031] [Diagram 5] Provided are examples of sulfur-containing ligands that can be used in the molybdenum precursors according to embodiments provided herein.

[0032] [Figure 6] Examples of molybdenum precursors according to embodiments provided herein are listed below.

[0033] [Figure 7] 1 is a schematic representation of an apparatus suitable for depositing molybdenum-containing films according to embodiments provided herein.

[0034] [Figure 8] 1 shows a schematic diagram of a multi-station processing system according to embodiments provided herein.

[0035] [Figure 9] 1 shows a schematic diagram of a multi-station processing system according to embodiments provided herein.

[0036] [Figure 10A] FIG. 13 is an experimental diagram for a comparative example showing molybdenum metal deposition selectivity over metal / over dielectric at different temperatures for silicon-free deposition.

[0037] [Figure 10B] FIG. 2 is an experimental diagram illustrating molybdenum-containing layer deposition selectivity on metal / on dielectric at 400° C. as a function of SiH4 pre-soak for silicon-assisted deposition according to embodiments provided herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0038] Methods are provided for depositing a molybdenum-containing film on a semiconductor substrate at relatively low temperatures below about 550° C., such as between about 100° C. and about 500° C., between about 200° C. and about 450° C., or between about 375° C. and about 450° C. The methods can be used, for example, to deposit a molybdenum metal layer and / or a molybdenum silicide layer. In some embodiments, the methods are used to form a thin molybdenum silicide layer on a substrate, followed by deposition of a thicker molybdenum metal layer. For example, the methods provided can be used to deposit a blanket molybdenum-containing layer on a flat substrate, to deposit a conformal molybdenum-containing layer on a substrate having one or more recessed or protruding features, and to fill the recessed features with a molybdenum-containing material.

[0039] In some embodiments, the provided method utilizes the reduction of a molybdenum-containing precursor with a reducing agent, and in addition, a silicon-containing reactant is used to assist the reduction process. In some embodiments, the provided method utilizes the reduction of a molybdenum-containing precursor with a reducing agent, and in addition, a silicon-containing reactant is used to adjust the selectivity of the deposition. It has been discovered that the silicon-containing reactant can be used to minimize the selectivity of depositing a molybdenum-containing layer on a substrate having different exposed materials, such as both metal and dielectric portions. In some embodiments, the use of a silicon-containing reactant in the deposition process results in a substantially non-selective deposition, whereas in the absence of a silicon-containing reactant, molybdenum typically deposits substantially faster on the exposed metal portions of the substrate than on the dielectric portions.

[0040] The provided methods can be used in a variety of applications, including, but not limited to, deposition of molybdenum metal in gap-fill applications, formation of conformal molybdenum metal films, and formation of molybdenum silicide. Examples of semiconductor device structures that can be fabricated using the provided methods include back end of the line (BEOL) metallization structures, front end of the line (FEOL) metallization structures, logic circuitry metallization structures, and memory structures, such as 3D NAND and DRAM. For example, the provided methods can be used for molybdenum silicide formation in 3D DRAM structure fabrication, and for molybdenum metallization in buried word line DRAM. In some embodiments, the methods can be used to deposit molybdenum-containing films having thicknesses ranging between about 0.5 nm and about 4 nm, and can be used to deposit molybdenum metal in a variety of recessed features, such as features with widths between about 1 nm and about 25 nm, features with depths between about 30 nm and about 200 nm or more, and features with a variety of aspect ratios, including high aspect ratios of at least 10:1, such as 30:1.

[0041] Although the methods provided herein are illustrated primarily in relation to the deposition of molybdenum-containing layers, they can be used to deposit other metals with vaporizable precursors, such as tungsten, cobalt, and ruthenium. For example, in another aspect, a method is provided for forming a metal-containing layer (e.g., a layer containing molybdenum, tungsten, cobalt, or ruthenium) on a semiconductor substrate. In some embodiments, the method includes: (a) providing a semiconductor substrate having recessed features to a processing chamber; and (b) exposing the semiconductor substrate to a metal precursor (e.g., a molybdenum precursor, a tungsten precursor, a cobalt precursor, or a ruthenium precursor), a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to reduce the metal precursor and form a metal-containing layer on the semiconductor substrate, wherein the metal-containing layer comprises a layer of metal (e.g., molybdenum, tungsten, cobalt, or ruthenium) in a zero oxidation state. In some embodiments, the metal-containing layer further comprises a layer of a metal silicide (eg, molybdenum silicide, tungsten silicide, cobalt silicide, or ruthenium silicide).

[0042] As used herein, "molybdenum metal" or "metallic molybdenum" refers to a material composed of molybdenum (Mo) in an essentially zero oxidation state. Other elements (e.g., C, N, or O) may be present in the molybdenum metal in small amounts (e.g., less than about 15 atomic %, not including hydrogen in the calculation, or in a total amount of about 10%). As used herein, "high purity molybdenum metal" refers to molybdenum metal containing less than about 5% of other elements, such as less than about 1% of other elements, where hydrogen is not included in the calculation. In some embodiments, the molybdenum metal deposited by the provided methods includes at least a portion that is at least about 90% pure molybdenum, such as at least about 95% or at least about 99%, where % is weight percent.

[0043] Molybdenum disilicide (MoSi x) refers to a material composed essentially of molybdenum and silicon, where x indicates that the stoichiometry may vary. Other elements may be present in molybdenum silicide in small amounts, for example less than about 10 atomic %, where hydrogen is excluded from the calculation.

[0044] As used herein, the term "semiconductor substrate" refers to a substrate at any stage of semiconductor device fabrication that contains semiconductor material somewhere within the structure of the semiconductor substrate. It is understood that the semiconductor material in the semiconductor substrate need not be exposed. A semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material is an example of a semiconductor substrate. The following detailed description assumes that the disclosed implementations are implemented on a semiconductor wafer, such as on a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed implementations are not so limited. Workpieces may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that may utilize the disclosed implementations include various articles such as printed circuit boards and the like.

[0045] As used herein, a "reducing agent" refers to a reactant that loses one or more electrons in a reaction.

[0046] As used herein, "heteroleptic complexes" refer to compounds that contain at least two different ligands attached to a metal center.

[0047] As used herein, "homoleptic complexes" refer to compounds that contain all identical ligands attached to the metal center.

[0048] The term "about" as used herein means ±10% of any stated value, unless otherwise specified. As used herein, the term modifies any stated value, range of values, or one or more endpoints of a range.

[0049] As used herein, "top", "bottom", "upper", "lower", "above" and "below" are used to provide relative relationships between structures. Use of these terms does not imply or require that a particular structure must be located at a particular location within an apparatus.

[0050] As used herein, "substantially non-selective deposition" refers to deposition in which the ratio of the deposition rate on a first surface to the deposition rate on a second surface (selectivity) is between about 0.7 and about 1.3. For example, the selectivity of a substantially non-selective deposition may be between about 0.9 and 1.1.

[0051] As used herein, the term "silicon-assisted deposition" refers to deposition that employs exposure of a substrate to a silicon-containing reactant in a deposition process. Exposure of a substrate to a silicon-containing reactant, a molybdenum-containing precursor, and a reducing agent to deposit molybdenum metal and / or molybdenum silicide is an example of silicon-assisted deposition.

[0052] As used herein, "non-silicon-containing deposition" refers to deposition that does not utilize a silicon-containing reactant. Exposing a substrate to a molybdenum-containing precursor and a reducing agent without exposure to a silicon-containing reactant to deposit molybdenum metal is an example of a non-silicon-containing deposition.

[0053] As used herein, the term "sublayer" refers to any portion of a larger layer. For example, a layer of molybdenum-containing material may include a sublayer of molybdenum metal and a sublayer of molybdenum silicide.

[0054] As used herein, the phrase at least one of A, B, and C should be interpreted to mean a logic using a non-exclusive logical OR (A OR B OR C, A or B or C), and not to mean "at least one of A, at least one of B, and at least one of C."

[0055] The terms "acyl" or "alkanoyl", as used interchangeably herein, refer to groups consisting of 1, 2, 3, 4, 5, 6, 7, 8, or 9 or more carbon atoms, or hydrogens, attached to the parent molecular group through a carbonyl group, as defined herein, of linear, branched, cyclic, saturated, unsaturated, and aromatic configurations, and combinations thereof. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, and the like. In some embodiments, an acyl or alkanoyl group, as defined herein, is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group.

[0056] By "alkanoyloxy" is meant an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. An example of this group is acetoxy (-OAc or -OC(O)Me). In some embodiments, an alkanoyloxy group is -OC(O)-R, as defined herein, where R is hydrogen, an aliphatic group, or an aromatic group.

[0057] By "aliphatic" we mean any group having 1 to 25 carbon atoms (C), including alkanes (or alkyls), alkenes (or alkenyls), and alkynes (or alkynyls). 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), and so on, with at least 1 carbon atom to 50 carbon atoms (C 1-50 ) including cyclic versions thereof, as well as linear and branched arrangements, and all stereoisomers and positional isomers. Aliphatic groups are unsubstituted or substituted, e.g., with functional groups as described herein. For example, aliphatic groups can be substituted with one or more substituents as described herein for alkyl.

[0058] By "aliphatic carbonyl" is meant an aliphatic group that is or can be linked to a compound disclosed herein, where the aliphatic group is or becomes linked through a carbonyl group (-C(O)-). In some embodiments, an aliphatic carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group, as defined herein.

[0059] By "aliphatic carbonyloxy" is meant an aliphatic group that is or can be linked to a compound disclosed herein, where the aliphatic group is or becomes linked through a carbonyloxy group (-OC(O)-). In some embodiments, an aliphatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group, as defined herein.

[0060] By "aliphatic oxy" is meant an aliphatic group that is or can be linked to a compound disclosed herein, where the aliphatic group is or becomes linked through an oxy group (-C(O)-). In some embodiments, the aliphatic oxy group is -OR, where R is an optionally substituted aliphatic group, as defined herein.

[0061] By "aliphatic oxycarbonyl" is meant an aliphatic group that is or can be linked to a compound disclosed herein, where the aliphatic group is or becomes linked through an oxycarbonyl group (-C(O)O-). In some embodiments, an aliphatic oxycarbonyl group is -C(O)OR, where R is an optionally substituted aliphatic group, as defined herein.

[0062] By "alkylaryl", "alkenylaryl", and "alkynylaryl" is meant an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, that is linked (or attached) or can be linked (or attached) to a parent molecular group through an aryl group, as defined herein. The alkylaryl group, the alkenylaryl group, and / or the alkynylaryl group can be substituted or unsubstituted. For example, the alkylaryl group, the alkenylaryl group, and / or the alkynylaryl group can be substituted with one or more substituents, as described herein for alkyl and / or aryl. Representative unsubstituted alkylaryl groups are those that consist of 7 to 16 carbons (C 7-16 alkylaryl), as well as alkyl groups with 1 to 6 carbons and alkyl groups with 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Representative unsubstituted alkenylaryl groups are groups having 7 to 16 carbon atoms (C 7-16 alkenylaryl), as well as alkenyl groups with 2 to 6 carbons and aryl groups with 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Representative unsubstituted alkynylaryl groups are groups having 7 to 16 carbon atoms (C 7-16 alkynylaryl), as well as alkynyl groups with 2 to 6 carbons and aryl groups with 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18In some embodiments, an alkylaryl group is -LR, where L is an aryl or arylene group, as defined herein, and R is an alkyl group, as defined herein. In some embodiments, an alkenylaryl group is -LR, where L is an aryl or arylene group, as defined herein, and R is an alkenyl group, as defined herein. In some embodiments, an alkynylaryl group is -LR, where L is an aryl or arylene group, as defined herein, and R is an alkynyl group, as defined herein.

[0063] "Alkenyl" refers to an alkyl group having 2 to 25 carbon atoms (C 2-25 ) and other olefins with at least 2 carbon atoms to 50 carbon atoms (C 2-50 ), or at least 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, which can be derived by removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Representative alkenyls include optionally substituted C 2-24 Alkyl groups include. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to remove a suitable attachment to the parent molecular group or between the parent molecular group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents as described herein for alkyl. Non-limiting alkenyl groups include aryl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0064] By "alkoxy" is meant -OR, where R is an optionally substituted aliphatic group as described herein. Representative alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more substituents as described herein for alkyl. Representative unsubstituted alkoxy groups are C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 The alkoxy group includes:

[0065] By "alkoxyalkyl," as defined herein, is meant an alkyl group substituted through an alkoxy group, as defined herein. Representative unsubstituted alkoxyalkyl groups contain between 2 and 12 carbons (C 2-12 Alkoxy groups with 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl group is -LOR, where each of L and R is independently an alkyl group, as defined herein.

[0066] By "alkoxylcarbonyl" is meant -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, the alkoxylcarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxylcarbonyl group can be substituted or unsubstituted. For example, the alkoxylcarbonyl group can be substituted with one or more substituents as described herein for alkyl. Representative unsubstituted alkoxylcarbonyl groups are C 2-3 , C2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 The alkoxycarbonyl group is

[0067] "Alkyl" refers to an alkyl group having 1 to 25 carbon atoms (C 1-25 ), and so on, with at least 1 carbon atom to 50 carbon atoms (C 1-50 ), or 1 to 10 carbon atoms (C 1-10 ), which can be derived by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). An alkyl group can be branched, straight chain, or cyclic (e.g., cycloalkyl). Representative alkyls include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Alkyl groups can also be substituted or unsubstituted. An alkyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable attachment to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group can be: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (2) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6alkyl), (4) amino (e.g., -NR 1 R 2 , where R 1 and R 2 Each of R is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or taken together with the nitrogen atom to which each is attached, 1 and R 2 can form a heterocyclyl group as defined herein), (5) aryl, (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl), (7) aryloyl (e.g., -C(O)-R, where R is aryl), (8) azido (e.g., -N), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11) C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein), (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl, as defined herein), (15) heterocyclyloyl (e.g., -C(O)-R, where R is heterocyclyl, as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO), (19) oxo (e.g., =O), (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl), (21) thiol (e.g., -SH), (22) -COR 1 , where R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Ariel C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (23) -C(O)NR aryl 1 R2 , where R 1 and R 2 Each of these is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (24) -SO2R 1 , where R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 (25)-SONR 1 R 2 , where R 1 and R 2 Each of these is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), and (26)-NR 1 R 2 wherein R 1 and R 2 each of which is (a) hydrogen, (b) an 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., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl) 1 R 2 In some embodiments, the alkyl group may be substituted with 2, 3, or 4 substituents in the case of an alkyl group consisting of 2, 3, or more than 2 carbons independently selected from the group consisting of: 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 is an alkyl group.

[0068] By "alkylene," "alkenylene," or "alkynylene" is meant a polyvalent (e.g., divalent) form of an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. Representative alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is one selected from the group consisting of C 1-3 , C 1-6 , 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 In another embodiment, the alkylene group is 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C2-20 , or C 2-24 The alkylene, alkenylene, or alkynylene group may be branched or unbranched. The alkylene, alkenylene, or alkynylene group may also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group may be substituted with one or more substituents as described herein for alkyl.

[0069] By "alkylsulfinyl" is meant an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is 1-6 or C 1-12 In another embodiment, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0070] By "alkylsulfinylalkyl" is meant an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is a C 2-12 or C 2-24 Alkyl sulfinyl alkyl groups (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl, or C 1-12 Alkylsulfinyl-C 1-12 In another embodiment, the alkylsulfinylalkyl group is -LS(O)-R, where each of L and R is independently an alkyl group, as defined herein.

[0071] By "alkylsulfonyl" is meant an alkyl group, as defined herein, attached to the parent molecular group through a -S(O)- group. In some embodiments, an unsubstituted alkylsulfonyl group is 1-6 or C 1-12In other embodiments, the alkylsulfonyl group is -SO-R, where R is an optionally substituted alkyl (e.g., optionally substituted C 1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0072] By "alkylsulfonylalkyl" is meant an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is selected from the group consisting of C 2-12 or C 2-24 Alkyl sulfonyl alkyl groups (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl, or C 1-12 Alkylsulfonyl-C 1-12 In another embodiment, the alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group, as defined herein.

[0073] "Alkynyl" refers to an alkyl group having 2 to 25 carbon atoms (C 2-25 ) and other olefins with at least 2 carbon atoms to 50 carbon atoms (C 2-50 ), at least 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, which can be derived by removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight chain, or cyclic (e.g., cycloalkynyl). Representative alkynyls include optionally substituted C 2-24Alkynyl groups include alkyl groups. Alkynyl groups can be cyclic or acyclic, examples being ethynyl and 1-propynyl. Alkynyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable attachment to the parent molecular group or between the 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.

[0074] By "ambient temperature" is meant a temperature ranging from 16°C to 26°C, such as from 19°C to 25°C, or from 20°C to 25°C.

[0075] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 wherein R 1 and R 2 Each of R is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group, as defined herein.

[0076] "Amino" means -NR 1 R 2 wherein R 1 and R 2 Each of R is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or a combination thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group, as defined herein. In certain embodiments, R 1 and R 2Each of R is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted silyl, or optionally substituted silyloxy. 1 and R 2 can be taken together with their attached nitrogen atoms to form an optionally substituted heterocyclyl.

[0077] By "aminoalkyl," as defined herein, is meant an alkyl group substituted with an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 where L is an alkyl group as defined herein and R 1 and R 2 Each of R is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or combinations thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group, as defined herein. In some embodiments, the aminoalkyl group can be -LC(NR 1 R 2 )(R 3 )-R 4 where L is a covalent bond or an alkyl group, and R 1 and R 2 Each of R is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or combinations thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group, as defined herein, and R 3 and R 4 Each of is independently H or alkyl, as defined herein.

[0078] By "aminooxy" is meant an oxy group substituted with an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 wherein R 1 and R 2 Each of R taken together with the attached nitrogen atom is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein. 1 and R 2 can form a heterocyclyl group, as defined herein. In certain embodiments, R 1 and R 2 Each of is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted silyl, or optionally substituted silyloxy.

[0079] By "aromatic", unless otherwise specified, it is meant a cyclic conjugated group or moiety consisting of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), where at least one ring is aromatic, i.e., at least one ring, and optionally multiple fused rings, have a contiguous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to 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, for example, by functional groups as described herein. For example, the aromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0080] By "aromatic carbonyl" is meant an aromatic group that is or can be linked to a compound disclosed herein, where the aromatic group is or becomes linked through a carbonyl group (-C(O)-). In some embodiments, an aromatic carbonyl group is -C(O)-R, as defined herein, where R is an optionally substituted aromatic group.

[0081] By "aromatic carbonyloxy" is meant an aromatic group that is or can be linked to a compound disclosed herein, where the aromatic group is or becomes linked through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0082] By "aromatic oxy" is meant an aromatic group that is or can be linked to a compound disclosed herein, where the aromatic group is or becomes linked through an oxy group (-O-). In some embodiments, the aromatic oxy group is -OR, where R is an optionally substituted aromatic group as defined herein.

[0083] By "aromatic oxycarbonyl" is meant an aromatic group that is or can be linked to a compound disclosed herein, where the aromatic group is or becomes linked through an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic carbonyl group is -C(O)OR, where R is an optionally substituted aromatic group, as defined herein.

[0084] By "aryl" is meant an aryl group having from 5 to 10 carbon atoms (C 5-10 ) and other cyclic alkyl chains with at least 5 to 15 carbon atoms (C 5-15), which fused ring may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Representative aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group with 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. Similarly, non-heteroaryl, also included within the term aryl, defines a group that contains any aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. An aryl group may be any of the following: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 (2) C 1-6 Alkyl, (3) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, where L and R are each independently C 1-6 (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, where L and R are each independently C 1-6 (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6(9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 Each of R is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or combinations thereof, as defined herein, or taken together with the nitrogen atom to which each is attached, 1 and R 2 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 is alkyl, and L 2 is a covalent bond or C 1-6 is alkyl, R 1 and R 2 Each of is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, heterohaloaliphatic, aromatic, or combinations thereof, as defined herein, or each taken together with the nitrogen atom to which it is attached is R 1 and R 2 can form a heterocyclyl, as defined herein, and R 3 and R 4 Each of is independently H or C 1-6 (12) heteroaryl, (13) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (14) aryloyl (e.g., -C(O)-R, where R is aryl), (15) azido (e.g., -N), (16) cyano (e.g., -CN), (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6(18) aldehydes (e.g., -C(O)H), (19) aldehydes-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 (20) C 3-8 Cycloalkyl, (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8 (22) halo, (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 is alkyl, and 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 of is independently H or C 1-6 (24) heterocyclyl (e.g., a five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms, as defined herein), (25) heterocyclyloxy (e.g., -OR, where R is heterocyclyl, as defined herein), (26) heterocyclyloyl (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 is alkyl, and L 2 is a covalent bond or alkyl, and R 1 and R 2 Each of is independently H or C, as defined herein. 1-6 (29) nitro, (30) C1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or alkyl, and R 1 and R 2 Each of is independently H or C, as defined herein. 1-6 (31) N-protected amino, (32) N-protected amino-C 1-6 Alkyl, (33) oxo (e.g., =O), (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, where L and R are each independently C 1-6 (36)-(CH2) r CO2R 1 In the formula, r is an integer from 0 to 4, and R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (37)-(CH2) r CONR 1 R 2 In the formula, r is an integer from 0 to 4, and each R 1 and R 2 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (38)-(CH2), independently selected from the group consisting of alkyl,r SO2R 1 In the formula, r is an integer from 0 to 4, and R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (39)-(CH2) r SO2NR 1 R 2 In the formula, r is an integer from 0 to 4, and R 1 and R 2 Each of these is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (40)-(CH2), independently selected from the group consisting of: r NR 1 R 2 In the formula, r is an integer from 0 to 4, and R 1 and R 2 each of which is (a) hydrogen, (b) an 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., -LR, 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., -LR, where L is C 1-6 alkyl and R is C 3-8(41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2) n CF3, where n is an integer from 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, where n is an integer from 0 to 10), (44) aryloxy (e.g., -OR, where R is aryl), (45) cycloalkoxy (e.g., -OR, where R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -OLR, where L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted alkyl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 is an alkyl group.

[0085] As defined herein, "arylalkyl", "arylalkenyl", and "arylalkynyl" refer to an aryl group that is linked (or attached) or can be linked (or attached) to a parent molecular group through an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein. The arylalkyl group, the arylalkenyl group, and / or the arylalkynyl group can be substituted or unsubstituted. For example, the arylalkyl group, the arylalkenyl group, and / or the arylalkynyl group can be substituted with one or more substituents, as described herein for the aryl and / or alkyl. Representative unsubstituted arylalkyl groups are aryl groups consisting of 7 to 16 carbons (C 7-16arylalkyl) as well as groups having aryl groups with 4 to 18 carbons and alkyl groups with 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Representative unsubstituted arylalkenyl groups are those containing 7 to 16 carbons (C 7-16 arylalkenyl) as well as groups having aryl groups with 4 to 18 carbons and alkenyl groups with 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Representative unsubstituted arylalkynyl groups are 7 to 16 carbon (C 7-16 arylalkynyl) as well as groups having aryl groups with 4 to 18 carbons and alkynyl groups with 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, an arylalkyl group is -LR, where L is an alkyl or alkylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, an arylalkenyl group is -LR, where L is an alkenyl or alkenylene group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, an arylalkynyl group is -LR, where L is an alkynyl or alkynylene group, as defined herein, and R is an aryl group, as defined herein.

[0086] By "arylene" is meant a polyvalent (e.g., divalent) form of an aryl group, as defined herein. Representative arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, acenaphthylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10The arylene group may be branched or unbranched. The arylene group may also be substituted or unsubstituted. For example, the arylene group may be substituted with one or more substituents as described herein for aryl.

[0087] By "arylalkoxy" is meant an arylalkyl group, as defined herein, attached to the parent molecular group through 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.

[0088] By "aryloxy" is meant -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is C 4-18 or C 6-18 In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0089] By "aryloxycarbonyl" is meant an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is C 5-19 In another embodiment, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group, as defined herein.

[0090] By "aryloyl" is meant an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is 7-11 Aryloyl group or C 5-19 In another embodiment, the aryloyl group is -C(O)-R, where R is an aryl group, as defined herein.

[0091] By "aryloyloxy" is meant an aryloyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, an unsubstituted aryloyloxy group is 5-19 In another embodiment, the aryloyloxy group is -OC(O)-R, where R is an aryl group, as defined herein.

[0092] By "azido" is meant the -N3 group.

[0093] By "azidoalkyl" is meant an azido group, as defined herein, attached to the parent molecular group through an alkyl group. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group, as defined herein.

[0094] By "azo" is meant an -N=N- group.

[0095] By "carbamoyl" is meant an amino group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, carbamoyl is -C(O)NR 1 R 2 is a group, wherein R 1 and R 2 Each of R is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or a combination thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group as defined herein.

[0096] By "carbamoyloxy" is meant a carbamoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. In some embodiments, carbamoyl is -OC(O)NR1 R 2 is a group, wherein R 1 and R 2 Each of R is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or a combination thereof, as defined herein, or each taken together with the attached nitrogen atom is R 1 and R 2 can form a heterocyclyl group as defined herein.

[0097] By "carbonimidoyl" is meant a -C(NR)- group. In some embodiments, R 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 alkylaryl, or optionally substituted arylalkyl, optionally substituted silyloxy, or any combination thereof, as defined herein.

[0098] "Carbonyl" means the group -C(O)-, which also can be depicted as >C=O.

[0099] "Carboxyl" means the -CO2H group or its anion.

[0100] By "catalyst," as one of ordinary skill in the art would readily understand, is meant a compound capable of catalyzing a synthetic reaction, usually present in small amounts relative to the reactants. In some embodiments, the catalyst may include a transition metal coordination compound.

[0101] By "cyanato" is meant the -OCN group.

[0102] By "cyano" is meant the radical --CN.

[0103] By "alicyclic" is meant a cyclic aliphatic group, as defined herein.

[0104] By "cycloalkoxy" is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group, as defined herein.

[0105] By "cycloalkylalkoxy" is meant an -OLR group where L is an alkyl or alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0106] By "cycloalkyl," unless otherwise specified, is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of three to eight carbons, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those groups described herein for alkyl. Additionally, cycloalkyl groups can contain one or more double and / or triple bonds.

[0107] By "cycloheteroaliphatic" is meant a cyclic heteroaliphatic group, as defined herein.

[0108] By "disilanyl" is meant a group containing a Si-Si bond. In some embodiments, the disilanyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 is a group, wherein R S1 , R S2 , R S3 , R S4 , and RS5 Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0109] By "disulfide" is meant -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0110] By "electron donating group" is meant a functional group that is capable of donating, such as by resonance, at least a portion of the electron density of the functional group into a ring to which the functional group is directly attached.

[0111] By "electron-withdrawing group" is meant a functional group that can accept electron density from a ring to which the functional group is directly attached, such as by an electron-withdrawing inductive effect.

[0112] By "halo" is meant F, Cl, Br, or I.

[0113] By "chalcogen" is meant O, S, Se, or Te.

[0114] By "haloaliphatic" is meant an aliphatic group, as defined herein, in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0115] By "haloalkyl" is meant an alkyl group, as defined herein, in which one or more hydrogen atoms, such as 1-10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, the haloalkyl can be a -CX group, where each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -LX, where L is an alkyl group, as defined herein, and X is fluoro, chloro, or iodo. In other embodiments, the haloalkyl group is -LC(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group, as defined herein, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is H or alkyl, as defined herein.

[0116] By "haloheteroaliphatic" is meant a haloheteroaliphatic group, as defined herein, in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0117] By "heteroaliphatic" is meant an aliphatic group containing at least one heteroatom to 20 heteroatoms, such as 1-15 heteroatoms or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group, as defined herein. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaliphatic groups can be substituted with one or more substituents as described herein for alkyl.

[0118] By "heteroaliphatic carbonyl" is meant a heteroaliphatic group that is or can be linked to a compound disclosed herein, where a heteroaromatic group is or becomes linked through a carbonyl group (-C(O)-). In some embodiments, a heteroaliphatic carbonyl group is -C(O)-R, as defined herein, where R is an optionally substituted heteroaliphatic group, as defined herein.

[0119] By "heteroaliphatic carbonyloxy" is meant a heteroaliphatic group that is or can be linked to a compound disclosed herein, where the heteroaliphatic group is or becomes linked through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group, as defined herein.

[0120] By "heteroaliphaticoxy" is meant a heteroaliphatic group that is or can be linked to a compound disclosed herein, where the heteroaliphatic group is or becomes linked through an oxy group (-C(O)-). In some embodiments, the heteroaliphaticoxy group is -OR, where R is an optionally substituted heteroaliphatic group, as defined herein.

[0121] By "heteroaliphaticoxycarbonyl" is meant a heteroaliphatic group that is or can be linked to a compound disclosed herein, where the heteroaliphatic group is or becomes linked through an oxycarbonyl group (-C(O)O-). In some embodiments, a heteroaliphaticoxycarbonyl group is -C(O)OR, as defined herein, where R is an optionally substituted heteroaliphatic group, as defined herein.

[0122] By "heteroalkyl", "heteroalkenyl", and "heteroalkynyl" is meant an alkyl, alkenyl, or alkynyl group, respectively (which may be branched, straight chain, or cyclic), containing at least one heteroatom to 20 heteroatoms, such as 1-15 heteroatoms or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group, as defined herein.

[0123] By "heteroalkylene," "heteroalkenylene," and "heteroalkynylene" is meant the polyvalent (e.g., divalent) forms of a heteroalkyl group, heteroalkenyl group, or heteroalkynyl group, respectively, as defined herein.

[0124] By "heteroaromatic" is meant an aromatic group containing at least one heteroatom to 20 heteroatoms, such as 1-15 heteroatoms, or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group, as defined herein. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups can be substituted with one or more substituents, as described herein for alkyl and / or aryl.

[0125] By "heteroaromatic carbonyl" is meant a heteroaromatic group that is or can be linked to a compound disclosed herein, where the heteroaromatic group is or becomes linked through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic carbonyl group is -C(O)-R, as defined herein, where R is an optionally substituted heteroaromatic group, as defined herein.

[0126] By "heteroaromatic carbonyloxy" is meant a heteroaromatic group that is or can be linked to a compound disclosed herein, where the heteroaromatic group is or becomes linked through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic carbonyloxy group is -OC(O)-R, as defined herein, where R is an optionally substituted heteroaromatic group, as defined herein.

[0127] By "heteroaromaticoxy" is meant a heteroaromatic group that is or can be linked to a compound disclosed herein, where the heteroaromatic group is or becomes linked through an oxy group (-O-). In some embodiments, the heteroaromaticoxy group is -OR, where R is an optionally substituted heteroaromatic group, as defined herein.

[0128] By "heteroaromatic oxycarbonyl" is meant a heteroaromatic group that is or can be linked to a compound disclosed herein, where the heteroaromatic group is or becomes linked through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic carbonyl group is -C(O)OR, where R is an optionally substituted heteroaromatic group, as defined herein.

[0129] By "heteroaryl" is meant an aryl group containing at least one heteroatom to six heteroatoms, such as, but not limited to, one to four heteroatoms selected from oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the ring. Such heteroaryl groups may have a single ring, or multiple fused rings, which may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Representative heteroaryls include the subset of heterocyclyl groups that are aromatic, i.e., contain 4n+2 pi-electrons in a monocyclic or polycyclic ring structure, as defined herein.

[0130] By "heteroarylene" is meant a multivalent (eg, divalent) form of a heteroaryl group, as defined herein.

[0131] By "heteroatom" is meant an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorous. In certain disclosed embodiments, heteroatoms do not include halogen atoms, such as when valence constraints do not permit.

[0132] By "heterocyclyl" is meant, unless otherwise specified, a five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). Five-membered rings have zero to two double bonds, and six- and seven-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles are fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homoperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, Examples of the alkyl groups include aryl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, urisyl, 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.

[0133] By "heterocyclyloxy" is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group, as defined herein.

[0134] By "heterocyclyloyl" is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is -C(O)-R, where R is a heterocyclyl group, as defined herein.

[0135] "Hydrazino" gives -NR 1 -NR 2 R 3 wherein R 1 , R 2 , and R 3 each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or each taken together with the nitrogen atom attached thereto is R 1 and R 2 or R 2 and R 3 Combinations of can form a heterocyclyl group, as defined herein. In some embodiments, R 1 , R 2 , or R 3 Each of R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl. In certain embodiments, R 2 and R 3 can be taken together with their attached nitrogen atoms to form an optionally substituted heterocyclyl.

[0136] By "hydroxyl" is meant --OH.

[0137] By "hydroxyalkyl" is meant an alkyl group substituted with one to three hydroxyl groups, as defined herein, with the proviso that only one hydroxyl group may be attached to a single carbon atom of the alkyl group, and 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 an alkyl group, as defined herein, and R 1 and R 2 Each of is independently H or alkyl, as defined herein.

[0138] By "imidoyl" is meant a moiety that contains a carbonimidoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2 where 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, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted silyloxy, or any combination thereof, as defined herein. In other embodiments, the imidoyl group is C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar where R 1is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl, or optionally substituted silyloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic, R Ar is an optionally substituted aryl or an optionally substituted aromatic.

[0139] By "imino" is meant the group -NR-. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, or optionally substituted arylalkyl.

[0140] By "isocyanato" is meant an --NCO group.

[0141] By "isocyano" is meant the -NC group.

[0142] By "ketone" is meant a -C(O)R, or a compound containing such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. An example of a ketone is R 1 C(O)R, where R and R 1 is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0143] By "nitro" is meant the -NO2 group.

[0144] By "nitroalkyl" is meant an alkyl group substituted with one to three nitro groups, as defined herein. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group, as defined herein. In other embodiments, the nitroalkyl group is -LC(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group, as defined herein, and R 1 and R 2 Each of is independently H or alkyl, as defined herein.

[0145] By "oxo" is meant the group ═O.

[0146] By "oxy" is meant --O--.

[0147] By "perfluoroalkyl" is meant an alkyl group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. Representative perfluoroalkyl groups include trifluoromethyl, pentafluoromethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer from 0 to 10.

[0148] By "perfluoroalkoxy" is meant an alkoxy group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group, as defined herein.

[0149] By "salt" is meant an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes cationic or anionic compounds that form an electrically neutral compound or structure. The salts can be prepared during the final isolation and purification of the compounds of the invention, or separately, in situ by reacting the free base with a suitable organic acid (thereby producing an anionic salt) or by reacting the acidic group with a suitable metal or organic base (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphor, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, and lactobionate. Salts include, but are not limited to, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, acetate, succinate, sulfate, tannate, tartrate, theophylline, thiocyanate, 3-ethyliodo compounds, trienesulfonate, undecanoate, valerate, and the like.Representative cationic salts include metal salts such as alkali or alkaline rare earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and other metal salts such as aluminum, bismuth, iron, and zinc, as well as non-toxic ammonium, quaternary ammonium, and amino cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc. 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, amidium, guanidium, phosphofazinium, phosphazenium, pyridinium, and the like, as well as other cationic salts described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridinium, ridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted isoxazolidinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prenium).

[0150] "Silyl" means -SiR 1 R 2 R 3 Group or -SiR 1 R2 In some embodiments, R 1 , R 2 , or R 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , or R 3 Each of is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, 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, and each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl.

[0151] By "silyloxy" is meant -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 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3Each of is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, or optionally substituted amino. In other embodiments, the silyl group is -O-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, and each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl.

[0152] By "sulfinyl" is meant the group -S(O)-.

[0153] By "sulfo" is meant the group -S(O)2OH.

[0154] By "sulfonyl" or "sulfonate" is meant a -S(O)- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0155] By "thioalkyl" is meant an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Representative unsubstituted thioalkyl groups include C 1-6 In some embodiments, the thioalkyl group is -SR, where R is an alkyl group, as defined herein.

[0156] By "thiol" is meant a -SH group.

[0157] Those skilled in the art will recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., methyl substituted with five different groups, etc.). Such impermissible substitution patterns are readily recognized by those skilled in the art. Any functional group disclosed herein and / or defined above may or may not be substituted unless otherwise indicated herein.

[0158] Other features and advantages of the invention will become apparent from the following description and from the claims.

[0159] Embodiment In some embodiments, the deposition method involves providing a semiconductor substrate having recessed features to a process chamber and exposing the semiconductor substrate to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to form a molybdenum-containing layer on the semiconductor substrate, the molybdenum-containing layer comprising a layer of molybdenum metal, or a layer of molybdenum silicide, or a combination of a layer of molybdenum metal and a layer of molybdenum silicide. In some implementations, the deposited molybdenum-containing layer comprises both molybdenum silicide (e.g., formed at the start of deposition at an interface with another layer of the substrate) and molybdenum metal (deposited after the molybdenum silicide is formed). In some embodiments, the deposition is performed at a temperature between about 200° C. and about 450° C., such as between about 375° C. and 450° C. The pressure during deposition can range, for example, between about 0.1 Torr and about 100 Torr, such as between about 10 Torr and about 100 Torr. The deposition can be performed in a CVD or ALD processing chamber (or multiple processing chambers) and does not require activation of the reactants with plasma (i.e., the entire deposition can be performed thermally). The molybdenum-containing precursor (or partially reduced molybdenum-containing precursor) during deposition is reduced (e.g., to molybdenum metal) by the reducing agent, while the role of the silicon-containing reactant is to at least one of facilitate the reduction reaction (e.g., by reducing the molybdenum in the precursor to a lower oxygen state) and adjust the selectivity of the deposition. In some embodiments, the silicon-containing reactant not only facilitates the reduction but also adjusts the selectivity of the deposition.

[0160] While the provided method can be used with a variety of substrates, in some embodiments, the method is used on a substrate having a recessed feature with different exposed materials on the sidewalls and bottom. For example, in some embodiments, the substrate has a recessed feature with exposed metal on the bottom and exposed dielectric on the sidewalls. FIG. 1A illustrates a schematic cross-sectional view of a portion of such a substrate provided for depositing molybdenum metal. The substrate has a recessed feature 101 formed in a layer of dielectric 103, and at the bottom of the recessed feature 101, a layer of metal 105 is exposed. The dielectric layer 103 may include a silicon-containing dielectric, such as, for example, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, and the like. The layer of metal 105 may include, for example, tungsten, copper, cobalt, molybdenum, and the like. In one example, the dielectric material in the dielectric layer 103 is silicon oxide, and the metal layer 105 is a tungsten layer. The provided methods can be used to deposit molybdenum-containing materials in a variety of different recessed features, but are particularly useful for depositing in features with aspect ratios of at least about 10:1, such as at least 30:1 or at least 50:1, since it is difficult to deposit molybdenum in a conformal manner in high aspect ratio features at low temperatures. The methods can be used to deposit thin molybdenum-containing layers conformally (e.g., 1 nm to 10 nm thick) and / or to fill recessed features with molybdenum metal, e.g., using conformal filling.

[0161] When molybdenum is deposited in the absence of a silicon-containing reactant, it is deposited mostly on the metal layer, not on the dielectric layer, leading to non-conformal coverage. For example, a selectivity of molybdenum metal deposition of 10 or more (referring to the ratio of the deposition rate on the metal to the deposition rate on the dielectric) is observed at 375°C, leading to thick bottom coverage and thin sidewall coverage. The deposition selectivity can be reduced by increasing the deposition temperature to 500°C or higher, but it is noted that molybdenum metal deposition at high temperatures is often undesirable due to thermal budget constraints. It has been found that the introduction of a silicon-containing reactant dramatically reduces the deposition selectivity at lower temperatures below about 450°C, such as temperatures between about 375°C and about 450°C, thereby providing a means to conformally deposit a molybdenum-containing layer at a relatively low temperature. In some embodiments, to achieve the desired selectivity loss, the substrate is exposed to a silicon-containing reactant before being contacted with a molybdenum-containing precursor. For example, the substrate may be exposed to the silicon-containing reactant for at least about 10 seconds, such as at least about 15 seconds, to allow for surface modification. In some embodiments, the exposure to the silicon-containing reactant and the molybdenum-containing precursor is sequential. FIG. 2B shows a structure formed after substantially non-selective deposition of molybdenum according to the methods provided herein. After exposing the substrate to the molybdenum-containing precursor, the reducing agent, and the silicon-containing reactant, a substantially conformal layer of molybdenum-containing material 107 is formed, the molybdenum-containing material 107 comprising molybdenum metal, molybdenum silicide, or a combination thereof. In some embodiments, the molybdenum-containing layer 107 comprises a molybdenum metal layer and a molybdenum silicide sublayer, the molybdenum silicide sublayer being formed at the interface between the dielectric layer 103 and the molybdenum metal layer of the substrate, and at the interface between the metal layer 105 and the molybdenum metal layer of the substrate. Processing may then continue to fill the recessed feature 101 with a molybdenum-containing layer 109. In some embodiments, the molybdenum-containing layer 109 is molybdenum metal, which may be deposited using the methods provided herein by exposing the semiconductor substrate to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant.In other embodiments, the majority of the molybdenum-containing layer 109 is molybdenum metal deposited without the addition of a silicon-containing reactant, and the silicon-free deposition involves exposing the substrate to a molybdenum-containing material and a silicon-containing reactant.

[0162] The reduced selectivity, in some embodiments, is due to direct modification of the substrate surface by silicon-containing reactants. For example, when the dielectric layer 103 is a silicon-containing dielectric, such as silicon oxide, the silicon-containing reactants can modify the dielectric to form Si-H and / or Si-OH bonds, which act as nucleation sites for the deposition of the molybdenum-containing layer, thereby increasing the deposition rate on the sidewalls and reducing the deposition selectivity on the dielectric / on the metal.

[0163] Although the examples shown relate to the reduction in selectivity achieved by silicon-assisted deposition, the methods provided are not limited by this advantage. In some embodiments, silicon-assisted deposition is used to assist the reduction process without regard to selectivity.

[0164] The process of adding a silicon-containing reactant to deposit a molybdenum-containing layer provided herein can be performed using a variety of process sequences. In some CVD-type implementations, the molybdenum-containing precursor, reducing agent, and silicon-containing reactant are simultaneously flowed into the process chamber (with at least some overlap in time during the flow of all three components) and allowed to mix in the process chamber. In other ALD-type implementations, at least two of the three components (silicon-containing reactant, molybdenum-containing precursor, and reducing agent) are not simultaneously flowed into the process chamber (with no overlap in delivery time). These implementations may include several substrate exposure steps forming a single deposition cycle, where the deposition cycle is repeated as many times as necessary to deposit a molybdenum-containing layer of a desired thickness.

[0165] In some embodiments, the process is performed such that the silicon-containing reactant and the molybdenum-containing precursor are not delivered to the process chamber at the same time. In some embodiments, the process is performed such that the silicon-containing reactant and the reducing agent are not delivered to the process chamber at the same time. In some embodiments, the process is performed such that the molybdenum-containing reactant and the reducing agent are not delivered to the process chamber at the same time. In some embodiments, the process is performed such that the silicon-containing reactant, the molybdenum-containing precursor, and the reducing agent are each delivered to the process chamber without overlapping in time.

[0166] One implementation of a deposition process is illustrated in FIG. 2A. The illustrated process is particularly useful for tuning the selectivity of deposition on a substrate, since it begins with exposing the substrate (e.g., a substrate having exposed metal and dielectric, such as shown in FIG. 1A) to a silicon-containing reactant, where the silicon-containing reactant can modify the surface of the substrate. With reference to FIG. 2A, the process begins in 201 by exposing a semiconductor substrate to a silicon-containing reactant. In some embodiments, step 201 involves delivering a silicon-containing reactant to a process chamber without simultaneously delivering a molybdenum-containing precursor to the process chamber. A reducing agent may be optionally delivered to the process chamber at this stage simultaneously with the silicon-containing reactant. The substrate is allowed to be exposed to the silicon-containing reactant for a period of time, such as at least about 10 seconds, such as at least about 15 seconds, at least about 20 seconds, or at least about 30 seconds, in some embodiments, to allow surface modification to occur. Next, in step 203, the substrate is exposed to a molybdenum-containing precursor. In the illustrated embodiment, a molybdenum-containing precursor is delivered to the process chamber while a silicon-containing reactant is not simultaneously added at this stage. A reducing agent may be optionally delivered at the same time as the molybdenum-containing precursor at step 203. The substrate is then exposed to a reducing agent at step 205 to reduce the molybdenum-containing precursor. In the depicted example, a reducing agent is delivered to the process chamber at this stage without simultaneously delivering a molybdenum-containing precursor and without simultaneously delivering a silicon-containing reactant. Completion of steps 201-205 constitutes one deposition cycle. As shown in step 209, steps 201-205 are optionally repeated in this case (e.g., at least 5 times, at least 10 times, or at least 100 times) and / or only the silicon-free steps 203-205 are repeated (e.g., at least 5 times, at least 10 times, or at least 100 times) until a molybdenum-containing layer of the desired thickness is formed.In some embodiments, after performing the first one or more cycles of steps 201-205, only the cycles of steps 203-205 are repeated, with the silicon-containing precursor exposure step 201 being inserted after a predetermined number of cycles, for example after 5 cycles each, or after 10 cycles each. In one example implementation of the process of FIG. 2A, deposition involves starting delivery of a silicon-containing reactant to the process chamber without delivering a reducing agent or a molybdenum-containing precursor after a period of flow, stopping delivery of the silicon-containing reactant, starting delivery of a molybdenum-containing precursor after stopping delivery of the silicon-containing reactant, then stopping delivery of the molybdenum-containing precursor, starting delivery of a reducing agent, and stopping delivery of the reducing agent. In a modification of this implementation, the reducing agent is allowed to flow simultaneously with the molybdenum-containing precursor and continues to flow into the process chamber after delivery of the molybdenum-containing precursor has stopped.

[0167] Another embodiment of the deposition process is illustrated by the process flow diagram shown in FIG. 2B. In this implementation, the process includes step 209 of exposing the substrate to a reducing agent and a silicon-containing reactant. In this step, the reducing agent and the silicon-containing reactant are delivered simultaneously into the process chamber in the absence of delivery of a molybdenum-containing precursor. Next, in step 211, the substrate is exposed to the molybdenum-containing precursor with or without simultaneous exposure to the reducing agent. In the depicted example, step 211 is performed without simultaneous exposure of the semiconductor substrate to the silicon-containing reactant. In other embodiments, the silicon-containing reactant may be delivered during step 211 as well. Next, in step 213, steps 209-211, which constitute one deposition cycle, are repeated as many times as necessary to form a molybdenum-containing layer of a desired thickness.

[0168] In some embodiments, the silicon-containing reactant is delivered simultaneously with the molybdenum-containing precursor. This is illustrated by the process diagram shown in FIG. 2C. The process begins in step 215 by exposing a semiconductor substrate to a molybdenum-containing precursor and a silicon-containing reactant. For example, the molybdenum-containing precursor and the silicon-containing reactant can be delivered simultaneously to a process chamber housing the substrate. Step 215 can be performed with or without the simultaneous delivery of a reducing agent. Next, in step 217, the substrate is exposed to a reducing agent. The reducing agent can be delivered to the process chamber with or without the simultaneous delivery of the silicon-containing reactant and with or without the simultaneous delivery of the molybdenum-containing precursor. Next, in step 219, steps 215-217 are repeated as many times as necessary to form a molybdenum-containing film of a desired thickness.

[0169] It is noted that all provided processes may optionally include a purging step to remove undesired reactants and / or by-products from the processing chamber after any of the exposure steps. In some embodiments, the purging step is performed by flowing an inert gas (e.g., argon, helium, nitrogen, etc.). In other embodiments, no dedicated purging step with an inert gas is used at all, and the purging step is performed by flowing a reducing agent (e.g., hydrogen). It is noted that in some implementations, it is preferred to expose the substrate containing the exposed dielectric layer and metal layer to a silicon-containing reactant before exposure to a molybdenum-containing precursor to modify the surface of the substrate and achieve the desired susceptibility loss, although the order of the exposure steps can be switched as desired.

[0170] In some embodiments, exposure to a silicon-containing reactant is used after performing one or more silicon-free deposition cycles. For example, a molybdenum-containing layer may be deposited as shown in the process flow diagram of FIG. 2D. In step 221, the semiconductor substrate is exposed to a molybdenum-containing precursor, and in step 223, the semiconductor substrate is exposed to a reducing agent. Both of these steps are performed in the absence of a silicon-containing reactant, constituting a silicon-free molybdenum metal deposition cycle. In step 225, steps 221-223 are repeated to perform multiple deposition cycles, inserting exposure of the substrate to a silicon-containing reactant after a predetermined number of silicon-free molybdenum metal deposition cycles. For example, the substrate may be exposed to a silicon-containing reactant as a single exposure after every 5, 10, 20, or 50 silicon-free deposition cycles. Alternatively, one or more silicon-assisted deposition cycles, such as any of those illustrated in FIG. 2A-FIG. 2C, may be inserted after a predetermined number of silicon-free cycles.

[0171] In some embodiments, the molybdenum-containing layer deposition involves depositing a molybdenum-containing precursor (e.g., molybdenum silicide and / or molybdenum metal) using silicon-assisted deposition as described herein, and then depositing molybdenum metal using silicon-free deposition. For example, 2-2,000 silicon-assisted deposition cycles may be followed by 2-2,000 silicon-free deposition cycles. In some embodiments, this process flow is used to deposit a molybdenum-containing layer including a molybdenum silicide layer at an interface with a silicon-containing dielectric, and then form a molybdenum metal layer on the molybdenum silicide layer. The molybdenum silicide layer of the molybdenum-containing layer may be deposited using silicon-assisted deposition, and the molybdenum metal layer of the molybdenum-containing layer may be deposited using silicon-free deposition.

[0172] In some embodiments, different molybdenum-containing precursors are used for silicon-assisted deposition and silicon-free deposition. In one implementation, molybdenum silicide and / or molybdenum metal are first deposited using molybdenum pentachloride (MoCl5) as a molybdenum-containing precursor in silicon-assisted deposition according to any of the methods provided in Figures 2A-2D. This is followed by depositing molybdenum metal in silicon-free deposition using a different molybdenum-containing precursor (e.g., MoO2Cl2). This process flow is illustrated in the process flow diagram of Figure 3. In step 301, a substrate is exposed to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant to deposit a molybdenum-containing layer. For example, 2 to 2,000 cycles of silicon-assisted deposition may be performed. The process then continues in step 303 with exposing the substrate to a different molybdenum-containing precursor and a reducing agent in the absence of the silicon-containing reactant to deposit a layer of molybdenum metal in silicon-free deposition. For example, between 2 and 2,000 silicon-free deposition cycles may be performed in step 303.

[0173] Silicon-Containing Reactants Silicon-containing reactants may serve various purposes and have different structures. In some embodiments, silicon-containing reactants may assist in the reduction of molybdenum-containing precursors, thereby reducing Mo(V) in the molybdenum-containing precursor to Mo(IV) or Mo(III). For example, silicon-containing reactants can be used to reduce MoCl5 molybdenum-containing precursors to MoCl4 or MoCl3 before the MoCl5 molybdenum-containing precursor is fully reduced to molybdenum metal by the reducing agent. Silicon-containing reactants with Si-H and / or Si-Si bonds are particularly useful as reduction-assisting reactants. In some embodiments, silicon-containing reactants act as impurity removers of halogen ligands that need to be removed when the molybdenum-containing precursor contains molybdenum halogen bonds. Since halogen ligands are typically removed as hydrogen halides (HCl, HBr, etc.), when halogens are used as reducing agents, the additional capture of halogens by silicon-containing reactants assists in halogen ligand removal. Silicon-containing precursors with Si-H and / or Si-Si bonds are particularly useful for this purpose. Finally, silicon-containing reactants can be used to modify the surface of the substrate to adjust deposition selectivity. For example, silicon-containing reactants can modify the surface of dielectrics (e.g., silicon-containing dielectrics) to facilitate subsequent nucleation of molybdenum on these surfaces. This can involve the formation of Si-H and Si-OH bonds on the dielectric surface. Silicon-containing reactants that contain Si-H and Si-Si bonds can be used for surface modification purposes. In some embodiments, the silicon-containing reactant has the structure of formula (I): S x R y (I)

[0174] wherein x is 1 to 4, y is 4 to 18, and each R is independently selected from the group consisting of H, halogen, and alkyl. In some embodiments, each R is independently selected from the group consisting of H and halogen (e.g., F, Cl, Br, or I), where the halogens can be the same or different.

[0175] In some embodiments, the silicon-containing reactant is a silane, such as silane (SiH4), disilane (Si2H6), etc. In some embodiments, the silicon-containing reactant is monochlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), tetrachlorosilane (SiCl4), hexachlorodisilane (Si2Cl6), pentachlorodisilane (Si2HCl5), tetrachlorodisilane (Si2H2Cl4), trichlorodisilane (Si2H3Cl3), dichlorodisilane (Si2H4Cl2), monochlorodisilane (Si2H5 Cl), monobromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (SiHBr3), tetrabromosilane (SiBr4), hexabromodisilane (Si2Br6), pentabromodisilane (Si2HBr5), tetrabromodisilane (Si2H2Br4), tribromodisilane (Si2H3Br3), dibromodisilane (Si2H4Br2), and monobromodisilane (Si2H5Br).

[0176] In some embodiments, the silicon-containing reactant comprises silane, chlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, trichlorodisilane, dichlorodisilane, chlorodisilane, disilane, or any combination thereof.

[0177] In some embodiments, the silicon-containing reactant does not contain carbon atoms, as non-carbon-containing reactants can be particularly useful for depositing high purity molybdenum metal with low carbon content. In other embodiments, carbon atoms may be present. For example, in some embodiments, the silicon-containing reactant may contain one alkyl, alkenyl, alkynyl substituent, and any combination thereof. In some embodiments, the silicon-containing reactant comprises a structure of formula (II): Si(R')4(II) wherein at least one R' comprises a carbon atom. In other embodiments, at least one R' comprises a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In yet other embodiments, at least one R' comprises a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In certain embodiments, R' does not comprise a halogen atom. In some embodiments, the silicon-containing reactant comprises a structure of formula (III): (R')3Si-[L-Si(R')2]-R' (III) In the formula, at least one R ' R comprises a carbon atom and L is a linker. In some embodiments, at least one R comprises a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In still other embodiments, at least one R comprises a carbon atom and a heteroatom (e.g., nitrogen, oxygen, and / or silicon). In certain embodiments, R does not comprise a halogen atom.

[0178] In formula (III), non-limiting linkers for L include a covalent bond, oxy (-O-), carbonyl (-C(O)-), optionally substituted carbonimidoyl (e.g., -C(NR)-), optionally substituted imino (e.g., -NR-), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, and the like.

[0179] In any of the formulas herein (e.g., in formula (I) or (II)), R' can be H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazinoazido, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, etc.), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), or isocyano (-NC), any of which may be optionally substituted.

[0180] In certain embodiments, at least one, two, three, four, or five or more R' in any of the formulas herein (e.g., in formula (II) or (III)) comprises an optionally substituted aliphatic. Non-limiting aliphatic groups include alkyl, alkenyl, or alkynyl, including linear, branched, cyclic, saturated, or unsaturated forms thereof. Such groups can be unsubstituted or substituted with one or more substituents, such as those described herein for alkyl. Other examples of aliphatic groups include methyl (Me), ethyl (Et), propyl (Pr), isopropyl (iPr), cyclopropyl (cPr), butyl (Bu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu), pentyl (Pe), tert-pentyl (tPe), allyl (All), vinyl (Vi), ethynyl, and the like.

[0181] In some embodiments, at least one, two, three, four, or more than two R' in any of the formulas herein (e.g., in formula (II) or (III)) comprises an optionally substituted heteroaliphatic. Heteroaliphatic groups can include any that contain one or more carbon atoms and one or more heteroatoms (e.g., oxygen, nitrogen, etc.).

[0182] Non-limiting heteroaliphatic groups include aliphatic carbonyls (e.g., alkanoyl or -C(O)R Ak ), aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)OR Ak ), aliphatic oxy (e.g., alkoxy or -OR Ak ), aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR Ak ), amino (e.g., -NR N1 R N2 ), aromatic carbonyl (e.g., aryloyl, or -C(O)R Ar ), aromatic carbonyloxy (e.g., aryloxy or -OC(O)R Ar ), aromatic oxy (e.g., aryloxy or -OR Ar), aromatic oxycarbonyl (e.g., aryloxycarbonyl or -C(O)OR Ar ), imidoyl (e.g., -C(NR N1 )H, -C(NR N1 )R Ak , or -C(NR N1 )R Ar ), carbamoyl (e.g., -C(O)NR N1 R N2 ), carbamoyloxy (e.g., -OC(O)NR N1 R N2 ), carboxyl (-COH), formyl (-C(O)H), heteroaromatic, heterocyclyl (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, etc.), hydrazino (e.g., -NR N1 -NR N2 R N3 ), silyl (e.g., -SiR S1 R S2 R S3 ), and silyloxy (e.g., -O-SiR S1 R S2 R S3 ), each of which can be optionally substituted with substituents described herein (e.g., as described herein for alkyl). Heteroaliphatic groups can include linear, branched, cyclic (e.g., heterocyclyl), saturated, or unsaturated forms thereof.

[0183] Heteroaliphatic groups are R Ak and / or R Ar In some embodiments, R Akis an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted cycloalkyl, an optionally substituted heteroalkyl, an optionally substituted heteroalkenyl, an optionally substituted heteroalkynyl, or an optionally substituted heterocyclyl. Ar is an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted aryl, or an optionally substituted heteroaryl.

[0184] Nitrogen-containing groups (e.g., amino, imidoyl, etc.) have an R attached to the nitrogen atom. N1 , R N2 , and / or R N3 In some embodiments, R N1 , R N2 , and R N3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy. N1 and R N2 , or R N2 and R N3 can be taken together with their respective attached nitrogen atoms to form an optionally substituted heterocyclyl. Such nitrogen-containing groups can be contained within other moieties, such as within a silyl or silyloxy group.

[0185] Silicon-containing groups (e.g., silyl) are R attached to a silicon atom. S1 , R S2 , and / or R S3 In some embodiments, R S1 , R S2 , and / or R S3Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted amino. Such silicon-containing groups may be contained within other moieties, such as within an amino group.

[0186] In some embodiments, the silyl group is an alkylsilyl group having one or more aliphatic groups attached to the silicon atom. In one example, the alkylsilyl group is -Si(R) a (R Ak ) b wherein R is independently H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Ak is an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl, where a > 0, b > 1, and a + b = 3. Yet another non-limiting alkylsilyl group is -SiHR Ak , -SiH[R Ak ]2, or -Si[R Ak ]3, wherein R Ak is any provided herein.

[0187] In some embodiments, the silyl group is an alkylsilyl group having one or more aliphatic groups attached to the silicon atom via an oxy (-O-) group. In one example, the alkoxyloxy group is -Si(R) a (OR Ak ) bwherein R is independently H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, each of which may be optionally substituted; Ak is an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl, where a > 0, b > 1, and a + b = 3. Yet another non-limiting alkylsilyl group is -SiH2[OR Ak ], -SiH[OR Ak ]2, or -Si[OR Ak ]3, wherein R Ak is any provided herein.

[0188] In some embodiments, the silyl group is an arylsilyl group having one or more aliphatic groups attached to the silicon atom. In one example, the arylsilyl group is -Si(R) a (R Ar ) b wherein R is independently H, aliphatic, heteroaliphatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, each of which may be optionally substituted; Ar is an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted alkyl, an optionally substituted aryl, or an optionally substituted heteroaryl, where a > 0, b > 1, and a + b = 3. Yet another non-limiting arylsilyl group is -SiH2R Ar , -SiH[RAr ]2, or -Si[R Ar ]3, wherein R Ar is any provided herein.

[0189] In yet another embodiment, the silyl group is an aryloxysilyl group having one or more aromatic groups attached to the silicon atom via an oxy (-O-) group. In one example, the arylsilyl group is -Si(R)a(OR Ar ) b wherein R is independently H, aliphatic, heteroaliphatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, each of which may be optionally substituted; Ar is an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted aryl, or an optionally substituted heteroaryl, where a > 0, b > 1, and a + b = 3. Yet another non-limiting aryloxysilyl group is -SiH2[OR Ar ], -SiH[OR Ar ]2, or -Si[OR Ar ]3, wherein R Ar is any provided herein.

[0190] Silyl groups may also include aminosilyl, which has one or more optionally substituted amino groups attached to the silicon atom. In one example, the aminosilyl group is -Si(R) a (NR N1 R N2 ) b wherein R is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted;N1 and R N2 is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, where R N1 and R N2 can be taken together with each attached nitrogen atom to form an optionally substituted heterocyclyl, where a > 0, b > 1, and a + b = 3. Yet another non-limiting embodiment of an aminosilyl group is -SiH2[NR N1 R N2 ], -SiH[R Ak ][NR N1 R N2 ], -SiH[R Ak ]2[NR N1 R N2 ], -SiH[NR N1 R N2 ]2, -Si[R Ak ][NR N1 R N2 ]2, or -Si[NR N1 R N2 ]3, e.g., SiH2[NH2], -SiHR Ak [NH2], -Si[R Ak ]2[NH2], -SiH2[NH(R Ak )], -SiHR Ak [NH(R Ak )], -Si[R Ak ]2[NH(R Ak )], -SiH 2 [N(R Ak )2], -SiHR Ak [N(R Ak )2], -Si[R Ak ]2[N(R Ak )2], -SiH[NH2]2, -SiR Ak [NH2]2, -SiH[NH(R Ak )]2, -SiR Ak [NH(R Ak )]2, -SiH[NH(R Ak )][NH2], -SiR Ak [NH(R Ak )][NH2], -SiH[N(RAk )2]2, -SiR Ak [N(R Ak )2]2, -SiH[N(R Ak )2][NH2], -SiR Ak [N(R Ak )][NH2]2, -Si[NH2]3, -Si[N(R Ak )2]2[NH2]2, -Si[N(R Ak )2]2[NH2], -Si[N(R Ak )2]3, -Si[NH(R Ak )][NH2]2, -Si[NH(R Ak )2]2[NH2], -Si[NH(R Ak )]3, -Si[NH(R Ak )][N(R Ak )2]2, -Si[NH(R Ak )]2[N(R Ak )2], etc., in which R Ak is an optionally substituted aliphatic, heteroaliphatic, alkyl, alkenyl, alkynyl, or alkoxy; R N1 and R N2 Each of the is any described herein.

[0191] In some embodiments, the silyl group is -Si(R') a (OR) b (NR2) c wherein each R is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and a, b, and c are > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl.

[0192] In other embodiments, any of the silyl groups herein can be attached to the parent compound through an oxy bond. In some embodiments, the silyloxy group is -O-Si(R') a (OR) b (NR 2 ) c wherein each R is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are ≧0, and a+b+c=3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkylaryl, or optionally substituted arylalkyl. Yet another non-limiting silyloxy group is -O-Si(R) a (R Ak ) b , -O-Si(R) a (OR Ak ) b , -O-Si(R) a (R Ar ) b , -O-Si(R) a (OR Ar ) b , -O-Si(R) a (NR N1 R N2 ) b wherein R is independently H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Akis an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; R Ar is an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted aryl, or an optionally substituted heteroaryl; R N1 and R N2 each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, where R N1 and R N2 can be taken together with each attached nitrogen atom to form an optionally substituted heterocyclyl, where a > 0, b > 1, and a + b = 3. Still other non-limiting silyloxy groups include alkylsilyloxy (e.g., -O-SiH Ak , -O-SiH[R Ak ]2, or -O-Si[R Ak ]3), alkoxysilyloxy (e.g., -O-SiH2[OR Ak ], -O-SiH[OR Ak ]2, or -O-Si[OR Ak ]3), arylsilyloxy (e.g., -O-SiH2R Ar , -O-SiH[R Ar ]2, or -O-Si[R Ar ]3), or aryloxysilyloxy (e.g., -O-SiH2[OR Ar ]2, -O-SiH[OR Ar ]2, or -O-Si[OR Ar In some embodiments, the silyl group includes aminosilyloxy (e.g., -O-SiH[NR N1 R N2 ], -O-SiH[R Ak ][NRN1 R N2 ], -O-Si[R Ak ]2[NR N1 R N2 ], -O-SiH[NR N1 R N2 ]2, -O-Si[R Ak ][NR N1 R N2 ]2, or -O-Si[NR N1 R N2 ]3).

[0193] Silyl and silyloxy groups may have mixed linkages of aliphatic and aromatic groups. In one example, the silyl group is -Si(R) a (R Ak ) b (R Ar ) c or -Si(R) a (OR Ak ) b (OR Ar ) c wherein R is independently H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, each of which may be optionally substituted; Ak is an optionally substituted aliphatic (e.g., optionally substituted alkyl) or an optionally substituted heteroaliphatic (e.g., optionally substituted alkoxy or optionally substituted amino), and R Ar is an optionally substituted aromatic or an optionally substituted heteroaromatic, each of a, b, and c is ≧0, and a+b+c=3.

[0194] In another embodiment, the silyl group is -Si(R) a (NR Ak 2) b , -Si(R) a (NR Ak R Ar ) b, or -Si(R) a (NR Ar 2) b wherein R is independently H, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), silyloxy (e.g., aminosilyloxy, alkoxysilyloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; N1 and R N2 each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, wherein R N1 and R N2 can be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl, where each of a and b is ≧0 and a+b=3.

[0195] In yet another embodiment, the silyloxy group is -O-Si(R) a (R Ak ) b (R Ar ) c , -O-Si(R) a (OR Ak ) b (OR Ar ) c , -O-Si(R) a (NR Ak 2) b , -O-Si(R) a (NR Ak R Ar ) b , or -O-Si(R) a (NR Ar 2) b where R, R Ak , R Ar is any of those described herein, and a, b, and c are any of those described herein.

[0196] In some embodiments, in any formula herein (e.g., in formula (I) or (II)), at least one, two, three, four, or five or more R ' includes optionally substituted aliphaticoxy, heteroaliphaticoxy, aromaticoxy, or heteroaromaticoxy. In illustrative examples, R' can be -OR, where R is an optionally substituted aliphatic (e.g., alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or cycloalkynyl), optionally substituted heteroaliphatic (e.g., heteroalkyl, heteroalkenyl, heteroalkynyl, or heterocyclyl), optionally substituted aromatic (e.g., aryl), optionally substituted heteroaromatic (e.g., heteroaryl), optionally substituted aliphatic carbonyl (e.g., alkanoyl or -C(O)R Ak , where R Ak is optionally substituted aliphatic, or any of those described herein), optionally substituted silyl (e.g., -SiR S1 R S2 R S3 or -Si(R') a (OR) b (NR2) c including any described herein), or optionally substituted amino (e.g., -NR N1 R N2 and any of those described herein.

[0197] In certain embodiments, in any formula herein (e.g., in formula (I) or (II)), at least one, two, three, four, or more than four R' comprises an optionally substituted aromatic or an optionally substituted heteroaromatic. Non-limiting aromatic and heteroaromatic groups include phenyl, benzyl, naphthyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, and the like.

[0198] In certain embodiments, in any formula herein (e.g., in formula (I) or (II)), at least one, two, three, four, five or more R ' is an optionally substituted amino (e.g., -NH, -NR N1 H, or -NR N1 R N2 In certain embodiments, R N1 and R N2 Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted silyl, or optionally substituted silyloxy. In certain embodiments, R N1 and R N2 can be taken together with their attached nitrogen atoms to form an optionally substituted heterocyclyl.

[0199] R N1 and R N2 Non-limiting examples of are H, aliphatic, alkyl (e.g., -R Ak ), alkenyl, alkynyl, aliphatic carbonyl (e.g., alkanoyl or -C(O)R Ak ), aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R Ak ), aliphatic oxy (e.g., alkoxy or -OR Ak ), aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR Ak ), amino (e.g., -NR, where each R is, for example, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), aromatic (e.g., aryl or -R Ar ), aromatic carbonyl (e.g., aryloyl or -C(O)RAr ), aromatic carbonyloxy (e.g., aryloyloxy or -OC(O)R Ar ), aromatic oxy (e.g., aryloxy or -OR Ar ), aromatic oxycarbonyl (e.g., aryloxycarbonyl or -C(O)OR Ar ), imidoyl (e.g., -C(NR)H, -C(NR)R Ak , or -C(NR)R Ar wherein each R is, for example, H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic), carbamoyl (e.g., -C(O)NR2, where each R is, for example, H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic), carbamoyloxy (e.g., -OC(O)NR2, where each R is, for example, H, an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carboxyl (-COH), formyl (-C(O)H), heteroaromatic, heterocyclyl (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, etc.), hydroxyl (-OH), silyl (e.g., -SiR S1 R S2 R S3 or -Si(R') a (OR) b (NR2) c ), and silyloxy (e.g., -O-SiR S1 R S2 R S3 or -O-Si(R') a (OR) b (NR2) c For any of these groups shown herein, R Ak , R Ar , R ', R, R S1 , R S2 , R S3 , a, b, and c can be any of those described herein.

[0200] Further non-limiting examples of amino groups include -NH2, -NHMe, -NMe2, -NHEt, -NMeEt, -NEt, -NHnPr, -NHenPr, -NnPr2, -NHiPr, -NMeiPr, -NiPr2, -NHsBu, -NMesBu, NsBu2, -NHtBu, -NMetBu, -NtBu2, -N[SiH3]2, -N[Si(Me)3]2, -N[Si(Et)3]2, -NH[SiH3], -NH[Si(Me)3], -NH[Si(Et)3], -NMe[SiH3], -NMe[Si(Me)3], NMe[Si(Et)3], -N[SiH2Me]2, -N[SiHMe2]2, -N[SiH2Et]2, N[SiHEt2]2, -N[SiHMeEt]2, -NH[SiH2Me], -NH[SiHMe2] , -NH[SiH2Et], -NH[SiHEt2]2, -NH[SiHMeEt], -NMe[SiH2Me], -NMe[SiHMe2], -NMe[SiH2Et], -NMe[SiHEt2]2, -NMe[SiHMeEt], etc.

[0201] In certain embodiments, in any of the formulas herein (e.g., in formula (II) or (III)), at least one, two, three, four, or five or more R ' is an optionally substituted hydrazine (e.g., -NH-NH or -NR N1 -NR N2 R N3 In certain embodiments, R N1 , R N2 , and R N3Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxyl, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkylaryl, optionally substituted arylalkyl, optionally substituted silyl, or optionally substituted silyloxy. In certain embodiments, R N1 and R N2 , or R N2 and R N3 can be taken together with each attached nitrogen atom to form an optionally substituted heterocyclyl. Further non-limiting hydrazino groups include -NH-NH, -NMe-NH, -NH-NHMe, -NH-NMe, -NMe-NMe, -NEt-NH, -NH-NHEt, -NH-NEt, -NMe-NEt, and the like.

[0202] In some embodiments, in any formula herein (e.g., in formula (II) or (III)), at least one, two, three, four, or five or more R' comprises an optionally substituted silyl. In one embodiment, silyl is -SiR S1 R S2 R S3 where R S1 , R S2 , and R S3Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, optionally substituted hydrazino, azido, hydroxyl, optionally substituted silyl, optionally substituted silyloxy, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted aryloxy, cyanato, isocyanato, cyano, isocyano, etc. Non-limiting silyl groups include -Si(R) a (R Ak ) b , -Si(R) a (OR Ak ) b , -Si(R) a (R Ar ) b , -Si(R) a (OR Ar ) b , -Si(R) a (NR N1 R N2 ) b , -Si(R') a (OR) b (NR2)c, etc. Still other non-limiting silyl groups include -SiH3, -SiH2Me, -SiHMe2, -SiMe3, -Si(OH)3, -SiH2(OMe), -SiH(OMe)2, -Si(OMe)3, -SiH2(NH2), -SiHMe(NH2), -SiMe2(NH2), -SiH(NH2)2, -SiMe(NH2)2, -Si(NH2)3, -SiH2(NMe2), -SiH2(NMe2), -SiHMe(NMe2), -Si(Me)2(NMe2)2, -Si(NMe2)3, -SiH2(NHMe), -SiHMe(NHMe), -SiH(NHMe)2, -SiMe(NHMe)2, -Si(NHMe)3, etc.

[0203] In other embodiments, in any of the formulas herein (e.g., in formula (II) or (III)), at least one, two, three, four, five or more R ' includes optionally substituted silyloxy. A non-limiting example of a silyloxy group is -O-Si(R) a (R Ak ) b , -O-Si(R) a (OR Ak ) b , -O-Si(R) a (R Ar ) b , -O-Si(R) a (OR Ar ) b , -O-Si(R) a (NR N1 R N2 ) b , -O-Si(R') a (OR) b (NR2) c Further non-limiting examples of silyloxy groups include any of those described herein, such as -O-SiH3, -O-SiH2Me, -O-SiHMe2, -O-SiMe3, -O-Si(OH)3, -O-SiH2(OMe), -O-SiH(OMe)2, -O-Si(OMe)3, -O-SiH2(NH2), -O-SiHMe(NH2), -O-SiMe2(NH2), -O-SiH(NH2)2, -O-SiMe(NH2)2, -O -Si(NH2)3, -O-SiH2(NMe2), -O-SiH2(NHMe), -O-SiHMe(NMe2), -O-Si(Me)2(NMe2)2, -O-SiMe(NMe2)2, - Includes O-Si(NMe2)3, -O-SiH2(NHMe), -O-SiHMe(NHMe), -O-SiH(NHMe)2, -O-SiMe(NHMe)2, -O-Si(NHMe)3, etc.

[0204] In still other embodiments, in any of the formulas herein (e.g., in formula (II) or (III)), at least one, two, three, four, or five or more R' include azido (-N3), hydroxyl (-OH), cyanato (-OCN), isocyanato (-NCO), cyano (-CN), and / or isocyano (-NC).

[0205] The organosilicon-containing precursor may be selected from the group consisting of silane, disilane, trisilane, tetrasilane, amine-substituted versions of any of the foregoing silanes, and trisilylamine.

[0206] Examples of inorganic silicon-containing reactants include, but are not limited to, silanes, polysilanes, halosilanes, and aminosilanes. Silanes contain hydrogen and / or carbon groups but do not contain halogens. Polysilanes have the formula (H3Si-(SiH2) n —SiH3), where n > 1. Examples of silanes include silane (SiH4), disilane (Si2H6), trisilane, tetrasilane, and organosilanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butylsilane, allylsilane, sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t-butyldisilane, tetraethylorthosilicate (also known as tetraethoxysilane or TEOS), and the like.

[0207] Aminosilanes contain at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes include mono-, di-, tri-, and tetra-aminosilane (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted mono-, di-, tri-, and tetra-aminosilanes, such as t-butylaminosilane, methylaminosilane, tert-butylsilane amine, bis(tertiary butylamino)silane (SiH2(NHC(CH3)3)2(BTBAS)), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2), SiHCl-(N(CH3)2), (Si(CH3)2NH), di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. Another example of an aminosilane is trisilylamine (N(SiH3)3).

[0208] Examples of silicon-containing reactants include siloxanes, alkylsilanes, or hydrocarbon-substituted silanes, or nitrogen-containing carbon-containing reactants. Examples of siloxanes include 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane (HMCTS), silsesquioxanes, disiloxanes such as pentamethyldisiloxane (PMDSO) or tetramethyldisiloxane (TMDSO), and trisiloxanes such as hexamethyltrisiloxane or heptamethyltrisiloxane. Alkylsilanes contain a central silicon atom, with one or more alkyl groups bonded to the central silicon atom as well as one or more hydrogen atoms bonded to the central silicon atom. In some embodiments, any one or more of the alkyl groups contain from 1 to 5 carbon atoms. The hydrocarbon group may be saturated or unsaturated (e.g., alkenes (e.g., vinyl), alkynes, and aromatic groups). Examples include, but are not limited to, trimethylsilane (3MS), triethylsilane, pentamethyl, disilamethane ((CH3)2Si-CH2-Si(CH3)3), and dimethylsilane (2MS). Additionally, disilane, trisilane, or other higher order silanes may be used in place of monosilane. In some embodiments, one of the silicon atoms may have a carbon-containing group or a hydrocarbon group attached thereto, and one of the silicon atoms may have a hydrogen atom attached thereto. Examples of carbon-containing reactants that contain nitrogen include methyl-substituted disilazanes and trisilazanes, such as tetramethyldisilazane and hexamethyltrisilazane.

[0209] Further examples of organosilicon-containing reactants may include siloxanes, such as cyclotetrasiloxanes, such as heptamethylcyclotetrasiloxane (HMCTS) and tetramethylcyclotetrasiloxane. Other cyclic siloxanes may also include, but are not limited to, cyclotrisiloxane and cyclopentasiloxane. Other examples of suitable precursors include linear siloxanes, such as, but not limited to, disiloxanes, such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO), hexamethyltrisiloxane, and heptamethyltrisiloxane. For undoped silicon carbide, examples of suitable precursors include monosilanes substituted with one or more alkyl, alkenes, and / or alkyne groups, such as containing 1 to 5 carbon atoms. Examples include, but are not limited to, trimethylsilane (3MS), dimethylsilane (2MS), triethylsilane (TES), and pentamethyldisilamethane. Additionally, disilane, trisilane, or other higher order silanes may be used instead of monosilane. An example of one such disilane from the alkylsilane class is hexamethyldisilane (HMDS). Another example of a disilane from the alkylsilane class may include pentamethyldisilane (PMDS). Other types of alkylsilanes may include alkylcarbosilanes that may have carbon alkyl groups bonded to silicon atoms as well as branched polymer structures with carbons bonded to silicon atoms. Examples include dimethyltrimethylsilylmethane (DTMSM) and bis-dimethylsilylethane (BDMSE). Examples of other suitable precursors include, for example, alkyldisilazanes and compounds that may include amino (-NH2) groups and alkyl groups bonded separately to one or more silicon atoms. Alkyldisilazanes include silazane and alkyl groups bonded to two silicon atoms. An example includes 1,1,3,3-tetramethyldisilazane (TMDSN).

[0210] In the Si-containing reactants described herein, different types of R 'can be attached to the silicon atom. Further Si-containing precursors are described herein.

[0211] Aminosilane The silicon-containing reactant may contain one or more optionally substituted amino groups, thereby providing, without limitation, aminosilanes. In one embodiment, the precursor is (R') 4-x Si(NR”2) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyan, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0212] In another embodiment, the precursor is (R″2N) x (R') 3-x Si-L-Si(R') 3-x (NR”2) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R" can be taken together with the nitrogen atom to which each is attached to form an optionally substituted heterocyclyl.

[0213] In certain embodiments, L is an optionally substituted imino, such as -NR-, where R is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl, such as -SiR-, where each R is independently H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic.

[0214] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., when L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0 and / or L comprises an optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy(-O-), imino, or silyl.

[0215] In certain embodiments, at least one R' or R" is not H. The precursors may have any useful combination of R' groups and amino groups (NR"2) attached to one or more silicon atoms.

[0216] In some embodiments, R' is H, an optionally substituted amino (e.g., -NR), an aliphatic oxy (e.g., alkoxy or -OR), an aliphatic carbonyl (e.g., alkanoyl or -C(O)R), an aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), an aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR), an aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0217] In other embodiments, R″ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R″ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is —SiR′, —SiR, —Si(R′) a (OR) b , -Si(R) a (OR) b , -Si(R') a (NR2) b , -Si(R) a (NR2) b , -Si(R') a (OR) b (NR2) c , -Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R ' )a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c wherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxy, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is > 0, and a + b + c = 3, or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0218] The silicon-containing reactant has at least one R attached to a silicon atom. ' In one embodiment, the precursor may include a (R')(H) group. 3-x Si(NR”2) x wherein R' and R" can be any of those described herein, where x is 1, 2, or 3. In another embodiment, the precursor has a formula of (R')(H)2Si(NR"2), where R' and R" can be any of those described herein. In one embodiment, the precursor has a formula of (R')(H)Si(NR"2), where R' and R" can be any of those described herein. In another embodiment, the precursor has a formula of (R')2(H)Si(NR"2), where R' and R" can be any of those described herein. In yet another embodiment, the precursor has a formula of (R')2Si(NR"2), where R ' and R ''may be any of those described herein. In one embodiment, the precursor has a formula of (R')3Si(NR"2), where R' and R" may be any of those described herein.

[0219] The silicon-containing reactant has at least one R attached to a silicon atom. ' In one embodiment, the precursor may lack a (H) group. 4-x Si(NR”2) x where each R" can independently be any described herein and x is 1, 2, 3, or 4. In another embodiment, the precursor has the formula Si(NR"2) x wherein each R″ can independently be any described herein. In certain embodiments, each R″ is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0220] The silicon-containing reactant can include at least one hydrogen atom attached to a silicon atom. In one embodiment, the precursor 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 certain embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which can be optionally substituted.

[0221] The silicon-containing reactant may include a heterocyclyl group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom. In a particular embodiment, the precursor is [ka] where the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as substituents for alkyl), and where n is 1, 2, 3, 4, or 5. In one embodiment, the formula has the formula R'3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom, and each R' can independently be any described herein. In certain embodiments, the precursor is [ka] wherein the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as substituents for alkyl), and each R' can independently be anything described herein, and n is 1, 2, 3, 4, or 5.

[0222] In some instances, the silicon-containing reactant may have two or more silicon atoms, where the precursor may contain a Si-Si bond. In certain embodiments, the precursor may be (R″2N) x (R') 3-x Si-Si(R') 3-x (NR”2) x where R' and R" may be any of those described herein. In one embodiment, the silicon-containing reactant has the formula (R"2N)(R')2Si-Si(R')2(NR"2), where R' and R" may be any of those described herein. In another embodiment, the silicon-containing reactant has the formula (R"2N)2(R')Si-Si(R')(NR"2), where R' and R" may be any of those described herein. In yet another embodiment, the silicon-containing reactant has the formula (R"2N)3Si-Si(R')(NR"2), where each R '' may independently be any described herein.

[0223] The silicon-containing reactant may contain different groups attached to the silicon atom. In one example, the precursor is (R″2N)x (R') 3-x It has a formula of Si-SiH3, where R' and R" can be any of those described herein.

[0224] A linker may be present between the two silicon atoms. In one example, the silicon-containing reactant is (R″2N) x (R') 3-x Si-NR-Si(R') 3-x (NR”2) x where R' and R" can be any described herein, where R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another example, the silicon-containing reactant is (R"N) x (H) 3-x Si-NR-Si(H) 3-x (NR”2) x where R′ and R″ can be any as described herein.

[0225] The silicon-containing reactant may include a combination of heteroatom-containing linkers and R' groups. In one example, the silicon-containing reactant has the formula (R')3Si-NR-Si(R')3, where R and R ' can be any of those described herein. In another example, the precursor has the formula (R')Si-L-Si(R')3, where L and R ' may be any described herein. In certain embodiments, L is oxy (-O-), optionally substituted imino (e.g., -NR-), or optionally substituted silyl (e.g., -SiR-).

[0226] The silicon-containing reactant may contain any useful combination of R' and NR" groups in combination with the two silicon atoms. In one example, the precursor is (R"N)(R')Si-L-Si(R')(NR"). xwhere L, R', and R" can be any of those described herein.

[0227] The silicon-containing reactant may include a heterocyclic group containing a silicon atom and a nitrogen atom. In one embodiment, the precursor is [ka] where R′ and R″ can be any described herein and where n is 1, 2, 3, or 4.

[0228] In another embodiment, the silicon-containing reactant is [ka] wherein R′ and R″ can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the precursor has a formula of: [ka] wherein each R″ can independently be any described herein, where n is 1, 2, 3, or 4.

[0229] In another embodiment, the silicon-containing reactant is [ka] wherein R′ and R″ can be any described herein, and wherein n is 1, 2, 3, or 4. In yet another embodiment, the silicon-containing reactant has the formula: [ka] wherein R″ can independently be any described herein and wherein n is 1, 2, 3, or 4.

[0230] In any of the silicon-containing reactants herein, two R″, together with their respective attached nitrogen atoms, can be taken to form an optionally substituted heterocyclyl.

[0231] The silicon-containing reactant can be, for example, (R Ak )Si(NH2)(NR Ak 2)2, (R Ak )Si(NR Ak 2)3, (R Ak )2Si(NHR Ak 2)2, (R Ak )(H)Si(NHR Ak )2, (R Ak )3Si(NR Ak 2), (R Ak )3Si(NHR Ak 2), H2Si(NHR Ak 2)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, R ' and R '' Each of R can independently be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In certain embodiments, R Akare methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu), etc.

[0232] Non-limiting examples of silicon-containing reactants include methylaminotrimethylsilane (SiMe3[NHMe]), dimethylaminodimethylsilane (SiMe2H[NMe2]), dimethylaminotrimethylsilane (SiMe3[NMe2]), dimethylaminodiethylsilane (SiHEt2[NMe2]), dimethylaminotriethylsilane (SiEt3[NMe2]), ethylmethylaminodimethylsilane (SiHMe2[NMeEt]), ethylmethylaminotrimethylsilane (SiMe3[NMeEt]), ethylmethylaminodiethylsilane (SiHEt2[NMeEt]), ethylmethylaminotriethylsilane (SiEt3[NMeEt]), diethylaminomethylsilane (SiH2Me[NEt2]), diethylaminoethylsilane (SiH2Et[N Et2]), ethylaminotrimethylsilane (SiMe3[NHEt]), diethylaminodimethylsilane (SiHMe2[NEt2]), diethylaminodiethylsilane (SiHEt2[NEt2]), diethylaminotrimethylsilane (SiMe3[NEt2]), diethylaminotriethylsilane (SiEt3[NEt2]), isopropylaminodimethylsilane (SiHMe2[NHiPr]), isopropylaminotrimethylsilane (SiMe3[NHiPr]), isopropylaminodiethylsilane (SiHEt2[NHiPr]), isopropylaminotriethylsilane (SiEt3[NHiPr]), diisopropylaminotrimethylsilane (SiMe3[NiPr2]), diisopropylaminosilane (SiH3[NiPr2], C6H 17NSi, or DIPAS), diisopropylaminomethylsilane (SiH2Me[NiPr2]), diisopropylaminodimethylsilane (SiHMe2[NiPr2]), diisopropylaminodiethylsilane (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]), tert-butylaminodimethylsilane (SiHMe2[NHtBu]), tert-butylaminotrimethylsilane (SiMe3[NHtBu], tert-butylaminodiethylsilane (SiHEt2[NHtBu])), tert-butylaminotriethylsilane (SiEt3[NHtBu]), dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl), N -propylisopropylaminosilane (SiH3[NiPrnPr]), N-methylcyclohexylaminosilane (SiH3[NMeCy]), N-ethylcyclohexylaminosilane (SiH3[NEtCy]), arylphenylaminosilane (SiH3[NAllPh]), N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]), arylcyclopentylaminosilane (SiH3[NAllCp]), phenylcyclohexylaminosilane (SiH3[NPhCy]), cyclohexylaminotrimethylsilane (Si Me3[NHCy], where Cy is cyclohexyl), pyrrolyltrimethylsilane (SiMe3[NHPy], where Py is pyrrolyl), pyrrolidinotrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolidinyl), piperidinotrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl), piperazinotrimethylsilane (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, CH, 22N2Si, or BDEAS), bis(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(dii 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]2 or BTBAS), bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2), bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2), bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2), bis(1-imidazoyl)dimethylsilane (SiMe2[Im]2, where Im is imidazoyl). silane (SiH[NMe2]3 or 3DMAS), tris(dimethylamino)phenylsilane (SiPh[NMe2]3), tris(dimethylamino)methylsilane (SiMe[NMe2]3), tris(dimethylamino)ethylsilane (SiEt[NMe2]3), tris(ethylmethylamino)silane (SiH[NEtMe]3), tris(diethylamino)silane (SiH[NEt2]3), tris(isopropylamino)silane (SiH[NHiPr]3, CH 25N3Si, or TIPAS), tris(dimethylamino)silylamide (Si[NMe2]3[NH2]), tetrakis(dimethylamino)silane (Si[NMe2]4), tetrakis(ethylmethylamino)silane (Si[NEtMe]4), tetrakis(diethylamino)silane (Si{NEt2}4), 1,2-diethyltetrakis(diethylamino)disilane ([Et2N]2EtSi-SiEt[NEt2]2), 1,2-dimethyltetrakis(dimethylamino)disilane disilane ([Me2N]2MeSi-SiMe[NMe2]2), 1,2-dimethyltetrakis(diethylamino)disilane ([Et2N]2MeSi-SiMe[NEt2]2), hexakis(methylamino)disilane ([MeHN]3Si-Si[NHMe]3), hexakis(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3), hexakis(dimethylamino)disilane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), etc.

[0233] Isocyanatosilane The silicon-containing reactant may contain one or more isocyanato groups, thereby providing, without limitation, an isocyanatosilane. In one embodiment, the silicon-containing reactant is (R') 4-x Si(NCO) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted.

[0234] In another embodiment, the silicon-containing reactant is (R')z Si(NCO) x (NR”2) y having the formula: x is 1, 2, 3, or 4; each of y and z is independently 0, 1, 2, or 3; x+y+z=4, each R' is independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0235] In yet another embodiment, the silicon-containing reactant is (NCO) x (R') 3-x Si-L-Si(R') 3-x (NCO) x having the formula: each x is independently 0, 1, 2, or 3; L is a linker such as a covalent bond, an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (-O-), an imino, or a 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted.

[0236] In some embodiments, R' is H, an optionally substituted amino (e.g., -NR), an aliphatic oxy (e.g., alkoxy or -OR), an aliphatic carbonyl (e.g., alkanoyl or -C(O)R), an aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), an aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR), an aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0237] In other embodiments, R″ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R″ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is —SiR′, —SiR, —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 (NR 2 ) c , -Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R')a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c where each R ' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxylyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c is > 0, and a + b + c = 3 or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0238] Silicon-containing reactants can include, for example, any of (R')Si(NCO)(NR"2)2, (R')2Si(NCO)(NR"2), (R')2Si(NCO)(N[SiR3]2), or tetraisocyanatosilane (Si[NCO]4). In some embodiments, each of R' and R" can independently be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl. Azidosilane The silicon-containing reactant may contain one or more azide groups, thereby providing, without limitation, azidosilanes. In one embodiment, the precursor is (R') 4-x Si(N3) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted. In another embodiment, the silicon-containing reactant is (R') z Si(N3) x (NR”2) y having the formula: x is 1, 2, 3, or 4; each of y and z is independently 0, 1, 2, or 3; x+y+z=4, each R' is independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0239] In yet another embodiment, the silicon-containing reactant is (N3) x (R') 3-x Si-L-Si(R') 3-x (N3) x having the formula: each x is independently 0, 1, 2, or 3; L is a linker such as a covalent bond, an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (-O-), an imino, or a 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted.

[0240] In some embodiments, R' is H, an optionally substituted amino (e.g., -NR), an aliphatic oxy (e.g., alkoxy or -OR), an aliphatic carbonyl (e.g., alkanoyl or -C(O)R), an aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), an aliphatic carbonyl (e.g., alkoxycarbonyl or -C(O)OR), a silyl (e.g., -SiR), an aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0241] In other embodiments, R″ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R″ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is —SiR′, —SiR, —Si(R′) a (OR) b , -Si(R) a (OR) b , -Si(R') a (NR2) b , -Si(R) a (NR2) b , -Si(R') a (OR) b (NR2) c , -Si(R) a (OR) b (NR2) c , -O-SiR ' 3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R ' ) a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c where each R 'is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c is > 0, and a + b + c = 3 or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0242] Silicon-containing reactants can include any of (R')3Si(N3), (R')2Si(N3)2, (R')Si(N3)3, or Si(N3)(NR"2)3. In some embodiments, each of R' and R" can independently be any described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). Non-limiting examples of precursors also include tris(dimethylamino)silyl azide ([Me2N]3SiN3), di-tert-butyl diazidosilane (tBu2Si(N3)2), ethyl silicon triazide (EtSi(N3)3), and the like.

[0243] Hydrazinosilane The silicon-containing reactant may contain one or more optionally substituted hydrazino groups, thereby providing, without limitation, hydrazinosilanes. In one embodiment, the precursor is (R') 4-x Si(NR”-NR”2) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl. In another embodiment, the precursor is (NR″2-NR”) x (R') 3-x Si-L-Si(R') 3-x (NR”-NR”2) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0244] In yet another embodiment, the precursor is (R') 4-x Si(NR”-L-NR”2) x where x is 1, 2, 3, or 4, and each L, R', and R" can be any described herein.

[0245] In certain embodiments, L is an optionally substituted imino, such as -NR-, where R is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl, such as -SiR2-, where each R is independently H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In yet other embodiments, L is -NR-NR-, where R is any described herein (e.g., R is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic).

[0246] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., when L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0 and / or L comprises an optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy(-O-), imino, or silyl.

[0247] The silicon-containing reactants may include any useful combination of R' and hydrazino groups. In one embodiment, the precursor has the formula (R')3Si(NR"-L-NR"2) or (R')3Si(NR"-NR"2), where L, R', and R" may be any of those described herein.

[0248] The silicon-containing reactant may contain multiple hydrazino groups. In one embodiment, the precursor has the formula (R')2Si(NR"-L-NR"2), (R')2Si(NR"-NR"2), or (R')2Si(NH-NHR")2, where L, R', and R" may be any of those described herein.

[0249] The silicon-containing reactant can include at least two silicon atoms. In one embodiment, the precursor has the formula (NR"2-NR")(R')2Si-Si(R')2(NR"-NR"2), where each R' and R" can be any described herein.

[0250] Non-limiting silicon-containing reactants can include bis(tert-butylhydrazino)diethylsilane (SiEt2[NH-NHtBu]2), tris(dimethylhydrazino)silane (SiH[NH-NMe2]3), and the like.

[0251] Siloxane and its derivatives The silicon-containing reactant may contain one or more aliphatic oxy groups, aromatic oxy groups, and / or oxy groups, thereby providing a siloxane or derivative thereof having one or more Si-O, O-Si-O, or Si-O-Si bonds. In one embodiment, the precursor is (R') 4-x Si(OR'") x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted. In another embodiment, the silicon-containing reactant is (R'"O) x (R') 3-x Si-L-Si(R) 3-x (OR'") x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0252] In certain embodiments, L is an optionally substituted imino, such as -NR-, where R is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl, such as -SiR-, where each R is independently H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In other embodiments, L is -O-L'-O-, where L' is an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl (e.g., -SiR-), an optionally substituted alkylene (e.g., -(CH) n , where n is 1-6), optionally substituted arylene, etc. In still other embodiments, L is oxy.

[0253] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., when L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0 and / or L comprises an optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy(-O-), imino, or silyl.

[0254] In some embodiments, R ' is H, optionally substituted amino (e.g., -NR2), aliphatic oxy (e.g., alkoxy or -OR), aliphatic carbonyl (e.g., alkanoyl or -C(O)R), aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0255] In other embodiments, R'" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R'" is an optionally substituted silyl (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 (NR 2 ) c , -Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R')a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c wherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is > 0, and a + b + c = 3, or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0256] The silicon-containing reactant can include at least one hydrogen atom attached to a silicon atom. In one embodiment, the precursor has a formula of H3Si(OR'"), H2Si(OR'")2, or HSi(OR'")3, where each R'" can independently be any described herein.

[0257] The silicon-containing reactant is R ' In one embodiment, the precursor has a formula of (R')3Si(OR'"), (R')2Si(OR'")2, or (R')Si(OR'")3, where each of R' and R'" can be independently any of those described herein. The precursor may include any combination of (R Ak )3Si(OR Ak ), (R Ak )2Si(OR Ak )2, or (R Ak )Si(OR Ak)3, wherein R Ak is optionally substituted alkyl.

[0258] In some instances, the silicon-containing reactant may contain two or more silicon atoms, where the precursor may contain a Si-Si bond. In certain embodiments, the precursor may be (R'"O) x (R') 3-x Si-Si(R') 3-x (OR'") x wherein R ' and R'" can be any described herein. In one embodiment, the precursor is (R'"O)(R')2Si-Si(R ' )2(OR′”), where R′ and R′″ can be any of those described herein.

[0259] The silicon-containing reactant may include a combination of R' groups and linkers having heteroatoms. In one example, the precursor has the formula (R')3Si-O-Si(R')3, where R ' may be any of those described herein. In another example, the precursor has a formula of (R')3Si-O-L'-O-Si(R')3, where L' and R' may be any of those described herein. In yet another example, the precursor has a formula of (R')3Si-(OSiR'2) z -R', where R' can be any described herein, where z is 1, 2, 3, 4, or 5 or more. In another example, the precursor has a formula of (R') 4-x Si[(OSiR'2) z -R'] x where R' can be any described herein, where x is 1, 2, 3, or 4, and z is 1, 2, 3, 4, or 5 or more.

[0260] Silicon-containing reactants combine with two silicon atoms to form R 'The precursor may contain any useful combination of (R'"O) groups and OR'" groups. In one example, the precursor may contain (R'"O) x (R') 3-x Si-O-Si(R') 3-x (OR'") x wherein R ' and R'" are any of those described herein. In another example, the precursor is (R'"O) x (R') 3-x Si-O-L'-O-Si(R') 3-x (OR'") x wherein L ’ , R ' and R'" can be any described herein.

[0261] Non-limiting examples of silicon-containing reactants include methoxydimethylsilane (SiHMe2[OMe]), ethoxydimethylsilane (SiHMe2[OEt]), isopropoxydimethylsilane (SiHMe2[OiPr]), t-butoxydimethylsilane (SiHMe2[OtBu]), t-pentoxydimethylsilane (SiHMe2[OtPe]), phenoxydimethylsilane (SiHMe2[OPh]), acetoxydimethylsilane (SiHMe2[OAc]), methoxydimethylsilane (SiHMe2[OMe]), dimethylsilane (Dimethylsilane) ... Oxytrimethylsilane (SiMe3[OMe]), ethoxytrimethylsilane (SiMe3[OEt]), isopropoxytrimethylsilane (SiMe3[OiPr]), t-butoxytrimethylsilane (SiMe3[OtBu]), t-pentoxytrimethylsilane (SiMe3[OtPe]), phenoxytrimethylsilane (SiMe3[OPh]), acetoxytrimethylsilane (SiMe3[OAc]), methoxytriethylsilane (SiEt3[ OMe]), ethoxytriethylsilane (SiEt3 "OEt"), isopropoxytriethylsilane (SiEt3[OiPr]), t-butoxytriethylsilane (SiEt3[OtBu]), t-pentoxytriethylsilane (SiEt3[OtPe]), phenoxytriethylsilane (SiEt3[OPh]), acetoxytriethylsilane (SiEt3 "OAc"), dimethoxysilane (SiH2[OMe]2), diethoxysilane (SiH2[O Di-tert-butoxysilane (SiH2[OtBu]2 or DTBOS), di-tert-pentoxysilane (SiH2[OtPe]2 or DTPOS), diacetoxysilane (SiH2[OAc]2), dimethoxydimethylsilane (SiMe2[OMe]2), diethoxydimethylsilane (SiMe2[OEt]2), diisopropoxydimethylsilane (SiMe2[OPr]2),Di-tert-butoxydimethylsilane (SiMe2[OtBu]2), diacetoxydimethylsilane (SiMe2[OAc]2), dimethoxydiethylsilane (SiEt2[OMe]2), diethoxydiethylsilane (SiEt2[OEt]2), diisopropoxydiethylsilane (SiEt2[OiPr]2), di-tert-butoxydiethylsilane (SiEt2[OtBu]2), diacetoxydiethylsilane (SiEt2[OAc]2), dimethoxydiphenylsilane (SiPh2[OMe]2), dimethoxydiisopropylsilane (Si [iPr]2[OMe]2), diethoxydiisopropylsilane (Si[iPr]2[OEt]2), diisopropoxydiisopropylsilane (Si[iPr]2[OiPr]2), di-tert-butoxydiisopropylsilane (Si[iPr]2[OtBu]2), diacetoxydiisopropylsilane (Si[iPr]2[OAc]2), dimethoxymethylvinylsilane (SiMeVi[OMe]2), diethoxymethylvinylsilane (SiMeVi[OEt]2), diisopropoxymethylvinylsilane (SiMeVi[OiPr]2), di-t ert-butoxymethylvinylsilane (SiMeVi[OtBu]2), diacetoxymethylvinylsilane (SiMeVi[OAc]2), triethoxysilane (SiH[OEt]3 or TES), trimethoxyethylsilane (SiMe[OMe]3), triethoxymethylsilane (SiMe[OEt]3), triethoxyphenylsilane (SiPh[OEt]3), tetramethoxysilane (Si[OMe]4), tetraethoxysilane (Si[OEt]4 or TEOS), tetra-n-propoxysilane (Si[OnPr]4), tetraisopropoxysilane (Si[OEt ... These may include tetra-n-butoxysilane (Si[OiPr]4), tetra-n-butoxysilane (Si[OnBu]4), tetra-t-butoxysilane (Si[OtBu]4), tetramethyldisiloxane (O[SiHMe2]2 or TMDO), hexamethyldisiloxane (O[SiMe3]2), hexaethyldisiloxane (O[SiEt3]2), hexapropyldisiloxane (O[SiPr3]2), hexaphenyldisiloxane (O[SiPh3]2), and hexamethyltrisiloxane (Me2SiH-O-SiMe2-O-SiHMe2). Mixed silanes containing oxygen and nitrogen

[0262] The silicon-containing reactant may include an amino group optionally substituted with one or more aliphatic or aromatic oxy groups, thereby providing a non-limiting mixed silane. In one embodiment, the precursor is (R') z Si(OR'") x (NR”2) y having the formula: each of x and y is independently 1, 2, 3, or 4; z is 0, 1, or 2; x+y+z=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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted, or optionally two R″, taken together with the nitrogen atom to which they are each attached, may form an optionally substituted heterocyclyl; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted. In another embodiment, the precursor is (R″2N) y (R'”O) x (R') z Si-L-Si(R') z (OR'") x (NR”2) y having the formula: each of x and y is 1 or greater (e.g., 1 or 2); z is 0 or 1, x+y+z=3, L is a linker such as a covalent bond, an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (-O-), an imino, or a 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally two R″, taken together with the nitrogen atom to which they are each attached, may form an optionally substituted heterocyclyl; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0263] Non-limiting examples of R', R'', and R''' are described herein, such as, for example, aminosilanes, siloxanes, or derivatives thereof.

[0264] The silicon-containing reactant may include any combination of R', NR", and OR'" groups. In one embodiment, the precursor has the formula (R')Si(OR'")2(NR"2) or (R')2Si(OR'")2(NR"2), where each of R', R", and R'" may independently be any of those described herein. In other embodiments, the precursor has the formula (R')2Si(OR'")(N[SiR3]2), where each of R' and R'" may independently be any of those described herein, and R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic.

[0265] The silicon-containing reactants may contain only amino and oxy-containing groups attached to silicon atoms. In one embodiment, the precursor has a formula of Si(OR'")3(NR"2), Si(OR'")2(NR"2)2, or Si(OR'")(NR"2)3, where each of R" and R'" may independently be any described herein.

[0266] Non-limiting examples of silicon-containing reactants include diethoxy(isopropylamino)silane (SiH[NHiPr][OEt]2), diethoxy(tert-butylamino)silane (SiH[NHtBu][OEt]2), diethoxy(tert-pentylamino)silane (SiH[NHtPe][OEt]2), di-tert-butoxy(methylamino)silane (SiH[NHMe][OtBu]2), di-tert-butoxy(ethylamino)silane (SiH[NHEt][OtBu]2), di-tert-butoxy(isopropylamino)silane (SiH[NHiPr][OEt ... di-tert-butoxy(isopropylamino)silane (SiH[NHiPr][OtBu]2), di-tert-butoxy(n-butylamino)silane (SiH[NHnBu][OtBu]2), di-tert-butoxy(sec-butylamino)silane (SiH[NHsBu][OtBu]2), di-tert-butoxy(isobutylamino)silane (SiH[NHiBu][OtBu]2), di-tert-butoxy(tert-butylamino)silane (SiH[NHtBu][OtBu]2), di-tert-pentoxy(methylamino)silane silane (SiH[NHMe][OtPe]2), di-tert-pentoxy(ethylamino)silane (SiH[NHEt][OtPe]2), di-tert-pentoxy(isopropylamino)silane (SiH[NHiPr][OtPe]2), di-tert-pentoxy(n-butylamino)silane (SiH[NHnBu][OtPe]2), di-tert-pentoxy(sec-butylamino)silane (SiH[NHsBu][OtPe]2), di-tert-pentoxy(isobutylamino)silane (SiH[NHi These may include di-tert-pentoxy(tert-butylamino)silane (SiH[NHtBu][OtPe]2), dimethoxy(phenylmethylamino)silane (SiH[NPhMe][OMe]2), diethoxy(phenylmethylamino)silane (SiH[NPhMe][OEt]2), dimethoxy(phenylmethylamino)methylsilane (SiMe[NPhMe][OMe]2), and diethoxy(phenylmethylamino)methylsilane (SiEt[NPhMe][OEt]2). Silylamine

[0267] The silicon-containing reactant may include one or more optionally substituted silyl groups attached to a nitrogen atom, thereby providing, without limitation, a silylamine. In one embodiment, the precursor is a silylamine having a structure represented by (R″). 3-y N(SiR'3) y having the formula: y is 1, 2, or 3; 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R '' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, silyl, or silyloxy, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl. In another embodiment, the silicon-containing reactant is (R'Si) y (R”) 2-y NLN(R) 2-y (SiR'3) y having the formula: each y is independently 0, 1, or 2; L is a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (—O—), imino, or silyl; each R' is independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl, where optionally, NLN taken together forms a polyvalent heterocyclyl group.

[0268] In one example, at least one y is not 0. In another embodiment, y can be 0 (e.g., when L includes a carbon atom or a heteroatom). In yet another embodiment, y is 0 and / or L includes an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (-O-), an imino (e.g., -NR- or -N(SiR3)-), or a silyl (e.g., -SiR2-), as well as combinations thereof (e.g., -SiR2-NR-, -NR-SiR2-, -SiR2-NR-SiR2-, etc.). In certain 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.

[0269] In some embodiments, R ' is H, optionally substituted amino (e.g., -NR2), aliphatic oxy (e.g., alkoxy or -OR), aliphatic carbonyl (e.g., alkanoyl or -C(O)R), aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3 or -SiR2-L-SiR3), aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2)b), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl. L can be any useful linker (eg, a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, etc.).

[0270] In other embodiments, R″ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R″ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is —SiR′, —SiR, —Si(R′) a (OR) b , -Si(R) a (OR) b , -Si(R') a (NR2) b , -Si(R) a (NR2) b , -Si(R')a (OR) b (NR2) c , -Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R') a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c And each R ' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, where each of a, b, and c is > 0, and a + b + c = 3, or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0271] The silicon-containing reactant may include at least one R″ group attached to a nitrogen atom. In one embodiment, the precursor has a formula of (R″N(SiR′3)2 or (R″2N(SiR′3), where R 'and R" can be any described herein. In another embodiment, the precursor has a formula of (R")N(SiH) or (R"N(SiH) where R" can be any described herein. In certain embodiments, R' is an optionally substituted alkyl, amino, or alkoxy, R" is an optionally substituted alkyl or amino, and optionally the two R" taken together with the nitrogen atom to which they are each attached form a heterocyclyl.

[0272] The silicon-containing reactant may include at least one hydrogen atom attached to a nitrogen atom. In one embodiment, the precursor has a formula of (H)N(SiR'3)2, where R ' may be any of those described herein. In another embodiment, the precursor is (H)N(SiR Ak 3) has the formula 2 and R Ak can be an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, or an optionally substituted alkynyl.

[0273] The silicon-containing reactant may contain three silicon atoms attached to a nitrogen atom. In one embodiment, the precursor has a formula of N(SiR'3)3, where R ' may be any of those described herein. In another embodiment, the precursor has a formula of N(SiH3)(SiR'3)2, where R' may be any of those described herein. In yet another embodiment, the precursor has a formula of N(SiH3)(SiR Ak 3) has the formula 2 and R Ak can be an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, or an optionally substituted alkynyl.

[0274] The silicon-containing reactant may include two or more nitrogen atoms in which the precursor contains an N-N bond. In one example, the precursor has the formula (R'Si)N-N(SiR') where R 'may be any of those described herein.

[0275] A linker may be present between the nitrogen atoms. In one example, the precursor has the formula (R'Si)(R"Si)(R)NLN(R")(SiR') or (R'Si)N-LN(SiR'), where R' and R" may be any described herein. In some embodiments, L is a covalent bond, an optionally substituted alkylene, an optionally substituted heteroalkylene, -O-, -SiR-, or -Si-. In certain embodiments, at least one of R" is not H. In another example, the precursor has the formula (HSi)(R")NLN(R")(SiH), where R" may be any described herein.

[0276] The linker may include a silicon atom. In one example, the precursor has the formula (R'Si)N-SiR'N(SiR'), where R ' may be any described herein. In another example, the precursor has a formula of (R'Si)(R")N-SiR'-N(R")(SiR') or (R'Si)N-SiR'-N(R"), where R' and R" may be any described herein.

[0277] The linker can include a SiH group. In one example, the precursor has the formula (R'Si)N-SiH-N(SiR') where R' can be any described herein. In another example, the precursor has the formula (R'Si)HN-SiH-NH(SiR') or (R'Si)N-SiH-N(R") where R ' and R″ can be any described herein.

[0278] There may be multiple nitrogen and silicon containing moieties within the precursor. In one embodiment, the precursor has the formula (R'Si)(R")N-SiR'-N(R")-SiR'-N(R")(SiR'), where R ' and R″ can be any described herein.

[0279] Non-limiting precursors include, for example, 1,1,3,3-tetramethyldisilazane (NH[SiHMe2]2 or TMDS), 1,1,2,3,3-pentamethyldisilazane (NMe[SiHMe2]2), 1,1,1,3,3,3-hexamethyldisilazane (NH[SiMe3]2 or HMDS), heptamethyldisilazane (NMe[SiMe3]2), 1,1,1,3,3,3-hexamethyl-2-ethyldisilazane (NEt[SiMe3]2), 1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane (NiPr[Si Me3]2), 1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane (NiPr[SiEt3]2), 1,1,3,3-tetramethyl-2-isopropyldisilazane (NiPr[SiHMe2]2), 1,1,3,3-tetraethyl-2-isopropyldisilazane (NiPr[SiHEt2]2), 1,3-diethyltetramethyldisilazane (NH[SiMe2Et]2), 1,1,3,3-tetraethyldisilazane (NH[SiHEt2]2), 1,1,3,3-tetraethyl-2-methyldisilazane (NMe[SiH Et2]2), 1,1,1,3,3,3-Hexaethyldisilazane (NH[SiEt3]2), 1,1,1,3,3,3-Hexaethyl-2-methyldisilazane (NMe[SiEt3]2), 1,1,1,2,3,3,3-Heptaethyldisilazane (NEt[SiEt3]2), 1,2,3-Trimethyldisilazane (N[SiH2Me]3), Nonmethyltrisilazane (N[SiMe3]3) Diisopropylsilylamine (NiPr2[SiH3]), Diethylsilylamine (NEt2[SiH3]), Diisopropylsilylamine (Ni These may include di-sec-butylsilylamine (NsBu2[SiH3]), di-tert-butylsilylamine (NtBu2[SiH3]), disilylmethylamine (NMe[SiH3]2), disilylethylamine (NEt[SiH3]2), disilylisopropylamine (NiPr[SiH3]2), disilyl-tert-butylamine (NtBu[SiH3]2), bis(trimethylsilyl)amine (NH[SiMe3]2), and bis(triethylsilyl)amine (NH[SiEt3]2).

[0280] Silazane and its derivatives The silicon-containing reactant may contain one or more amino, silyl, and / or imino groups, thereby providing a silane or derivative thereof having one or more Si-N, N-Si-N, Si-N-Si, N-Si-Si, or N-Si-N-Si bonds. In one embodiment, the precursor comprises a (R") 3-y N(SiR'2-L-SiR'3) y having the formula: y is 1, 2, or 3; L is a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; Each R ' are independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, silyl, or silyloxy, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0281] In another embodiment, the silicon-containing reactant is (R″) 3-y N(SiR'2-L-SiR ' 2-NR”2) y where y is 1, 2, or 3, and L, R', and R" can be any as described herein.

[0282] In yet another embodiment, the silicon-containing reactant is (R″) 3-y N(SiR'2-L-NR"2) y where y is 1, 2, or 3, and L, R', and R" can be any as described herein. In one embodiment, the silicon-containing reactant is (R') 4-x Si(NR”-L-SiR'3) x having the formula: x is 1, 2, 3, or 4; L is a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; Each R ' are independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, silyl, or silyloxy, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0283] In another embodiment, the silicon-containing reactant is (R″N)—(SiR′-L) z It has the formula -SiR'3, where z is 1, 2, or 3, and each of L, R', and R'' can be any described herein.

[0284] In some embodiments, L includes optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino (e.g., -NR- or -N(SiR)-), or silyl (e.g., -SiR-), as well as combinations thereof (e.g., -SiR-NR-, -NR-SiR-, -SiR-NR-SiR-, etc.). In certain 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.

[0285] In some embodiments, R ' is H, optionally substituted amino (e.g., -NR2), aliphatic oxy (e.g., alkoxy or -OR), aliphatic carbonyl (e.g., alkanoyl or -C(O)R), aliphatic carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3 or -SiR2-L-SiR3), aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl. L can be any useful linker (eg, a covalent bond, optionally substituted alkylene, optionally substituted heteroalkylene, oxy, imino, silyl, etc.).

[0286] In other embodiments, R″ is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R″ is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R″ is —SiR′, —SiR, —Si(R′) a (OR) b , -Si(R) a (OR) b , -Si(R') a (NR2) b , -Si(R) a (NR2) b , -Si(R') a (OR) b (NR2) c , -Si(R) a (OR) b(NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b , -O-Si(R) a (OR) b , -O-Si(R ' ) a (NR2) b , -O-Si(R) a (NR2) b , -O-Si(R') a (OR) b (NR2) c , or -O-Si(R) a (OR) b (NR2) c where each R ' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c is > 0, and a + b + c = 3 or (if c is absent) a + b = 3. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0287] The silicon-containing reactant may include one or more disilanyl groups and an amino group. In one embodiment, the precursor has a formula of R″2N—SiR′2—SiR′3, where L, R′, and R″ may be any of those described herein. In another embodiment, the precursor has a formula of R″2N—SiH2—SiH3, where R″ is any of those described herein. In another embodiment, the precursor has a formula of (R″ 3-y N-(SiR'2-SiR'3) y where y, R', and R" can be any of those described herein. In yet another embodiment, the precursor has a formula of (R") 3-yN-(SiH2-SiH3) y where y and R″ can be any of those described herein.

[0288] The silicon-containing reactant can include a divalent disilanyl group. In one embodiment, the precursor has the formula R″2N—SiR′2-SiR′2-L—NR″2, where L, R′, and R″ can be any of those described herein. In another embodiment, the precursor has the formula R″2N—SiR′2-SiR′2-NR″2, where R′ and R″ can be any of those described herein.

[0289] A linker L may be present between the two silyl groups. In one embodiment, the precursor has a formula of R″2N-SiR′2-L-SiR′3 or R″N-(SiR′2-L-SiR′3)2, where L, R′, and R″ may be any of those described herein. In another embodiment, the precursor has a formula of R″2N-SiR′2-L-SiR′2-NR″2, where L, R′, and R″ may be any of those described herein. In yet another embodiment, the precursor has a formula of (R″ 3-y N-(SiR'2-L-SiH3) y where L, R', and R" can be any of those described herein.

[0290] The silicon-containing reactant may include -SiH as the silyl group. In one embodiment, the precursor has the formula R"N-SiH-SiH, where R '' may be any described herein. In another embodiment, the precursor has a formula of (R″N—(SiH2-L-SiH3)2 or (R″2N—(SiH2-L-SiH3), where L and R″ may be any described herein.

[0291] The silicon-containing reactant may be, for example, -NR"-SiR ' 3, where R 'and R" can be any described herein. In one embodiment, the precursor is (R') 4-x Si(NR”-SiR’3) x or (R') 4-x Si(NH-SiR'3) x where x is 1, 2, 3, or 4, and where R′ and R″ can be any of those described herein. In another embodiment, the precursor has a formula of HSi(NR″—SiR′) where R ' and R″ can be any described herein.

[0292] The silicon-containing reactant may include a bis-trisilylamino group, such as, for example, -N(SiR'3)2, where R' may be any of those described herein. In one embodiment, the precursor has the formula R"2N-SiR'2-N(SiR'3)2, where R' and R" may be any of those described herein. In another embodiment, the precursor has the formula R"2N-SiH2-N(SiH3)2, where R' may be any of those described herein. In yet another embodiment, the precursor has the formula (R'3Si)2N-[SiR'2-N(SiR'3)] z (SiR'3), where z is 0, 1, 2, or 3, and where R' and R'' can be any of those described herein.

[0293] The silicon-containing reactant may include a linker, L, disposed between the silicon atom and the nitrogen atom. In one embodiment, the precursor has a formula of R″2N—SiR′2-L—NR″2, where L, R′, and R″ may be any of those described herein.

[0294] The silicon-containing reactant may include a linker, L, disposed between two nitrogen atoms. In one embodiment, the precursor has the formula R'3Si-SiR'2-NR"-L-NR"-SiR'2-SiR'3, where L, R', and R" may be any of those described herein.

[0295] The linker may include a silylimino group, such as, for example, -N(SiR'3)-, where R' may be any of those described herein. In one embodiment, the precursor is R"2N-[SiR'2-N(SiR'3)] z -SiR'3 or R"2N-[N(SiR'3)] z It has the formula -SiR'3, where z is 1, 2, 3, or 4 or more, where R' and R'' can be any of those described herein.

[0296] The linker may contain both silyl and imino groups. In one embodiment, the precursor is R″2N—[SiR′2-NR″] z -SiR'3, where z is 1, 2, 3, or 4 or more, and where R ' and R″ can be any described herein.

[0297] Non-limiting examples of silicon-containing reactants include diisopropylaminodisilane ([iPrN]-SiH-SiH), di-sec-butylaminodisilane ([sBuN]-SiH-SiH), methylcyclohexylaminodisilane ([MeCyN]-SiH-SiH), methylphenylaminodisilane ([MePhN]-SiH-SiH), piperidinodisilane, 3,5-dimethylpiperidinodisilane, diisopropylaminotrisilylamine ([iPrN]-SiH-N[SiH]), diethylaminotrisilylamine ([EtN]-SiH-N[SiH]), isopropylaminotrisilylamine ([iPrHN]-SiH-N[SiH]), and the like.

[0298] Mixed amines containing silicon and oxygen The silicon-containing reactant may contain one or more amino groups substituted with silyl groups, thereby providing non-limiting mixed amines. In one embodiment, the precursor is (R″) 3-y N[Si(OR'”) x R' 3-x ] yhaving the formula: each of x and y is independently 1, 2, or 3; Each R ' are independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally two R″, taken together with the nitrogen atom to which they are each attached, may form an optionally substituted heterocyclyl; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0299] Non-limiting examples of R', R'', and R''' are described herein, such as aminosilanes, siloxanes, silylamines, or derivatives thereof.

[0300] The silicon-containing reactant may contain any combination of R″ groups and silicon-containing groups. In one embodiment, the precursor is (R″ 3-y N[Si(OR Ak ) x R Ak 3-x ] y or (R Ak ) 3-y N[Si(OR Ak ) x R Ak 3-x ] y wherein R″, x, and y are as described herein;Ak is H, optionally substituted aliphatic or optionally substituted heteroaliphatic. In certain embodiments, R Ak is H, optionally substituted alkyl, optionally substituted alkylene, or optionally substituted alkynyl. In other embodiments, the precursor is (R″) 3-y N[Si(OR Ak ) x H 3-x ] y or (R”) 3-y N[Si(OR Ak )H(R Ak )] y where R″, R Ak , x, and y are as described herein.

[0301] The silicon-containing reactant may contain two silicon-containing groups. In one embodiment, the precursor is (R″N[Si(OR Ak ) x R Ak 3-x ]2 or (R Ak )N[Si(OR Ak ) x R Ak 3-x ]2, wherein R '' , R Ak , x, and y are any described herein. In certain embodiments, x is 1 or 2.

[0302] The silicon-containing reactant may include a hydrogen atom attached to a nitrogen atom. In one embodiment, the precursor is (H) 3-y N[Si(OR Ak ) x R Ak 3-x ] y Or (H) 3-y N[Si(OR Ak ) x H 3-x ] y Or (H) 3-y N[Si(OR Ak )H(R Ak )] ywherein R Ak , x, and y are any described herein. In certain embodiments, x is 1 or 2.

[0303] Non-limiting silicon-containing reactants include, for example, bis(dimethoxysilyl)amine (NH[Si(OMe)H]), bis(diethoxysilyl)amine (NH[Si(OEt)H]), N-isopropyl bis(diethoxysilyl)amine (NiPr[Si(OEt)H]), bis(methoxymethylsilyl)amine (NH[Si(OMe)MeH]), tris(dimethoxysilyl)amine (N[Si(OMe)H]), tris(methoxymethylsilyl)amine (N[Si(OMe)MeH]), tris(diethoxysilyl)amine (N[Si(OEt)H]), tris(trimethoxysilyl)amine (N[Si(OMe)]), and the like. Cyclic Silazane The silicon-containing reactant may include a cyclic group having one or more nitrogen atoms. In one embodiment, the precursor is [NR '' -(SiR ' 2) n ] z having the formula: z is 1, 2, 3, 4, 5, or 6 or more; n is 1, 2, or 3; Each R ' are independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, silyl, or silyloxy, any of which may be optionally substituted, or optionally, two R '' can be taken together with their attached nitrogen atoms to form an optionally substituted heterocyclyl. In one embodiment, the silicon-containing reactant is [NR″-(SiR′2) n -L-(SiR'2) n ] z having the formula: z is 1, 2, 3, 4, 5, or 6 or more; each n is independently 1, 2, or 3; L is independently a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; each 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, silyl, or silyloxy, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0304] In another embodiment, the silicon-containing reactant is [NR″-L-NR″-(SiR′2) n ] zwherein z is 1, 2, 3, 4, 5, or 6 or more, and each n is independently 1, 2, or 3, and wherein R ' and R″ can be any described herein. In yet another embodiment, the precursor is [L-(SiR'2) n ] z having the formula: z is 1, 2, 3, 4, 5, and 6 or more; each n is independently 1, 2, or 3; L is imino (e.g., -NR-), optionally substituted aliphatic, optionally substituted heteroaliphatic, or combinations thereof; ' can be any described herein. In certain embodiments, when L does not contain a heteroatom, R' contains one or more heteroatoms (e.g., nitrogen atoms).

[0305] In one embodiment, the silicon-containing reactant is [ka] and having the formula

[0306] wherein R′ and R″ can be any as described herein, and n is 1, 2, 3, or 4.

[0307] In another embodiment, the silicon-containing reactant is [ka] where R′ and R″ can be any described herein and where n is 1, 2, 3, or 4.

[0308] In yet another embodiment, the silicon-containing reactant is [ka] where R″ and R′″ can be any described herein, and where n is 1, 2, 3, or 4. In certain embodiments, each R′″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0309] In one embodiment, the silicon-containing reactant is [ka] where R″ may contain heteroatoms (e.g., nitrogen atoms such as in optionally substituted amino, azido, isocyanato, or optionally substituted hydrazino) and where n is 1, 2, 3, or 4.

[0310] In some embodiments, L includes optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (-O-), imino (e.g., -NR- or -N(SiR3)-), or silyl (e.g., -SiR2-), as well as combinations thereof (e.g., -SiR2-NR-, -NR-SiR2-, -SiR2-NR-SiR2-, etc.). In certain 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.

[0311] In other embodiments, L is an optionally substituted alkylene and at least one R' comprises an optionally substituted heteroaliphatic, an optionally substituted amino, an optionally substituted aliphaticoxy, or an optionally substituted alkoxy.

[0312] In some embodiments, each R ' is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aromatic, or optionally substituted aryl. In other embodiments, each R' is independently optionally substituted heteroaliphatic, optionally substituted amino, or optionally substituted alkoxy.

[0313] In other embodiments, each R″ is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted silyl, optionally substituted amino, optionally substituted aromatic, optionally substituted aryl, optionally substituted heteroaromatic, or optionally substituted heteroaryl.

[0314] Non-limiting silicon-containing reactants include 1,3,3-trimethylcyclodisilazane ([NH-SiMe2][NH-SiMeH]), hexamethylcyclotrisilazane ([NH-SiMe2]3), octamethylcyclotetrasilazane ([NH-SiMe2]4), and the like. Cyclic Siloxane The silicon-containing reactant may include a cyclic group having one or more oxygen atoms. In one embodiment, the precursor is [L-(SiR'2) n ] z having the formula: z is 1, 2, 3, 4, 5, or 6 or more; n is 1, 2, or 3; L is an oxygen-containing linker (e.g., oxy or heteroalkylene); 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted. In one embodiment, the precursor is [OL ' -O-(SiR ' 2) n ] z having the formula: z is 1, 2, 3, 4, 5, or 6 or more; n is 1, 2, or 3; Each L' is independently an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl (e.g., -SiR2-), an optionally substituted alkylene (e.g., -(CH2) n -, where n is 1 to 6, an optionally substituted arylene, or other linker; In the formula, R ' is any of those described herein.

[0315] In another embodiment, the silicon-containing reactant is [O—(SiR′2) n -L-(SiR'2) n ] z having the formula: z is 1, 2, 3, 4, 5, or 6 or more; each n is independently 1, 2, or 3; each L is independently a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (-O-), imino, or silyl, as well as combinations thereof; wherein R' is any as described herein.

[0316] In yet another embodiment, the silicon-containing reactant is [L-(SiR') n ] z having the formula:

[0317] z is 1, 2, 3, 4, 5, or 6 or more; each n is independently 1, 2, or 3; L is oxy (e.g., -O-), optionally substituted aliphatic, optionally substituted heteroaliphatic, or a combination thereof; ' can be any described herein. In certain embodiments, when L does not contain a heteroatom, R' contains one or more heteroatoms (e.g., oxygen atoms).

[0318] In one embodiment, the silicon-containing reactant is [ka] where R′ can independently be any described herein and where n is 1, 2, 3, or 4.

[0319] In another embodiment, the silicon-containing reactant is [ka] where R′ and R″ can be any described herein and where n is 1, 2, 3, or 4.

[0320] In yet another embodiment, the silicon-containing reactant is [ka] where R'" can independently be any described herein, and where n is 1, 2, 3, or 4. In certain embodiments, each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0321] In one embodiment, the silicon-containing reactant is [ka] wherein R ' may contain heteroatoms (e.g., oxygen atoms such as in optionally substituted aliphatic oxy, aliphatic oxycarbonyl, aliphatic carbonyl, aliphatic carbonyloxy, optionally substituted alkoxy, optionally substituted alkoxycarbonyl, optionally substituted alkanoyl, optionally substituted alkanoyloxy, etc.), where n is 1, 2, 3, or 4.

[0322] In some embodiments, each R' is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted aromatic, or optionally substituted aryl. In other embodiments, R' is independently optionally substituted heteroaliphatic, optionally substituted amino, or optionally substituted alkoxy.

[0323] Non-limiting examples of silicon-containing reactants include tetramethylcyclotetrasiloxane ([OSiHMe]4 or TMCTS), hexamethylcyclotetrasiloxane ([OSiMe2OSiHMe]2 or HMCTS), octamethylcyclotetrasiloxane ([OSiMe2]4, CH 24 O4Si4, or OMCTS), decamethylcyclopentasiloxane ([OSiMe2]5, or C 10 H 30O5Si5), 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane ([OSiMe2]2[OSiMe(NMe2)]), and 2-dimethylamino-2,4,4,6,6,8,8,-heptamethylcyclotetrasiloxane ([OSiMe2]3[OSiMe(NMe2)]).

[0324] Aminosiloxane and its derivatives The silicon-containing reactant may include a siloxane or derivative thereof having one or more amino substitutions, thereby providing a siloxane or derivative thereof having one or more Si-O, O-Si-O, or Si-O-Si bonds and one or more -NR2 substitutions. In one embodiment, the precursor is a siloxane having a moiety such as (R") 3-y N[SiR'2-(OSiR'2) z -R'] y having the formula: y is 1, 2, or 3; z is 1, 2, 3, or 4 or more; Each R ' are independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R″ is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted, or optionally, two R″, taken together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0325] In another embodiment, the silicon-containing reactant is (R″) 3-y N[(SiR'2-O)z -SiR'3] y where R′, R″, y, and z can be any of those described herein.

[0326] The silicon-containing reactant may include an optionally substituted amino group with an optionally substituted silyl group. In one embodiment, the precursor is R″N—SiR′—(OSiR′) z In another embodiment, the precursor has a formula of R″N(SiR′-O) z -SiR'3, where R', R", and z can be any of those described herein.

[0327] The silicon-containing reactant may contain two optionally substituted amino groups. In one embodiment, the precursor is R″2N—SiR′2-(OSiR′2) z It has the formula -NR"2, where R', R", and z can be any of those described herein.

[0328] In some embodiments, R' is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. '' is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In certain embodiments, z is 1, 2, or 3.

[0329] Non-limiting silicon-containing reactants may include, for example, 1-dimethylaminopentamethyldisiloxane (MeN-SiMe2-OSiMe3), 1-diethylaminopentamethyldisiloxane (EtN-SiMe2-OSiMe3), 1-ethylmethylaminopentamethyldisiloxane (EtMeN-SiMe2-OSiMe3), 1,3-bis(dimethylamino)tetramethyldisiloxane (MeN-SiMe2-OSiMe2-NMe2), 1-dimethylaminoheptamethyltrisiloxane (MeN-SiMe2-[OSiMe2]2-Me), 1,5-bis(dimethylamino)hexamethyltrisiloxane (MeN-SiMe2-[OSiMe2]2-NMe2), and the like.

[0330] Silanols including alkylsilanols or alkoxysilanols The silicon-containing reactant may contain one or more hydroxyl groups, thereby providing non-limiting silanols. In one embodiment, the precursor is (R') 4-x Si(OH) x having the formula: 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, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted. In other embodiments, the precursor is (R') z Si(OH) x (OR'") y having the formula: x is 1, 2, 3, or 4; each of y and z is independently 0, 1, 2, or 3; x+y+z=4, each R' is independently H, aliphatic, aliphatic carbonyl, aliphatic carbonyloxy, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic carbonyloxy, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic carbonyloxy, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or silyloxy, any of which may be optionally substituted.

[0331] The silicon-containing reactant may have one hydroxyl group. In one embodiment, the precursor has the formula (R')3Si(OH), where R ' may be any described herein. In another embodiment, the precursor has a formula of Si(OH)(OR'")3, where each R'" may be any described herein. In certain embodiments, R'" is an optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu), where the optionally substituted alkyl is linear, branched, substituted, or unsubstituted.

[0332] Non-limiting silicon-containing reactants include, for example, tri(t-butoxy)silanol (SiOH[OtBu]3), tri(t-pentoxy)silanol (SiOH[OtPe]3), and the like. Carbonyloxysilane

[0333] The silicon-containing reactant may contain one or more optionally substituted aliphatic carbonyloxy groups, thereby providing, without limitation, carbonyloxysilanes. In one embodiment, the precursor is (R') 4-x Si(OC(O)-R'") xhaving the formula: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic carbonyl, aliphatic oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, or aminooxy, any of which may be optionally substituted. In another embodiment, the silicon-containing reactant is (R""-C(O)O). x (R') 3-x Si-L-Si(R ' ) 3-x (OC(O)-R””) x having the formula: 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 oxy, aliphatic oxycarbonyl, heteroaliphatic, heteroaliphatic carbonyl, heteroaliphatic oxy, heteroaliphatic oxycarbonyl, aromatic, aromatic carbonyl, aromatic oxy, aromatic oxycarbonyl, heteroaromatic, heteroaromatic oxy, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; Each R"" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, or aminooxy, any of which may be optionally substituted.

[0334] In some embodiments, R' is H, an optionally substituted amino (e.g., -NR), an aliphatic oxy (e.g., alkoxy or -OR), an aliphatic carbonyl (e.g., alkanoyl or -C(O)R), an aliphatic oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), a silyl (e.g., -SiR), an aliphatic oxysilyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic oxysilyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic (e.g., aryl), aromaticoxy (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, taken together with the nitrogen atom to which each is attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0335] In some embodiments, R"" is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted amino, or optionally substituted aminooxy.

[0336] Non-limiting silicon-containing reactants include reactants having the formula (R')2Si(OC(O)-R"")2, where R' and R"" can be any of those described herein. Molybdenum-Containing Precursors

[0337] In general, the molybdenum-containing precursor may contain molybdenum in a wide range of oxidation states, ranging from 0 to +6. In some embodiments, molybdenum compounds with molybdenum in the lower oxidation states +3, +4, and +5 are preferred. The provided methods are particularly useful for depositing molybdenum-containing materials from halogen-containing molybdenum-containing compounds, since the silicon-containing reactant assists in halogen scavenging, although halogen-free molybdenum-containing precursors may be used as well. Suitable molybdenum-containing precursors include molybdenum halides and oxyhalides, such as fluorides, sulfides, bromides, oxyfluorides, oxychlorides, oxybromides, etc., in which the molybdenum may be in any of the oxidation states from +2 to +6. Examples of suitable halogen-free molybdenum-containing precursors include halogen-free organometallic molybdenum-containing precursors, such as bis(ethylbenzene)molybdenum.

[0338] To maintain adequate volatility, in many of the embodiments discussed herein, precursors are selected to have molecular weights less than about 450 g / mole, such as less than about 400 g / mole.

[0339] In some embodiments, the molybdenum-containing precursor has the formula MoX n Y m where X is a chalcogen (e.g., oxygen or sulfur), Y is a halogen (e.g., fluorine, chlorine, bromine, or iodine), n is 0, 1, or 2, and m is 2, 3, 4, 5, or 6. Examples of halogen-containing molybdenum-containing precursors include, but are not limited to, MoCl5, Mo2Cl 10 , MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6.

[0340] In some embodiments, the molybdenum-containing precursor comprises a carbonyl ligand. An example of a carbonyl-containing precursor is Mo(CO). Halide-Containing Heteroleptic Molybdenum Compounds

[0341] In one embodiment, the halide-containing heteroleptic molybdenum compound is used as a precursor for depositing a molybdenum-containing film, such as for depositing molybdenum metal. In one embodiment, the precursor is a compound that includes molybdenum, at least one halide that forms a bond with the molybdenum, and at least one organic ligand having any of the elements N, O, and S, where an atom of any of these elements forms a bond with the molybdenum. Examples of suitable organic ligands that provide nitrogen or oxygen bonds include amidinates, amidates, iminopyrrolidinates, diazadienes, β-iminoamides, α-iminoalkoxides, β-aminoalkoxides, β-diketiminates, β-ketoiminates, β-diketonates, amines, and pyrazolates. Examples of suitable organic ligands that provide sulfur bonds include thioethers, thiolates, dithiolenes, dithiolates, and α-iminothiolenes. These ligands may be substituted or unsubstituted. In some embodiments, the ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The organic ligands can be neutral or anionic (e.g., monoanion or dianion), and the molybdenum can be in various oxidation states, including +1, +2, +3, +4, +5, and +6.

[0342] Structures of representative suitable N- and / or O-containing organic ligands 1-17 are shown in FIG. 4, and examples of representative suitable S-containing organic ligands 18-26 are shown in FIG. 5, where R is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each R is independently selected from H, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, and cyclobutylethyl. In some embodiments, each R is an independently selected alkyl. In some embodiments, ligands with branched alkyl substituents, such as isopropyl and isobutyl, are preferred as such ligands provide volatile molybdenum precursors.

[0343] In some embodiments, at least one organic ligand in the precursor is an amine. Suitable amines include monodentate amines (e.g., monoalkylamines, dialkylamines), bidentate amines (such as unsubstituted ethylenediamine or N-alkyl substituted ethylenediamine), and higher dentate amines (e.g., substituted diethylenetriamine or unsubstituted diethylenetriamine). An example of a monodentate amine is amine 1 shown in FIG. 1, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments, at least one R is alkyl, and each R is independently selected from H and alkyl. In some embodiments, at least one organic ligand is an amide, such as monoanionic amide 16, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, at least one organic ligand is an imide, such as dianionic imide 17, where R is alkyl or fluoroalkyl. In general, imide-containing precursors can be used to deposit a variety of molybdenum-containing films (including molybdenum metal), but in some embodiments are more preferred for depositing molybdenum nitrides and molybdenum carbonitrides, as they form strong molybdenum nitrogen bonds and act as a nitrogen source for the resulting films. In some embodiments, at least one organic ligand in the precursor is an amidinate. An example of an amidinate is amidinate 2, shown in FIG. 4, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidinate 2 is a monovalent anionic ligand that can form two molybdenum nitrogen bonds and acts as a bidentate ligand.

[0344] In some embodiments, at least one organic ligand in the precursor is an amidate.An example of an amidate is amidate 3 shown in Figure 2, where each R is independently selected from H, alkyl, and fluoroalkyl.Amidate 3 is a monovalent anionic ligand that can form one molybdenum nitrogen bond and one molybdenum oxygen bond, and plays the role of a bidentate ligand.

[0345] In some embodiments, at least one organic ligand in the precursor is a diazadiene. Examples of diazadiene are 1,4-diazabuta-1,3-diene (DAD) 5, 6, and 7, where each R is independently selected from H, alkyl, and fluoroalkyl. An interesting property of this ligand is that it can exist in a neutral form 5, a monovalent anion radical form 6, and a divalent anion form 7. Due to the redox activity of the monovalent anion (radical) form 6, the monovalent anion (radical) form 6 can be relatively easily removed during deposition, making the complex of DAD 6 particularly useful for depositing molybdenum metal and high purity molybdenum metal. DAD ligands 5, 6, and 7 can act as bidentate ligands, each forming two molybdenum nitrogen bonds. In some embodiments, the molybdenum precursor comprises DAD ligand 5, 6, or 7 as the organic ligand, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0346] In some embodiments, the at least one organic precursor is selected from the group consisting of iminopyrrolidinates (such as iminopyrrolidinates 4, where each R is independently selected from H, alkyl, and fluoroalkyl), β-iminoamides (such as β-imidoiminoamides 8, where each R is independently selected from H, alkyl, and fluoroalkyl), α-iminoalkoxides (such as α-iminoalkoxides 9, where each R is independently selected from H, alkyl, and fluoroalkyl), β-diketiminates (such as β-diketiminates 10, where each R is independently selected from H, alkyl, and fluoroalkyl), β-ketoiminates (β-keto iminatates 11, where each R is independently selected from H, alkyl, and fluoroalkyl), β-diketonates 12, where each R is independently selected from H, alkyl, and fluoroalkyl, pyrazolates 13, where each R is independently selected from H, alkyl, and fluoroalkyl, β-aminoalkoxides 14, where each R is independently selected from H, alkyl, and fluoroalkyl, or guanidates 15, where each R is independently selected from H, alkyl, and fluoroalkyl. These are monoanionic ligands that can bind to molybdenum in a bidentate fashion.

[0347] In some embodiments, at least one organic precursor is a sulfur-containing ligand capable of forming a molybdenum-sulfur bond. In some embodiments, at least one organic ligand in the precursor is a thioether. The term "thioether" is used broadly herein to include both monodentate and polydentate (e.g., bidentate or tridentate) thioethers, as well as ligands containing both a thioether moiety and a thiolate (or other) moiety. An example of a monodentate thioether is a dialkyl sulfide, R2S, where each R is an alkyl, such as dimethyl sulfide, diethyl sulfide, diisobutyl sulfide, and the like. An example of a polydentate thiothioether ligand, also containing a thiolate moiety, is (SCH2CH2SCH2CH2S). 2-An example of a monodentate thioether is thioether 18 shown in FIG. 5, where each R is independently selected from the group consisting of alkyl and fluoroalkyl. In some embodiments, each R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. In some embodiments, at least one organic ligand is a thiolate, such as monoanionic thiolate 19, where R is an alkyl or fluoroalkyl. For example, R can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl. In some embodiments, the thiolate is a dithiolate, such as dianionic α-dithiolate 24, where each R is independently selected from H, alkyl, and fluoroalkyl, or a dianionic β-dithiolate 25, where each R is independently selected from H, alkyl, and fluoroalkyl. Dithiolates can form two molybdenum-sulfur bonds with molybdenum.

[0348] In some embodiments, at least one organic ligand in the precursor is a dithiolene. Examples of dithiolene are structures 20, 21, and 22, in which each R is independently selected from H, alkyl, and fluoroalkyl. This ligand (similar to DAD) can exist in neutral form 20, monovalent anion radical form 21, and divalent anion form 22. Due to the redox activity of monovalent anion radical form 21, it can be relatively easily removed during deposition and reduction of the molybdenum precursor, making the dithiolene 21 complex particularly useful for depositing molybdenum metal and high purity molybdenum metal. Dithiolene ligands 20, 21, and 22 can act as bidentate ligands and each can form two molybdenum sulfur bonds. In some embodiments, the molybdenum precursor comprises dithiolene ligands 20, 21, and / or 22 as organic ligands, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl.

[0349] In some embodiments, at least one organic ligand in the precursor is an α-iminothiolene, such as structure 23, where each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each R substituent at a carbon atom is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, while the R substituent at a nitrogen is independently selected from alkyl and fluoroalkyl. In some embodiments, the R substituent at a nitrogen is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl. This ligand (similar to DAD and dithiolene) has a monovalent anion radical form as shown in structure 23, is redox active, and can be easily removed during reduction processing.

[0350] In some embodiments, the precursor has the formula Mo(X) m (L) n wherein m is selected from 1-4, n is selected from 1-3, each X is a halide independently selected from F, Cl, Br, and I, and each L is an organic ligand as described above, e.g., amidinates, amidates, iminopyrrolidinates, diazadienes, β-iminoamides, α-aminoalkoxides, β-aminoalkoxides, β-diketiminates, β-diketoiminates, β-diketonates, amines, and pyrazolates, thioethers, thiolates, dithiolenes, dithiolates, and α-iminothiolenes. In some embodiments, each R in the named ligands is independently selected from H, alkyl, and fluoroalkyl.

[0351] In some embodiments, L is a bidentate ligand. Examples of suitable molybdenum-containing precursors containing the formula Mo(L)Cl4 utilizing a bidentate ligand are shown in Figure 6. These Mo(V) compounds include amidinates, molybdenum complexes 27, DAD complexes 28, β-diketiminate complexes 29, pyrazolate complexes 30, amidate complexes 31, β-iminoamide complexes 32, β-ketoiminate complexes 33, β-aminoalkoxide complexes 34, iminopyrrolidinate complexes 35, α-iminoalkoxide complexes 36, and β-diketonate complexes 37.

[0352] Heteroleptic complexes involving molybdenum halides and organic ligands as described herein can be synthesized using the reaction of a molybdenum halide starting material with a compound that comprises an organic ligand in neutral or anionic form. For example, a molybdenum(V) precursor can be prepared using MoCl5 as a starting material. A Mo(III) precursor can be prepared using MoX3(THF)3 as a starting material, where X is selected from chloride, bromide, and iodide, and THF is tetrahydrofuran. The starting material can be treated with a neutral or anionic form of the ligand (e.g., a salt such as a lithium salt or a sodium salt) to form a heteroleptic complex as described herein.

[0353] Heteroleptic molybdenum compounds containing molybdenum halide bonds and organic ligands can advantageously provide high purity molybdenum metal in the CVD-type and ALD-type deposition methods provided herein. Furthermore, the use of these compounds can be associated with reduced substrate material etching compared to conventional homoleptic molybdenum halides. These advantages are described for illustrative purposes and are not intended to limit the use of these compounds to molybdenum metal deposition or deposition on substrates susceptible to etching.

[0354] In some embodiments, when deposition is performed on fluorine-sensitive materials (e.g., silicon-containing materials), the precursors are selected to be fluorine-free, for example, to include any of Cl, Br, and I as the halide in the complex. Additionally, the use of compounds with fluoroalkyl substituents may be avoided in these embodiments.

[0355] Sulfur-containing molybdenum compounds In one embodiment, the sulfur-containing molybdenum compound is used as a molybdenum-containing precursor for depositing a molybdenum-containing film, such as for depositing molybdenum metal and molybdenum silicide. In some embodiments, the molybdenum compound comprises molybdenum and at least one sulfur-containing ligand that provides a molybdenum-sulfur bond. Due to the ease of removing sulfur impurities compared to oxygen, carbon, and nitrogen impurities, molybdenum precursors based on sulfur-containing ligands can be used to deposit molybdenum-containing films that are substantially free of impurities. In some embodiments, the molybdenum compound does not contain a molybdenum carbon bond and / or does not contain a molybdenum oxygen double bond. In some embodiments, the molybdenum compound does not contain a molybdenum nitrogen double bond. In some embodiments, in the provided molybdenum precursor, molybdenum forms bonds only with sulfur atoms.

[0356] Examples of suitable sulfur-containing ligands that provide sulfur bonds include thioethers, thiolates, dithiolenes, dithiolates, thiocarbamates, and α-iminothiolenes. The ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The ligands can be neutral or anionic (e.g., monoanion or dianion), and the molybdenum can be in various oxidation states, including 0, +1, +2, +3, +4, +5, and +6.

[0357] In some embodiments, the sulfur-containing ligand is ligand 18-25 shown in FIG. 5, where the R substituents are as previously described. An example of a suitable molybdenum precursor includes molybdenum thiolate Mo(SR)4, where R is alkyl, e.g., methyl, ethyl, propyl. In one specific example, the precursor is tetrakis(tert-butylthiolate)molybdenum(IV), i.e., Mo(SR)4, where R is t-butyl. Another example of a suitable molybdenum precursor is tetrakis(diethyldithiocarbamate)molybdenum(IV). [ka] where each R is independently selected from alkyl (e.g., ethyl, methyl, butyl) and fluoroalkyl (e.g., CF3). In one specific example, the precursor is tetrakis(diethyldithiocarbamate)molybdenum(IV).

[0358] In some embodiments, dithiolene complexes of molybdenum are provided, where the dithiolene can be in either the neutral form 20, the anion radical form 21, or the dianion form 22, where each R is independently H, alkyl, or fluoroalkyl. The dithiolene complexes are redox active and support molybdenum in a variety of oxidation states. The redox reactions of the dithiolene ligands 20, 21, and 22 are shown in Equation 1. [ka]

[0359] In one implementation, the precursor is Mo(21)3, where 21 each R is independently selected from H, alkyl, and fluoroalkyl. For example, R can be methyl, ethyl, CF3, etc. This is a homoleptic Mo(III) compound that contains exclusively molybdenum sulfur bonds.

[0360] In some embodiments, the ligand may provide a nitrogen bond in addition to the sulfur bond. An example of such a ligand is α-iminothiolene 23, a redox-active radical anion ligand that may exhibit behavior similar to that of thiolene. In some embodiments, the precursor is the Mo(III) compound Mo(23)3, where each R in compound 23 is independently selected from H, alkyl, and fluoroalkyl.

[0361] In some embodiments, the precursor is MoL n wherein n is 2-6 and L is a sulfur-containing ligand, such as any of the sulfur-containing ligands described herein. In some embodiments, each L is the same sulfur-containing ligand. In other embodiments, the precursor may include different sulfur-containing ligands L. Examples of precursors include Mo(19)2, Mo(19)3, Mo(19)4, Mo(19)5, Mo(19)6, Mo(19)2(18)2, Mo(19)3(18), Mo(19)4(18)2, Mo(21)3, Mo(20)(21)2, Mo(22)3, Mo(21)(22)2, Mo(20)(22)2, Mo(23)3, Mo(24)3, Mo(25)3. The sulfur-containing molybdenum compounds described herein can be synthesized using the reaction of a compound with an organic sulfur-containing ligand in neutral or anionic form with a molybdenum halide starting material. For example, a molybdenum(V) precursor may be prepared using MoCl5 as a starting material. Mo(III) or Mo(IV) precursors may be prepared using the corresponding halide or MoX3(L)3 or MoX4(L)2 as a starting material, where X is selected from chloride, bromide, and iodide, and L is a neutral Lewis base such as tetrahydrofuran or diethyl ether. The starting material may be treated with a neutral or negative form of a desired sulfur-containing ligand (e.g., a salt such as a lithium or sodium salt) to form a sulfur-containing complex as described herein.

[0362] In one example, Mo(IV) thiolate complexes are prepared by reacting lithium thiolate with molybdenum tetrachloride. For example, MoCl4 can be reacted with t-BuSLi in 1,2-dimethoxyethane solution to form the compound Mo(t-BuS)4.

[0363] The α-iminothiolene ligands can be prepared from the corresponding α-imino ketones by polymerization using a suitable reagent, such as Lawesson's reagent. The radical anion forms of the α-iminothiolenes can be prepared by subsequent treatment with an alkali metal, such as lithium. The resulting ligands and ligand salts can be reacted with molybdenum halides to form α-iminothiolene-containing molybdenum compounds.

[0364] Molybdenum complexes can also be prepared using compounds in which molybdenum is in the zero oxidation state, such as molybdenum hexacarbonyl. The starting material can be treated with a neutral ligand, such as a thioether (dialkylsulfide), to induce redox neutral ligand exchange. The zero-valent starting material can also be treated with a ligand precursor, such as bis(diethylthiocarbamoyl) disulfide or bis(trifluoromethyl)-1,2-dithieto, to induce oxygen addition to form the sulfur-containing complexes described herein.

[0365] The reaction may be carried out in a variety of aprotic solvents. For example, the reaction may be carried out in ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, etc., in hydrocarbon solvents such as toluene, benzene, heptane, hexane, pentane, etc., or in halocarbon solvents such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc. The reaction may be carried out over a wide temperature range depending on the boiling point of the solvent and the solubility of the product. In some embodiments, the starting materials, reaction intermediates, and desired products are sensitive to moisture and oxygen. Accordingly, the reaction process should be carried out using anhydrous, air-free conditions using a protective inert gas such as nitrogen or argon.

[0366] 1,4-Diazabutadiene (DAD)-containing precursors In another aspect, a molybdenum-containing precursor containing a DAD is provided. The DAD can bind to molybdenum in its neutral form 5, its radical anion form 6, and its divalent anion form 7. In some embodiments, the molybdenum-containing precursor can be represented by the formula Mo(DAD) m where m is 1-3 and each DAD is independently selected from the neutral DAD5, the radical anion DAD6, and the divalent anion DAD7. The oxidation states of molybdenum in these complexes can range from 0 to +6. Non-limiting examples of suitable homoleptic DAD complexes include the trisDAD Mo(III) precursor Mo(6)3, the bis-DAD Mo(IV) precursor Mo(7)2, the bis-DAD Mo(III) precursor Mo(6)(7), and the bis-DAD Mo(II) precursor Mo(6)2.

[0367] In some embodiments, homoleptic DAD complexes are prepared using a reaction between a molybdenum halide and a DAD ligand source with the required electronic configuration. For example, the trisDAD Mo(III) precursor Mo(6)3 can be synthesized by reacting MoCl3 with three equivalents of the radical anion form of the DAD ligand, which can be prepared from the DAD ligand by treatment with an alkali metal such as lithium in a solvent such as THF, as shown in Equation 2. [ka]

[0368] In some embodiments, a heteroleptic DAD-containing molybdenum compound is provided. In some implementations, the precursor comprises molybdenum, at least one DAD ligand bound to the molybdenum, and at least one second ligand, where the DAD can be a neutral DAD6, a radical anion DAD7, or a divalent anion DAD8, and the second ligand is independently selected from an anionic ligand and a neutral ligand. In some embodiments, the precursor does not contain a CO ligand as the only second ligand. In some embodiments, the precursor is Mo(DAD) m (L) n (X) p where L is a neutral Lewis base ligand, each L is independently selected from CO, amine, phosphine, thioether, nitrile, and isonitrile, and X is an anionic ligand, each X is independently selected from halide, alkyl, allyl, and cyclopentadienyl, m is 1-3, n is 0-4, and p is 0-4. Nitriles are RCN compounds, where R is an alkyl. Isonitriles are RNC compounds, where R is an alkyl. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligand containing a donor atom selected from C, N, O, B, S, Si, Al, and P.

[0369] Examples of heteroleptic DAD-containing precursors include, but are not limited to, Mo(7)2(RCN)Cl, Mo(7)2(RNC)Cl, Mo(8)(CO), Mo(6)(13)Cl, Mo(6)(18)Cl, Mo(6)2Cl, Mo(6)2(14), Mo(6)2(19), Mo(6)2(24).

[0370] Heteroleptic DAD-containing precursors can be prepared in one pot or using multiple steps by sequential salt metathesis reactions. Molybdenum halide starting materials such as Mo(V), Mo(IV), or Mo(III) halides can be treated with the anionic form of the DAD ligand or other anionic ligands. Neutral Lewis base ligands can be exchanged using thermal treatment or photoexcitation.

[0371] Heteroleptic DAD-containing precursors can also be prepared using zero-valent molybdenum starting materials, such as molybdenum hexacarbonyl, which can undergo oxidative addition with redox-active ligands, such as DAD ligands.

[0372] In some embodiments, precursors containing radical anionic DAD ligands 8 are particularly preferred for depositing molybdenum metal and high purity molybdenum metal. In the radical anionic form 7, the DAD ligand is believed to act as an electron source that electronically links to vacant molybdenum d orbitals and reduces the molybdenum ion to a zero-valent metallic state. After electron transfer from the ligand to the metal, the volatile neutral DAD ligands 6 can be purged away from the molybdenum metal growth surface. Because the DAD ligands can be removed unaffected from the growth surface, the incorporation of impurity elements such as C and N is reduced when using DA precursors compared to other metal organic precursors. Thus, molybdenum precursors containing radical anionic DAD ligands can be used to deposit high purity molybdenum metal at low temperatures.

[0373] Dimolybdenum Precursor In another aspect, precursors for depositing molybdenum-containing films are dimolybdenum compounds that contain molybdenum-molybdenum bonds (e.g., multiple molybdenum-molybdenum bonds, such as double bonds or any multiple bonds having a bond order of 2 to 5). Such precursors are particularly useful for depositing molybdenum metal and high purity molybdenum metal, since it is easier to reduce such compounds to metallic molybdenum than many mononuclear molybdenum compounds.

[0374] In some embodiments, a precursor for depositing a molybdenum-containing film is provided, the precursor being MoL n where each L is independently selected from amidate, amidinate, and guanidinate ligands, and n is 2-5, where the precursor comprises a number of molybdenum molybdenum bonds. In some embodiments, each L is independently selected from amidinate ligand 2, amidate ligand 3, and guanidinate ligand 15, where each R in the amidinate, amidate, and guanidinate is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each L is an amidinate, and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is an amidinate, and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is a guanidinate and the precursor has the formula Mo2(L)3 or Mo2(L)4. In these complexes, molybdenum has the low oxidation states +2 (in Mo2(L)3) and +3 (in Mo2(L)4), making these complexes particularly suitable for easy reduction to molybdenum metal. One representative structure of an amidate paddlewheel di-Mo(II) precursor with four-fold molybdenum molybdenum bonds is shown by Structure 38. [ka]

[0375] In some embodiments, R and R ' is independently selected from alkyl, such as methyl, ethyl, isopropyl, and t-butyl. In some embodiments, one, two, three, or four of the amidate ligands in 38 may be replaced by an amidinate ligand or a guanidinidate ligand. The dimolybdenum precursors described herein can be synthesized using molybdenum tetraacetate as the starting material by treatment with a ligand salt such as lithium amidate.

[0376] Cobalt Precursor Cobalt metal can be deposited using a variety of cobalt precursors, where cobalt can be in the +1, +2, or +3 oxidation state. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., cobalt(III) bis(acetylacetonate)), cobalt amidinate (e.g., bis(Nt-butyl-N'-ethylpropanimidamidate)cobalt(II)), cobaltocene, and cobalt-containing carbonyl precursors (e.g., cobalt tricarbonyl nitrosyl and cyclopentadiethylcobalt dicarbonyl). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine.

[0377] Ruthenium Precursors Ruthenium metal can be deposited using vaporizable ruthenium precursors such as, for example, bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienylpropylcyclopentadienylruthenium(II).

[0378] Tungsten Precursor Tungsten can be deposited using a variety of volatile precursors. In some embodiments, WHalx In some embodiments, tungsten chlorides are used. Tungsten chlorides include tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In other examples, tungsten fluorides such as tungsten hexafluoride may be used.

[0379] Reducing Agent A number of reducing agents can be used to deposit the molybdenum-containing or other metal-containing films provided herein. In some embodiments, the reducing agent is selected so that it can reduce the molybdenum-containing precursor to molybdenum metal or the other metal precursor to metal in the zero oxidation state. In some embodiments, the partial reduction of the molybdenum-containing precursor (or other metal precursor) can be performed by a silicon-containing reactant, and the reducing agent functions to reduce the partially reduced molybdenum-containing precursor to molybdenum metal (or other metal precursor to metal). For example, the silicon-containing reactant can reduce a Mo(V) precursor, such as MoCl5, to the Mo(IV) or Mo(III) state, such as MoCl4 or MoCl3. The reducing agent then further reduces these partially reduced precursors to molybdenum metal. Examples of suitable reactants for forming molybdenum metal include hydrogen (H2), ammonia (NH3), hydrazine (N2H4), amines, diborane (B2H6), silane (SiH4), disilane (Si2H6), alcohols, hydrogen sulfide (HS), thiols, and combinations thereof. In some embodiments, the reducing agent is hydrogen. It is noted that when the reducing agent is a silicon-containing compound (e.g., silane), a silicon-containing reactant can still be used for surface modification. For example, the deposition process may involve exposing the substrate to a silicon-containing reactant for a period of time (e.g., at least 10 seconds or at least 15 seconds) to modify the surface of the substrate containing the exposed metal layer and the exposed dielectric layer, followed by exposure to a silicon-containing reducing agent and a molybdenum-containing precursor. In some embodiments, the silicon-containing reactant and the silicon-containing reducing agent are different.

[0380] Device The deposition methods described herein can be carried out in a variety of apparatus. Suitable apparatus include a process chamber having one or more inlets for introducing reactants, a substrate holder in the process chamber configured to hold the substrate in place during deposition, and optionally a plasma generating mechanism configured to generate a plasma in the process gas. The apparatus may include a controller having program instructions configured to cause any of the steps of the methods described herein to be performed. The deposition methods described herein can be carried out in corresponding ALD and CVD apparatus available from Lam Research Corp., Fremont, Calif., such as Altus®, Vector®, and Striker® tools.

[0381] For example, in some embodiments, the apparatus includes a controller having program instructions including instructions for exposing a semiconductor substrate to a silicon-containing reactant, a molybdenum-containing precursor, and a reducing agent in any of the process sequences described herein at a temperature between about 100° C. and about 500° C. to deposit molybdenum metal and / or molybdenum silicide. The controller may include program instructions for effecting any of the methods described herein.

[0382] An example of a deposition apparatus suitable for depositing molybdenum-containing films using the provided methods is shown in FIG. 7. FIG. 7 illustrates generally an embodiment of a processing station 700 that may be used to deposit materials using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), both of which may be plasma-enhanced. For clarity, the processing station 700 is depicted as a stand-alone processing station having a processing chamber body 702 for maintaining a low pressure environment. However, it will be appreciated that multiple processing stations 700 may be included within a common processing tool environment. Additionally, it will be appreciated that in some embodiments, one or more hardware parameters of the processing station 700, including the hardware parameters discussed in detail below, may be programmatically adjusted by one or more system controllers.

[0383] The processing station 700 is in fluid communication with a reactant delivery system 701 for delivering process gases to a distributed showerhead 706. The reactant delivery system 701 includes a mixing vessel 704 for mixing and / or conditioning process gases for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 may control the introduction of process gases to the gas mixing vessel 704. Similarly, a showerhead inlet valve 705 may control the introduction of process gases to the showerhead 706.

[0384] Some molybdenum-containing precursors may be stored in solid or liquid form prior to vaporization and after delivery to the processing station. For example, the embodiment of FIG. 7 includes a vaporization point 703 for vaporizing solid reactants that feed into a mixing vessel 704. In some embodiments, the vaporization point 703 may be a heated vaporizer. In some embodiments, a flow of inert gas is bubbled over or through the heated solid molybdenum precursor under subatmospheric pressure to carry the precursor vapor to the processing chamber. The precursor vapor produced from such a vaporizer condenses in the downstream delivery piping. Exposing the condensed reactants to incompatible gases can generate small particles. These small particles can clog the piping, interfere with valve operation, contaminate the substrate, etc. Some approaches to address these issues involve cleaning and / or emptying the delivery piping to remove remaining reactants. However, cleaning the delivery piping increases the processing station cycle time and reduces the efficiency of the processing station. Thus, in some embodiments, the delivery piping downstream of vaporization point 703 may be heat traced. In some examples, mixing vessel 704 may also be heat traced. In one non-limiting example, the piping downstream of vaporization point 703 has an increasing temperature profile ranging from approximately 100° C. to approximately 200° C. at mixing vessel 704.

[0385] The showerhead 706 distributes process gases toward the substrate 712. In the embodiment shown in FIG. 7, the substrate 712 is shown disposed below the showerhead 706 and resting on a pedestal 708. It will be appreciated that the showerhead 706 may have any suitable shape and may have any suitable number and arrangement of ports for dispersing process gases to the substrate 712. Although not explicitly shown, in some embodiments, the showerhead 706 is a dual plenum showerhead including at least two types of conduits, where a first type of conduit is dedicated to the delivery of a molybdenum-containing precursor vapor and a second type of conduit is dedicated to the delivery of a second (other) reactant. In these embodiments, the molybdenum-containing precursor and reactants do not become mixed in the conduits prior to entering the processing chamber and do not share conduits if delivered to the chamber sequentially.

[0386] In some embodiments, a microvolume 707 is located below the showerhead 706. By performing ALD and / or CVD processes in a microvolume rather than the entire volume of the processing station, reactant exposure and clean-up times may be reduced, time to change processing conditions (e.g., pressure, temperature, etc.) may be reduced, exposure of processing station robots to processing gases may be limited, etc. Examples of microvolume sizes include, but are not limited to, volumes between 0.1 liters and 2 liters. This microvolume also impacts productivity efficiency. The deposition rate per cycle is reduced, but cycle time is also reduced at the same time. In certain cases, the impact of cycle time reduction is dramatic enough to improve the overall efficiency of the module for a given target thickness of the film.

[0387] In some embodiments, the pedestal 708 may be raised or lowered to expose the substrate 712 to the micro-volume 707 and / or to change the volume of the micro-volume 707. For example, during a substrate transfer phase, the pedestal 708 may be lowered to allow the substrate 712 to be placed on the pedestal 708. During a deposition processing phase, the pedestal 708 may be raised to position the substrate 712 within the micro-volume 707. In some embodiments, the micro-volume 707 may completely surround a portion of the pedestal 708 as well as the substrate 712 to create an area of ​​high flow impedance during the deposition processing phase.

[0388] Optionally, the pedestal 708 may be lowered and / or raised during portions of the deposition process to adjust the process pressure, reactant concentration within the micro-volume 707, etc. In one scenario where the process chamber body remains at base pressure during the deposition process, lowering the pedestal 708 may allow the micro-volume 707 to be emptied. Examples of ratios of the micro-volume to the process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It will be appreciated that in some embodiments, the height of the pedestal may be programmatically adjusted by a suitable computer controller.

[0389] While the examples of micro-volume variations described herein refer to a height-adjustable pedestal, it will be appreciated that in some embodiments, the position of the showerhead 706 relative to the pedestal 708 may be adjusted to vary the volume of the micro-volume 707. Further, it will be appreciated that the vertical position of the pedestal 708 and / or the showerhead 706 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 708 may include a rotation axis for rotating the orientation of the substrate 712. It will be appreciated that in some embodiments, one or more of these example adjustments may be programmatically adjusted by one or more suitable computer controllers.

[0390] Returning to the embodiment shown in FIG. 7, the showerhead 706 and pedestal 708 are in electrical communication with an RF power source 714 and a matching network 716 for powering the plasma. In other embodiments, a plasma generator-less apparatus is used to deposit molybdenum-containing films using the methods provided. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, radio frequency (RF) power source, RF source frequency, and plasma power pulse timing. For example, the RF power source 714 and matching network 716 may be operated at any suitable power to form a plasma having a desired radical species composition. Similarly, the RF power source 714 may provide RF power of any suitable frequency. In some embodiments, the RF power source 714 may be configured to control high frequency RF power and low frequency RF power independently of each other. Examples of low frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 700 kHz. Examples of high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be adjusted, either discretely or continuously, to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be pulsed intermittently to reduce ion bombardment with the substrate surface relative to a continuously powered plasma.

[0391] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, the plasma power may be monitored by one or more voltage and current sensors (e.g., VI probes). In another scenario, the plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements by such in-situ monitors. For example, an OES sensor may be used in a feedback loop to provide programmatic plasma power control. It will be appreciated that in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0392] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting plasma conditions for a plasma processing step may be included in a corresponding plasma activation recipe step of a deposition processing recipe. In some cases, the process recipe steps are sequenced, so that all instructions for a deposition processing step are executed simultaneously with that processing step. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe step preceding a plasma processing step. For example, a first recipe step may include instructions for setting flow rates of an inert gas and / or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe step. A second recipe step that follows may include instructions for enabling the plasma generator and time delay instructions for the second recipe step. A third recipe step may include instructions for disabling the plasma generator and time delay instructions for the third recipe step. It will be appreciated that these recipe steps may be further subdivided and / or repeated in any suitable manner within the scope of the present disclosure.

[0393] In some embodiments, the pedestal 708 may be temperature controlled via a heater 710. Additionally, in some embodiments, pressure control for the deposition processing station 700 may be provided by a butterfly valve 718. As shown in the embodiment of FIG. 7, the butterfly valve 718 stops the flow of vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the processing station 700 may also be adjusted by varying the flow rate of one or more gases introduced to the processing station 700.

[0394] FIG. 8 shows a schematic diagram of an embodiment of a multi-station processing tool 800 with an inward load lock 802 and an outward load lock 804, either or both of which may be equipped with a remote plasma source. Such a tool may be used to process substrates using the methods provided herein. A robot 806 is configured to move wafers into the inward load lock 802 from a cassette loaded through a pod 808 via an atmospheric port 810 at atmospheric pressure. The wafer is placed on a pedestal 812 in the inward load lock 802 by the robot 806, the atmospheric port 810 is closed, and the load lock is pumped down. If the inward load lock 802 is equipped with a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock before being introduced into the processing chamber 814. Additionally, the wafer may also be heated in the inward load lock 802 as well, for example to remove moisture and desired gases. A chamber transfer port 816 to the processing chamber 814 then opens and another robot (not shown) places the wafer on a pedestal in the first station shown in the reactor for processing within the reactor. While the embodiment depicted in Figure 8 includes a load lock, it will be appreciated that in some embodiments direct input of the wafer into the processing stations may be provided.

[0395] The depicted processing chamber 814 includes four processing stations, numbered 1-4 in the embodiment shown in FIG. 8. Each station has a heated pedestal (shown at 818 for station 1) and a gas line inlet. It will be appreciated that in some embodiments, each processing station may have a different or multiple purpose. Although the depicted processing station 814 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments, a processing chamber may have three or fewer stations.

[0396] FIG. 8 also illustrates an embodiment of a wafer handling system 890 for transferring wafers inside the processing chamber 814. In some embodiments, the wafer handling system 890 may transfer wafers between various processing stations and / or between processing stations and load locks. It will be appreciated that any suitable substrate handling system may be used. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 8 also illustrates an embodiment of a system controller 850 used to control the processing conditions and hardware states of the processing tool 800. The system controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processor 852 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0397] In some embodiments, the system controller 850 controls all of the activity of the processing tool 800. The system controller 850 executes system control software 858, which is stored in the mass storage device 854, loaded into the memory device 856, and executed by the processor 82. The system control software 858 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequency, substrate, pedestal, chuck, and / or susceptor position, and other parameters of a particular process performed by the processing tool 800. The system control software 858 may be configured in any suitable manner. For example, subroutines or control objects of various processing tool components may be written to control the operation of the processing tool components necessary to perform the various processing tool processes in accordance with the disclosed methods. The system control software 858 may be coded in any suitable computer readable programming language.

[0398] In some embodiments, system control software 858 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of an ALD process may include one or more instructions for execution by system controller 850. Instructions for setting process conditions for an ALD process step may be included in the corresponding ALD recipe step. In some embodiments, the ALD recipe steps are sequenced sequentially, such that all instructions for an ALD process step are executed contemporaneously with that process step.

[0399] In some embodiments, other computer software and / or programs stored on the mass storage device 854 and / or memory device 856 associated with the system controller 850 may be used. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0400] The substrate positioning program may include program code for controlling processing tool components used to load the substrate onto the pedestal 818 and control the spacing between the substrate and other parts of the processing tool 800.

[0401] The process gas control program may include code for controlling the composition and flow rate of gases, and optionally code for flowing gases into one or more process stations prior to deposition to stabilize the pressure in the process station. The process gas control program may include code for controlling the composition and flow rate of gases within any of the disclosed ranges. The pressure control program may include code for controlling the pressure in the process station by, for example, adjusting a throttle valve in the exhaust system of the process station, the flow of gas into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any of the disclosed pressure ranges.

[0402] The heater control program may include code for controlling current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions for maintaining the temperature of the substrate within any of the disclosed pressure ranges.

[0403] The plasma control program may include code for setting the RF power levels and RF frequencies applied to the processing electrodes in one or more processing stations, for example using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0404] In some embodiments, there may be a user interface associated with the system controller 850. The user interface may include a display screen, a graphical software representation of the equipment and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0405] In some embodiments, the parameters adjusted by the system controller 850 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (RF power levels, RF frequency, RF exposure time, etc.), etc. These parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

[0406] Signals for monitoring the process may be provided from various process tool sensors via analog and / or digital input connections of the system controller 850. Signals for controlling the process may be output to analog and digital output connections of the process tool 800. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data obtained from these sensors to maintain process conditions.

[0407] Any suitable chamber may be used to implement the disclosed embodiments. Examples of deposition equipment include, but are not limited to, equipment from the Altus® line of products available from Lam Research Corp., Fremont, Calif., or various other commercially available processing systems. Two or more of the stations may perform the same function. Similarly, two or more of the stations may perform different functions. Each station can be designed / configured to perform a particular function / method as desired.

[0408] FIG. 9 is a block diagram of a processing system suitable for performing thin film deposition processing, according to certain embodiments. System 900 includes a transfer module 903. The transfer module 903 provides a clean, pressurized environment that minimizes the risk of contaminating the substrate being processed when moving the substrate between various reactor modules. Mounted on top of the transfer module 903 are two multi-station reactors 909 and 910, each capable of performing atomic layer deposition (ALD) and / or chemical vapor deposition (CVD) according to certain embodiments. The reactors 909 and 910 may include multiple stations 911, 913, 915, and 917 that may perform operations sequentially or non-sequentially according to disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets or showerheads, or a distribution plate.

[0409] Also mounted on the transfer module 903 may be one or more single or multi-station modules 907 capable of performing plasma pre-cleaning or (non-plasma) chemical pre-cleaning or any other process described with respect to the disclosed methods. The module 907 may be used in some cases for various handling to prepare the substrate for, for example, deposition processing. The module 907 may also be designed / configured to perform various other processes, such as etching or polishing. The system 900 also includes one or more wafer source modules 901 that store wafers before or after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 919 may initially transfer the wafer from the source module 901 to the load lock 921. A wafer transfer device (typically a robot arm unit) in the transfer module 903 moves the wafer from the load lock 921 to the modules mounted on the transfer module 903 and between the modules mounted on the transfer module 603.

[0410] In various embodiments, a system controller 929 is used to control the process conditions during deposition. The controller 929 typically includes one or more memory devices and one or more processors. The processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0411] The controller 929 may control all of the deposition apparatus activities. The system controller 929 executes system control software that includes sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. In some embodiments, other computer programs stored on memory devices associated with the controller 929 may be used.

[0412] Typically, there is a user interface associated with the controller 929. The user interface may include a display screen, a graphical software representation of the equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0413] The system control logic may be configured in any suitable manner. In general, logic may be designed or configured in hardware and / or software. Instructions for controlling the drive circuitry may be hard-coded or provided as software. Instructions may be provided by "programming." Such programming is understood to include any form of logic, including logic hard-coded into digital signal processors, application specific integrated circuits, and other elements that implement specific algorithms as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. The system control software may be coded in any suitable computer readable programming language.

[0414] Computer code for controlling silicon-containing reagent flow, reducing agent flow, and metal-containing precursor pulses, as well as other operations in the process sequence, can be written in any conventional computer-readable programming language, such as assembly language, C, C++, Pascal, Fortran, etc. The processor executes compiled object code or script to perform the tasks identified in the program. As also shown, the program code can be hard-coded.

[0415] The controller parameters relate to process conditions such as process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters may be provided to a user in the form of a recipe and entered using a user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 929. Signals for controlling the process may be output to analog and digital output connections of the deposition apparatus 900.

[0416] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control the operation of the chamber components necessary to perform deposition processes (and possibly other processes) in accordance with the disclosed methods. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0417] In some implementations, the controller 929 is part of a system that may be part of the examples described above. Such a system may 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 may be integrated with electronics to control their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as a "controller" that may control various components or subdivisions of one or more systems. Depending on the processing requirements and / or type of system, the controller 929 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow settings, fluid delivery settings, position and motion settings, wafer transfer into and out of tools and other transfer tools, and / or load locks connected to or interfaced with specific systems.

[0418] Broadly speaking, the controller may be defined as an electronic circuit having various integrated circuits, logic circuits, memory, and / or software that receives instructions, issues instructions, controls operations, enables cleaning operations, enables endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute the program instructions (e.g., software). The program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing specific operations on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon oxides, surfaces, circuits, and / or dies of the wafer.

[0419] The controller, in some implementations, may be part of or coupled to a computer that is integrated with, coupled to, otherwise networked to, or a combination of the above. For example, the controller may be in the "cloud" or may be all or part of a host computer system in a semiconductor fab, thereby enabling remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a fabrication operation, examine the history of past fabrication operations, examine trends or performance indicators from multiple fabrication operations, modify parameters of a current process, set up processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows for entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool the controller is configured to interface with or control. Thus, as described above, the controller may be distributed, such as by having one or more separate controllers networked together that operate toward a common goal, such as the process and control described herein. One example of a distributed controller for such purposes is one or more integrated circuits on the chamber in communication with one or more remotely located integrated circuits (such as at the platform level or as part of a remote computer) that combine to control the process on the chamber.

[0420] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin and rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer deposition (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0421] As noted above, depending on the processing step or steps to be performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, nearby tools, adjacent tools, tools located throughout the factory, a main computer, another controller, or tools used in material transport to carry containers of wafers to and from tool locations and / or load ports within the semiconductor manufacturing factory.

[0422] Other implementations The apparatus and methods described herein may be used in association with lithographic patterning tools or patterning processes, for example to fabricate or manufacture semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, but not necessarily, such apparatus are used together in a common fabrication facility or such processes are performed together in a common fabrication facility. Lithographic patterning of a film typically comprises some or all of the following steps, each of which can be accomplished using several possible tools: (1) applying photoresist onto a workpiece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hotplate or furnace or a UV curing tool; (3) exposing the photoresist to visible or UV or X-ray light using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist, thereby patterning the resist, using a tool such as a wet bench; (5) transferring the resist pattern into the underlying film or workpiece by using a dry etching tool or a plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0423] Experimental Example Example 1 (Comparative). Molybdenum metal was deposited on a dielectric (silicon oxide) and on a metal (low fluorine tungsten) using a sequence of silicon-free deposition cycles. Each cycle included a first exposure step in which MoCl5 and hydrogen were delivered to the process chamber and allowed to contact the substrate, and a second exposure step in which hydrogen was delivered to the process chamber in the absence of molybdenum precursor delivery. Deposition was performed by performing 200 deposition cycles at different temperatures ranging from 375°C to 500°C. The thickness of the deposited molybdenum was measured by XRF (X-ray fluorescence). Figure 10A provides a diagram illustrating the thickness of molybdenum obtained at each temperature. The top dot for each temperature refers to deposition on tungsten. The bottom dot for each temperature refers to deposition on the dielectric. At all temperatures, the thickness deposited on tungsten was thicker than on the dielectric. It can be seen that the on-metal / on-dielectric selectivity (ratio of the thickness of molybdenum deposited on tungsten to the thickness deposited on the dielectric) is very large at temperatures below 500° C., reaching 13 at 375° C. The selectivity decreases with increasing temperature, reaching a selectivity of 1.3 at 500° C. This figure illustrates that it is not possible to achieve a selectivity below 1.3 at temperatures below 500° C.

[0424] Example 2. According to the embodiments provided herein, silicon-assisted deposition of molybdenum-containing materials was performed on tungsten and silicon oxide at 400°C. Each cycle of silicon-assisted deposition included three stages. In the first stage, silane (SiH4) was delivered into the process chamber and allowed to contact the substrate with silane for a predetermined time (ranging from 10 seconds to 30 seconds) in the absence of hydrogen delivery and in the absence of molybdenum precursor delivery. This stage is called silane pre-soak. In the second stage, MoCl5 and H2 were delivered simultaneously into the process chamber and allowed to contact the substrate. In the third stage, H2 was delivered into the process chamber without the simultaneous delivery of a molybdenum precursor. Deposition was performed by performing 200 cycles of silicon-assisted deposition, where each cycle included a silane pre-soak stage, a molybdenum delivery stage with hydrogen, and a hydrogen delivery stage. The thickness of the resulting molybdenum-containing film was measured by XRF. FIG. 10B illustrates the thickness of molybdenum-containing material deposited on tungsten and silicon oxide for different durations of silane pre-soak. The upper dots refer to deposition on tungsten. The lower dots refer to deposition on silicon oxide. It can be seen that pre-soak times of less than 15 seconds did not lead to significant loss of selectivity on metal / dielectric, whereas for pre-soak durations of 15 and 30 seconds, the selectivity was 1.33 and 1.20, respectively. It is noted that such low selectivity could not be achieved at temperatures as low as 400° C. using silicon-free deposition. This example illustrates the selectivity loss obtained at low temperatures using the silicon-assisted deposition provided herein.

Claims

1. 1. A method of forming a molybdenum-containing layer, comprising: (a) providing a semiconductor substrate having recessed features to a processing chamber; (b) exposing the semiconductor substrate to a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to reduce the molybdenum-containing precursor to form the molybdenum-containing layer on the semiconductor substrate, wherein the molybdenum-containing layer comprises a layer of molybdenum metal; A method for providing the above.

2. 10. The method of claim 1, wherein the molybdenum-containing layer further comprises a sublayer of molybdenum silicide.

3. 10. The method of claim 1, wherein the molybdenum-containing precursor is MoX n Y m wherein X is a chalcogen, Y is a halogen, n is 0, 1, or 2, and m is 2, 3, 4, 5, or 6.

4. 10. The method of claim 1, wherein the molybdenum-containing precursor is MoCl 5 , Mo 2 Cl 10 , MoO 2 Cl 2 , MoOCl 4 , bis(ethylbenzene)molybdenum, or any combination thereof.

5. 10. The method of claim 1, wherein the silicon-containing reactant is Si x R y wherein x is 1 to 4, y is 4 to 18, and each R is independently selected from the group consisting of H, halogen, and alkyl.

6. 10. The method of claim 1, wherein the silicon-containing reactant comprises silane, chlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, trichlorodisilane, dichlorodisilane, chlorodisilane, disilane, or any combination thereof.

7. 2. The method of claim 1, wherein (b) comprises: (i) contacting the semiconductor substrate with the silicon-containing reactant for a period of time without simultaneously delivering the molybdenum-containing precursor to the processing chamber; (ii) after (i), contacting the semiconductor substrate with the molybdenum-containing precursor and the reducing agent; A method for providing the above.

8. 8. The method of claim 7, (A) (ii) comprises contacting the semiconductor substrate with the molybdenum-containing precursor without simultaneously delivering the reducing agent to the processing chamber; (B) (ii) comprises simultaneously contacting the semiconductor substrate with the molybdenum-containing precursor and the reducing agent; (C) (ii) comprises sequentially contacting the semiconductor substrate with the molybdenum-containing precursor and the reducing agent, and repeating the sequentially contacting with the molybdenum-containing precursor and the reducing agent, the method further comprising (iii) after (ii) contacting the semiconductor substrate with the silicon-containing reactant.

9. 8. The method of claim 7, further comprising repeating steps (i) and (ii).

10. 10. The method of claim 1, wherein (b) comprises simultaneously contacting the semiconductor substrate with the reducing agent, the molybdenum-containing precursor, and the silicon-containing reactant.

11. 2. The method of claim 1, wherein (b) comprises: (A)(i) simultaneously contacting the semiconductor substrate with the reducing agent and the silicon-containing reactant; and (ii) contacting the semiconductor substrate with the molybdenum-containing precursor without simultaneously delivering the silicon-containing reactant to the processing chamber; or (B)(i) simultaneously contacting the semiconductor substrate with the molybdenum-containing precursor and the silicon-containing reactant; and (iii) contacting the semiconductor substrate with the reducing agent without simultaneously delivering the silicon-containing reactant to the processing chamber. A method for providing the above.

12. 2. The method of claim 1, wherein the recessed feature in (a) comprises exposed silicon-containing dielectric on sidewalls of the recessed feature and exposed metal at a bottom of the recessed feature, and wherein the molybdenum-containing layer is deposited both on the bottom of the recessed feature and on the sidewalls of the recessed feature with a selectivity (of the sidewalls to the bottom) of about 1.3:

1.

13. 10. The method of claim 1, wherein (b) comprises completely filling the recessed feature with the molybdenum-containing layer, the molybdenum-containing layer comprising a molybdenum metal layer.

14. 2. The method of claim 1, wherein the reducing agent is hydrogen (H 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), amine, diborane (B 2 H 6 ), silane (SiH 4 ), disilane (Si 2 H 6 ), alcohol, hydrogen sulfide (H 2 S), and thiols.

15. 1. An apparatus for processing semiconductor substrates, comprising: (a) a processing chamber having a substrate holder for holding the semiconductor substrate and one or more inlets for introducing reactants into the processing chamber; (b) a controller, contacting a semiconductor substrate having recessed features with a molybdenum-containing precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to form a layer of molybdenum-containing material on the semiconductor substrate; a controller having program instructions for An apparatus comprising:

16. 16. The apparatus of claim 15, wherein the program instructions comprise: (i) contacting the semiconductor substrate with the silicon-containing reactant without simultaneously delivering the molybdenum-containing precursor to the processing chamber; (ii) after (i), contacting the semiconductor substrate with the molybdenum-containing precursor and the reducing agent; 11. An apparatus comprising instructions configured to:

17. 16. The apparatus of claim 15, wherein the program instructions comprise: (i) simultaneously contacting the semiconductor substrate with hydrogen and the silicon-containing reactant without simultaneously delivering the molybdenum-containing precursor to the processing chamber; (ii) contacting the semiconductor substrate with the molybdenum-containing precursor without simultaneously delivering the silicon-containing reactant to the processing chamber; 11. An apparatus comprising instructions configured to:

18. 16. The apparatus of claim 15, wherein the program instructions comprise: (i) simultaneously contacting the semiconductor substrate with the molybdenum-containing precursor and the silicon-containing reactant without simultaneously delivering hydrogen to the processing chamber; (ii) contacting the semiconductor substrate with hydrogen without simultaneously delivering the silicon-containing reactant to the processing chamber; 11. An apparatus comprising instructions configured to:

19. 1. A method of forming a metal-containing layer, comprising: (a) providing a semiconductor substrate having recessed features to a processing chamber; (b) exposing the semiconductor substrate to a metal precursor, a reducing agent, and a silicon-containing reactant at a temperature between about 100° C. and about 500° C. to reduce the metal precursor and form a metal-containing layer on the semiconductor substrate, the metal-containing layer comprising a layer of metal in a zero oxidation state; A method for providing the above.

20. 20. The method of claim 19, wherein the metal-containing layer further comprises a layer of a metal silicide.

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