Deposition of metal-containing films using halogen-containing activator molecules

Abstract

Metal-containing films (e.g., molybdenum and molybdenum carbide films) are deposited on a semiconductor substrate in a deposition process conditioned by the addition of halogen-containing activator molecules (e.g., alkyl halides, halosilanes, or I2). In some implementations, a substrate is contacted first with a metal-containing precursor (e.g., MoCl5), followed by a halogen-containing activator (e.g., tert-butyl chloride), followed by a reducing agent (e.g., H2). The treatment may be repeated multiple times as needed to form a film of a desired thickness. In some embodiments, a metal film is formed and deposited on the substrate inside the recessed feature by such methods to fill the recessed feature. In other embodiments, a metal carbide film (e.g., a molybdenum carbide film) is deposited by these methods as a liner between the dielectric layer and the metal layer.

Description

[0001] Incorporation by Reference The PCT Application Table, which is part of this application, is filed concurrently with this specification. Each of the applications listed in the concurrently filed PCT Application Table from which this application claims benefit or priority is incorporated by reference herein in its entirety and for all purposes. TECHNICAL FIELD

[0002] The present invention relates to methods of semiconductor device manufacturing. In particular, embodiments of the present invention relate to the deposition of metal-containing layers, such as molybdenum layers and molybdenum carbide layers, in semiconductor processing. BACKGROUND

[0003] In the manufacture of semiconductor devices, deposition and etching techniques are used to form patterns of material, such as for forming metal lines embedded in dielectric layers. Some patterning schemes require conformal deposition of material, where the deposited layer should follow the contours of raised and / or recessed features on the substrate surface. Atomic layer deposition (ALD) is generally the preferred method for forming conformal films on substrates because ALD relies on the adsorption of one or more reactants (precursors) to the substrate surface, and the subsequent chemical transformation of the adsorbed layer into the desired material. Because ALD uses sequential reactions that occur on the substrate surface, these reactions are separated in time and are generally limited by the amount of adsorbed reactant, this method can provide thin conformal layers with excellent step coverage.

[0004] Chemical vapor deposition (CVD) is another deposition method that is widely used in semiconductor processing. In CVD, reactions occur in the volume of the processing chamber and are not limited by the amount of reactant adsorbed onto the substrate. As a result, CVD-deposited films are generally less conformal than ALD-deposited films. CVD is generally used in applications where step coverage is less important.

[0005] ALD and CVD can use plasma to facilitate the reaction of the deposition precursors, thereby forming the desired film. Methods that utilize plasma are referred to as plasma-enhanced ALD (PEALD) and plasma-enhanced CVD (PECVD). Methods that do not use plasma are referred to as thermal ALD and thermal CVD.

[0006] While ALD and CVD are most commonly used for the deposition of silicon-containing films (e.g., silicon oxides, silicon nitrides, and silicon carbides), these methods are also applicable to the deposition of certain metals.

[0007] The background description provided herein is for the purpose of generally presenting the context of the disclosure. The work of the presently named inventors, to the extent the work is described in this background section, as well as aspects of the description that can not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY

[0008] Methods for depositing metal-containing layers (e.g., molybdenum and molybdenum carbide layers) on semiconductor substrates using halogen-containing activator molecules are provided. The halogen-containing activator is used in conjunction with a metal precursor and a reducing agent, typically after the substrate has been previously exposed to the metal precursor. In some implementations, the deposition rate of the metal-containing material (e.g., metal or metal carbide) is significantly increased (e.g., at least about 20%, such as at least about 100%) by contacting the semiconductor substrate with a halogen-containing activator molecule (e.g., an alkyl halide, dihalogen, halosilane, or any combination thereof) after the semiconductor substrate has been previously contacted with the metal precursor.

[0009] In one aspect, a method of forming a metal-containing layer (e.g., a metal layer, a metal carbide layer, or a metal nitride layer) is provided. In some embodiments, the method includes: (a) contacting a semiconductor substrate with a metal precursor in a processing chamber; (b) contacting the semiconductor substrate with a halogen-containing deposition activator, wherein the halogen-containing deposition activator is different from the metal precursor; and (c) contacting the semiconductor substrate with a reducing agent to form a metal-containing layer on the semiconductor substrate. In some embodiments, steps (a), (b), and (c) are performed sequentially without simultaneously (together) flowing into the processing chamber any two components selected from the group consisting of the metal precursor, the halogen-containing deposition activator, and the reducing agent. In some embodiments, the method includes performing at least 2 (e.g., at least 50) deposition cycles, wherein each cycle includes steps (a), (b), and (c) performed sequentially. In some embodiments, steps (b) and (c) are performed simultaneously (i.e., at least partially overlapping in time).

[0010] Examples of halogen-containing deposition activators include hydrogen halides, alkyl halides, halosilanes, dihalogens, halides of Group 13 elements, halides of Group 15 elements, and metal halides. In some embodiments, the halogen-containing deposition activator is a tertiary alkyl halide (e.g., tert-butyl chloride). In some embodiments, the halogen-containing deposition activator is an iodine-containing deposition activator. Examples of iodine-containing deposition activators include hydrogen iodide (HI), iodine (I2), tert-butyl iodide (C4H9I), allyl iodide (C3H5I), iodosilane (SiH3I), disilane (SiH2I2), trisilane (SiHI3), and silicon tetraiodide (SiI4). In some embodiments, the halogen-containing deposition activator is a bromine-containing deposition activator. Examples of bromine-containing deposition activators include hydrogen bromide (HBr), bromine (Br2), tert-butyl bromide, bromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (SiHBr3), and silicon tetrabromide (SiBr4). In some embodiments, the halogen-containing deposition activator is selected from the group consisting of titanium tetrabromide, tungsten pentabromide, tungsten hexabromide, boron tribromide, and aluminum tribromide. In some embodiments, the halogen-containing deposition activator is selected from the group consisting of titanium tetraiodide, boron triiodide, and aluminum triiodide.

[0011] Metal-containing layers deposited by the provided methods include, but are not limited to, metal layers, metal carbide layers, and metal nitride layers. A molybdenum-containing layer, a cobalt-containing layer, a ruthenium-containing layer, a tungsten-containing layer, a titanium-containing layer, or any combination thereof can be deposited by the provided methods. In some embodiments, the deposited layer is a metal layer (e.g., molybdenum, cobalt, ruthenium, tungsten, titanium, or any combination thereof). In some embodiments, the metal-containing layer includes a metal nitride layer, such as a titanium nitride layer, a molybdenum nitride layer, or any combination thereof. In some embodiments, the metal-containing layer is a metal carbide layer, such as a molybdenum carbide.

[0012] In some implementations, the deposited metal-containing layer is a molybdenum-containing layer (e.g., a molybdenum metal layer, a molybdenum nitride layer, or a molybdenum carbide layer). In an embodiment, the deposited metal-containing layer is a molybdenum-containing layer, and the metal precursor is a molybdenum precursor comprising a molybdenum-halogen bond. For example, the molybdenum precursor can include MoCl5, Mo2Cl 10 , MoO2Cl2, MoOCl4, or MoF6, or any combination thereof. Other examples include, but are not limited to, Mo(PF3)6, Mo(CO)6, i PrCp)2MoH2, Mo(hfac)3, MoO(OiPr)4, bis(ethylbenzene)Mo, or Mo2(TFA)4, where i PrCp = isopropylcyclopentadiene, hfac = hexafluoroacetylacetonate.

[0013] In some embodiments, the metal precursor comprises a metal-chlorine bond, and the halogen-containing deposition activator comprises at least one of bromine and iodine. Examples of bromine-containing deposition activators include hydrogen bromide (HBr), bromine (Br2), t-butyl bromide, bromosilane (SiH3Br), disilane bromide (SiH2Br2), trisilane bromide (SiHBr3), and silicon tetrabromide (SiBr4). Examples of iodine-containing deposition activators include hydrogen iodide (HI), iodine (I2), t-butyl iodide (C4H9I), allyl iodide (C3H5I), iodosilane (SiH3I), disilane iodide (SiH2I2), trisilane iodide (SiHI3), and silicon tetraiodide (SiI4).

[0014] In some embodiments, the deposited metal-containing layer is a molybdenum carbide (MoC or MoCN) layer deposited onto a semiconductor substrate comprising a plurality of recessed features as a liner, wherein the recessed features comprise a dielectric on the sidewalls. In some embodiments, the deposited layer is a MoC layer. In some embodiments, the deposited layer is a MoCN layer. After the molybdenum carbide layer has been deposited as a liner, the recessed features can be filled with a metal.

[0015] In some embodiments, the metal-containing layer is a metal layer (e.g., a molybdenum layer) deposited into a recessed feature of a semiconductor substrate to at least partially fill the recessed feature.

[0016] In some embodiments, the deposition of the metal-containing layer is performed at a temperature between about 250 °C and about 600 °C and at a pressure less than about 300 Torr.

[0017] In one aspect, a method is provided, the method comprising: (a) providing a semiconductor substrate having an exposed dielectric layer; (b) forming a molybdenum carbide liner on the dielectric layer by exposing the semiconductor substrate to a molybdenum precursor, an alkyl halide, and a reducing agent; and (c) depositing a metal layer on the molybdenum carbide liner.

[0018] In some embodiments, the provided method is integrated with a photolithographic patterning sequence and further comprises: applying a photoresist to the semiconductor substrate; exposing the photoresist to light; patterning the photoresist and transferring the pattern to the substrate; and selectively removing the photoresist from the substrate. For example, these steps can be performed to form recessed features on the semiconductor substrate prior to depositing the metal-containing layer.

[0019] In another aspect, an apparatus is provided, where the apparatus includes a controller having program instructions configured to cause the method steps of any of the methods provided herein to be implemented. For example, in some embodiments, an apparatus for processing a substrate is provided, where the apparatus includes: (a) a processing chamber having a substrate holder for holding a semiconductor substrate and one or more inlets for introducing reactants into the processing chamber; and (b) a controller including program instructions for: (i) contacting the semiconductor substrate with a metal precursor in the processing chamber; (ii) contacting the semiconductor substrate with a halogen-containing deposition activator, where the halogen-containing deposition activator is different from the metal precursor; and (iii) contacting the semiconductor substrate with a reducing agent to form a metal-containing layer on the semiconductor substrate. In some embodiments, a system for processing a substrate is provided, where the system includes: (a) one or more processing chambers; and (b) a controller including program instructions for: (i) depositing a molybdenum carbide underlayer on a semiconductor substrate having an exposed deposition layer by exposing the semiconductor substrate to a molybdenum precursor, an alkyl halide, and a reducing agent; and (ii) depositing a metal layer on the molybdenum carbide underlayer.

[0020] In another aspect, a non-transitory machine-readable medium is provided, where the non-transitory machine-readable medium includes code for causing the steps of any of the methods provided herein to be implemented. For example, the code can include code for (i) contacting the semiconductor substrate with a metal precursor in the processing chamber; (ii) contacting the semiconductor substrate with a halogen-containing deposition activator, where the halogen-containing deposition activator is different from the metal precursor; and (iii) contacting the semiconductor substrate with a reducing agent to form a metal-containing layer on the semiconductor substrate. In some embodiments, the non-transitory machine-readable medium can include code for: (i) depositing a molybdenum carbide underlayer on a semiconductor substrate having an exposed deposition layer by exposing the semiconductor substrate to a molybdenum precursor, an alkyl halide, and a reducing agent; and (ii) depositing a metal layer on the molybdenum carbide underlayer.

[0021] These and other aspects of implementations of the subject matter described in this specification are set forth in the accompanying drawings and the detailed description below. BRIEF DESCRIPTION OF DRAWINGS

[0022] FIGS. 1A-1C show schematic cross-sectional views of a substrate during deposition of a metal-containing film according to embodiments provided herein.

[0023] FIGS. 2A-2C show schematic cross-sectional views of a substrate during deposition of a metal-containing film according to another embodiment provided herein.

[0024] FIG. 3A is a process flow diagram of a method of forming a metal-containing film according to embodiments provided herein.

[0025] Figure 3B is a process flow diagram of a method of forming a metal-containing film according to embodiments provided herein.

[0026] Figure 4 provides examples of ligands that can be used for molybdenum precursors according to embodiments provided herein.

[0027] Figure 5 provides examples of sulfur-containing ligands that can be used for molybdenum precursors according to embodiments provided herein.

[0028] Figure 6A lists examples of molybdenum precursors according to embodiments provided herein.

[0029] Figure 6B lists examples of molybdenum precursors according to embodiments provided herein.

[0030] Figure 6C lists examples of molybdenum precursors according to embodiments provided herein.

[0031] Figure 7 is a schematic of an apparatus suitable for depositing a metal-containing film according to embodiments provided herein.

[0032] Figure 8 shows a schematic of a multi-station processing system according to embodiments provided herein.

[0033] Figure 9 shows a schematic of a multi-station processing system according to embodiments provided herein.

[0034] Figure 10 is a graph showing the thickness of molybdenum deposited on titanium nitride as a function of temperature with and without the use of a halogen-containing activator. DETAILED DESCRIPTION

[0035] Methods are provided for depositing metal-containing layers (e.g., metal, metal carbide, and metal nitride layers) on semiconductor substrates using vapor deposition (e.g., CVD or ALD). The methods generally do not require the use of plasma activation, and include, but are not limited to, processing sequences in which all steps are performed in the absence of plasma (although in some embodiments, one or more steps can be plasma-assisted). The methods can be used to deposit metals, such as molybdenum, ruthenium, tungsten, titanium, and cobalt, as well as metal carbides (including oxycarbides and carbonitrides), such as molybdenum carbide (including MoC and MoCN), ruthenium carbide, tungsten carbide, and cobalt carbide. Other metal-containing films, such as metal nitrides (e.g., molybdenum nitride or titanium nitride) and metal borides, can also be deposited. Deposition can be performed at low temperatures, below about 600 °C (e.g., below about 500 °C), at high deposition rates.

[0036] The method utilizes a halogen-containing deposition activator to increase the deposition rate on the substrate, where the halogen-containing deposition activator is contacted with the substrate after the substrate has been previously contacted with a metal precursor, and where the halogen-containing deposition activator molecule is different from the metal precursor. In some implementations, the substrate is contacted with a reducing agent after the substrate has been contacted with the halogen-containing deposition activator. In other implementations, the substrate is simultaneously contacted with the halogen-containing deposition activator and the reducing agent.

[0037] In some implementations, the halogen-containing deposition activator increases the deposition rate by at least about 20%, such as at least 50%, or at least about 100%, compared to a process performed under the same deposition conditions in the absence of the activator. For example, the metal deposition rate can be increased from about 20 A per 100 deposition cycles to about 90 A per 100 deposition cycles.

[0038] The provided methods can be used to deposit a metal (e.g., molybdenum, ruthenium, titanium, cobalt, or tungsten) to fill a recessed feature on a semiconductor substrate. The recessed feature can be filled by a conformal or bottom-up mechanism. The thickness of the metal layer deposited within the recessed feature ranges, in some examples, from about 0.1 μιη to about 500 μιη. In other embodiments, the deposited film is used as a liner, for example, at the interface between a dielectric layer and a metal layer (e.g., a film having a thickness between about 0.5 nm and about 200 nm, such as between about 1 nm and about 100 nm). For example, a metal carbide film (e.g., a molybdenum carbide film) can be conformally deposited as a liner on a substrate having a recessed feature formed in a dielectric layer using the provided methods. After the liner has been deposited by the methods provided herein, the recessed feature can be filled with a metal (e.g., molybdenum, tungsten, or ruthenium) using the methods provided herein or by other deposition methods (e.g., CVD without the use of a halogen-containing deposition activator molecule).

[0039] The provided methods can be used to deposit a metal-containing film on a variety of surfaces, including but not limited to on metals (e.g., molybdenum, tungsten, cobalt, ruthenium, copper, titanium, and combinations thereof), metal nitrides (e.g., titanium nitride, tantalum nitride, and combinations thereof), metal carbides (e.g., tungsten carbide), metal oxides (e.g., aluminum oxide, hafnium oxide, titanium oxide, and combinations thereof), metal silicides (e.g., titanium silicide), silicon (e.g., amorphous silicon, polysilicon, hydrogen-terminated silicon, and combinations thereof), silicon germanium, silicon-containing dielectrics (e.g., silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, and combinations thereof), carbon (e.g., amorphous carbon), and any combination thereof. In some embodiments, deposition is performed on substrates having different exposed materials. For example, the metal-containing films provided herein can be deposited in a substrate having a recessed feature, where a dielectric is exposed in a field region and at the sidewalls of the recessed feature, and a metal is exposed at the bottom of the recessed feature.

[0040] The provided methods can be used for various applications, including but not limited to depositing metals (e.g., molybdenum) in gap fill applications, and forming conformal metal-containing metal films. Examples of semiconductor device structures that can be fabricated using the provided methods include back end of line (BEOL) metallization structures, front end of line (FEOL) metallization structures, logic metallization structures, and memory structures, such as 3D NAND and DRAM. In some embodiments, the method is used to deposit metal-containing films having a thickness in a range between about 0.5 nm and about 4 nm, and can be used to deposit molybdenum metal in various recessed features, such as features having a width between about 1 nm and about 25 nm, a depth between about 30 nm and about 200 nm or greater depths, and various aspect ratios, including high aspect ratios of at least 10: 1 (e.g., 30: 1).

[0041] As used herein, "metal" refers to a material consisting essentially of a metal in a zero oxidation state. Other elements (e.g., C, N, or O) can be present in the metal in small amounts (e.g., less than about 15 atomic %, or less than about 10%, where hydrogen is not included in the calculation). In some embodiments, a metal film having less than 3% atomic carbon can be obtained by the provided methods. Examples of metal films that can be obtained by the provided methods include 97% pure molybdenum, 97% pure cobalt, 97% pure tungsten, and 97% pure ruthenium, where % refers to weight %.

[0042] As used herein, "metal carbide" refers to a material containing a metal and carbon. In some embodiments, the carbon content is greater than about 10 atomic %, such as greater than 20 atomic %, or greater than 40 atomic % (where hydrogen is not included in the calculation). Metal carbides as used herein can include other elements, such as N, O, and B. For example, "molybdenum carbide" as used herein encompasses MoC, MoOC, and MoCN (also referred to as molybdenum carbonitride or molybdenum nitrocarbide), where the formula does not indicate a particular stoichiometry. For example, in some embodiments, MoC has a carbon content between about 40-60 atomic %, without necessarily being 50 atomic %.

[0043] As used herein, the term "semiconductor substrate" refers to a substrate at any stage of semiconductor device fabrication that contains semiconductor material at any location within its structure. It is understood that the semiconductor material in a semiconductor substrate need not be exposed. An example of a semiconductor substrate is a semiconductor wafer having multiple other material (e.g., dielectric) layers covering the semiconductor material. The detailed description below assumes that the disclosed implementations are implemented on a semiconductor wafer (e.g., on a 200 mm, 300 mm, or 450 mm semiconductor wafer). However, the disclosed implementations are not limited thereto. The workpiece can be of various shapes, sizes, and materials. In addition to a semiconductor wafer, other workpiece types that can utilize the disclosed implementations include various articles, such as printed circuit boards, etc.

[0044] As used herein, the term "halogen-containing deposition activator" refers to a substance (e.g., a compound) that includes one or more halogen atoms (e.g., F, CI, Br, I, or any combination thereof), wherein use of the activator in the deposition of a metal-containing material results in a higher deposition rate of the metal-containing material compared to the same deposition process conducted in the absence of the halogen-containing activator. Examples of halogen-containing deposition activators include alkyl halides, metal halides, halosilanes, dihalogens, hydrogen halides, halides of Group 13 elements, and halides of Group 15 elements.

[0045] As used herein, the term "reducing agent" refers to a substance that is oxidized (loses one or more electrons) during the course of a deposition process. For example, H2with a zero oxidation state (reducing agent) can be oxidized to HCI during a deposition process in which hydrogen is in a +1 oxidation state.

[0046] The term "about" as used herein, unless otherwise indicated, means ± 10% of any stated value. When used, this term causes the endpoints of any stated value, range, or one or more ranges to be modified by the term "about."

[0047] The terms "top," "bottom," "upper," "lower," and the like are used herein to provide relative relationships among multiple structures. The use of these terms does not indicate or require a specific location in the device.

[0048] As used herein, the phrase "at least one of A, B, and C" should be interpreted as meaning A or B or C using non-exclusive logical OR (OR), and not as meaning "at least one A, at least one B, and at least one C."

[0049] As used herein, "a" should be understood to mean "one or more" of the referenced elements. For example, "a surface of a substrate" should be understood to mean "one or more surfaces of a substrate" and can include recessed feature sidewall surfaces, field surfaces, recessed feature bottom surfaces, and combinations thereof.

[0050] As used herein, "reducing agent" refers to a reactant that loses one or more electrons in a reaction.

[0051] As used herein, "heteroleptic complex" refers to a compound that includes at least two different ligands attached to a metal center.

[0052] As used herein, "homoleptic complex" refers to a compound that includes ligands that are all the same and attached to a metal center.

[0053] The term "activator-free deposition cycle" refers to sequentially exposing a substrate to a metal precursor and a reducing agent without a deposition activator.

[0054] The term "activator-assisted deposition cycle" refers to exposing a semiconductor substrate to a deposition activator, a metal precursor, and a reducing agent, where at least some of these exposures are performed sequentially.

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

[0056] "Alkanoyloxy" refers to 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 acetyloxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0057] "Aliphatic" refers to hydrocarbon radicals containing at least one carbon atom with the number of carbon atoms in any aliphatic radical being an integer from 1 to 50 (C 1-50 ), such as from 1 to 25 carbon atoms (C 1-25 ), or from 1 to 10 carbon atoms (C 1-10 ), and includes alkane (or alkyl), alkene (or alkenyl), alkyne (or alkynyl) hydrocarbon groups, including cyclic versions, and also includes straight- chain and branched-chain versions, as well as all stereo and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups can be substituted with one or more substituents as described herein for alkyl groups.

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

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

[0060] "Aliphatic-oxy ​​group" refers to an aliphatic group that is coupled to or can be coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or becomes coupled via an oxygen group (-C(O)-). In some embodiments, the aliphatic-oxy ​​group is -OR, where R is an optionally substituted aliphatic group as defined herein.

[0061] "Aliphatic-oxycarbonyl" refers to an aliphatic group coupled to or potentially coupled to the compounds disclosed herein, wherein the aliphatic group is coupled or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted aliphatic group as defined herein.

[0062] “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” refer to an alkyl, alkenyl, or alkynyl group as defined herein, which is coupled (or linked) or may be coupled (or linked) to a parent molecule group by an aryl group as defined herein. Alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted with one or more substituents, as described herein with respect to alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbons (C60-C60). 7-16 Alkyl-aryl), and those having alkyl groups containing 1 to 6 carbons and aryl groups containing 4 to 18 carbons (i.e., C10, C20, C30, C40, C50, C6 ... 1-6 Alkyl-C 4-18 Aryl). Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbons (C). 7-16 Alkenyl-aryl), and those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C). 2-6 alkenyl-C 4-18 Aryl). Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbons (C). 7-16 (alkynyl-aryl), and those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C10-C ... 2-6 alkynyl-C 4-18 Aryl). In some embodiments, alkyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, where L is an aryl or arylene as defined herein, and R is an alkynyl as defined herein.

[0063] "Alkenyl" refers to a group having at least 2 to 50 carbon atoms (C2+1 ...3+12+12+12+13+12+12+13+12+12+13+12+1 2-50), such as 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon double bond. The unsaturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of a parent olefin. Alkenyl groups can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 alkyl groups having one or more double bonds. Alkenyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to a parent molecular group or between a 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 groups. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0064] “Alkoxy” refers to -OR, wherein R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propyloxy, i-propyloxy, n-butyloxy, t-butyloxy, sec-butyloxy, n-pentyloxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkoxy groups.

[0065] “Alkoxyalkyl” refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include 2 to 12 carbon (C 2-12 alkoxyalkyl groups, as well as those having an alkyl group containing 1 to 6 carbons and an alkoxy group containing 1 to 6 carbons (i.e., C 1-6 alkoxy-C 1-6 alkyl groups). In some embodiments, alkoxyalkyl groups are -L-O-R, wherein L and R are each independently alkyl groups, as defined herein.

[0066] “Alkoxycarbonyl” means -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In particular embodiments, alkoxycarbonyl is -C(O)-OAk, where Ak is an alkyl group as defined herein. Alkoxycarbonyl groups can be substituted or unsubstituted. For example, an alkoxycarbonyl group can be substituted with one or more substituents as described herein for alkyl groups. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 alkoxycarbonyl.

[0067] “Alkyl” means a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), where the saturated monovalent hydrocarbon can be obtained by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). Alkyl groups can be branched, straight-chain, or cyclic (e.g., cycloalkyl). Exemplary alkyl groups 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), t-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), t-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Alkyl groups can also be substituted or unsubstituted. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to a parent molecular group or between a parent molecular group and another substituent. For example, an alkyl group can be substituted with one, two, three, or, in the case of alkyl groups of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl); (2) C 1-6 alkylsulfinyl (e.g., C 1-6 , where R is C1-6alkyl); (3) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl); (4) amino (e.g., -NR 1 R2 wherein R 1 and R 2 are each independently selected from hydrogen, an aliphatic group as defined herein, a heteroaliphatic group, a haloaliphatic group, a haloheteroaliphatic group, an aromatic group, or any combination thereof, or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein); (5) aryl; (6) aralkoxy (e.g., -O-L-R, wherein L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, wherein R is heterocyclyl as defined herein); (15) heterocyclylcarbonyl (e.g., -C(O)-R, wherein R is heterocyclyl as defined herein); (16) hydroxyl (e.g., -OH); (17) N protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 thioalkyl (e.g., -S-R, wherein R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 wherein R 1 is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 4-18 aryl); (23) -C(O)NR 1 R 2 wherein R 1 and R 2 are each independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, wherein L is C 1-6 alkyl and R is C 4-18 aryl); (24) -SO2R 1 wherein R 1 is selected from the group consisting of (a) C 1-6alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (25) -SO2NR 1 R 2 where R 1 and R 2 are each independently selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); and (26) -NR 1 R 2 where R 1 and R 2 are each independently selected from the group consisting of (a) hydrogen, (b) N -protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), where in one embodiment no two groups are bound to the nitrogen atom through a carbonyl or sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 alkyl.

[0068] As used herein, "alkyl halide" refers to a compound comprising one or more carbon-halogen bonds. As used herein, an alkyl halide can be a saturated compound having no carbon-carbon double or triple bonds, or an unsaturated compound (e.g., can include carbon-carbon double and triple bonds). Examples of alkyl halides include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides. Examples of t-butyl alkyl halides include t-butyl fluoride, t-butyl chloride, t-butyl bromide, and t-butyl iodide.

[0069] "Alkylene," "alkenylene," or "alkynylene" refers to a polyvalent (e.g., divalent) version of an alkyl, alkenyl, or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, the alkylene group is C 1-3 , 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 alkylene. In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 alkenylene or alkynylene. The alkylene, alkenylene, or alkynylene group can be branched or unbranched. The alkylene, alkenylene, or alkynylene group can also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group can be substituted with one or more substituents as described herein for an alkyl group.

[0070] "Alkylsulfinyl" refers to an alkyl group as defined herein attached to the parent molecular group through a -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 alkylsulfinyl. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group as defined herein.

[0071] "Alkylsulfinylalkyl" refers to an alkyl group as defined herein substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is C 2-12 or C 2-24 alkylsulfinylalkyl (e.g., C1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, the alkylsulfonylalkyl is -L-S(O)2-R, wherein L and R are each independently alkyl as defined herein.

[0072] “Alkylsulfonyl” refers to an alkyl group as defined herein attached to the parent molecular group through a -SO2- group. In some embodiments, an unsubstituted alkylsulfonyl is C 1-6 or C 1-12 alkylsulfonyl. In other embodiments, the alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., comprising optionally substituted C 1-12 alkyl, haloalkyl, or perfluoroalkyl) as described herein.

[0073] “Alkylsulfonylalkyl” refers to an alkyl group as defined herein substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24 alkylsulfonylalkyl (e.g., C 1-6 alkylsulfonyl-C 1-6 alkyl or C 1-12 alkylsulfonyl-C 1-12 alkyl). In other embodiments, the alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0074] “Alkynyl” refers to an unsaturated monovalent hydrocarbon radical of from at least 2 carbon atoms to 50 carbon atoms (C 2-50 ), for example, from 2 to 25 carbon atoms (C 2-25 ), or from 2 to 10 carbon atoms (C 2-10 ), and at least one carbon-carbon triple bond, where the unsaturated monovalent hydrocarbon can be derived by the removal of one hydrogen atom of a parent alkyne. The alkynyl radical can be straight, branched, or cyclic (e.g., a cycloalkynyl radical). An exemplary alkynyl includes an optionally substituted C 2-24 alkyl radical having one or more triple bonds. The alkynyl radical can be monovalent or polyvalent (e.g., divalent) by the removal of one or more hydrogens to form appropriate linkages to the parent molecular group or between the parent molecular group and another substituent. The alkynyl radical can also be substituted or unsubstituted. For example, the alkynyl radical can be substituted with one or more substituents as described herein for alkyl groups.

[0075] "ambient temperature" refers to a temperature in the range of 16 °C to 26 °C, for example, 19 °C to 25 °C or 20 °C to 25 °C.

[0076] "amide" refers to -C(O)NR 1 R 2 or -NHCOR 1 wherein R 1 and R 2 are each independently selected from hydrogen, an aliphatic group, a heteroaliphatic group, an aromatic group, or any combination thereof, as defined herein, or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein.

[0077] "amino" refers to -NR 1 R 2 wherein R 1 and R 2 are each independently selected from hydrogen, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted silyl group, or an optionally substituted siloxy group, or any combination thereof, as defined herein; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein. In specific embodiments, R 1 and R 2 are each independently H, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted alkyl-aryl group, an optionally substituted aryl-alkyl group, an optionally substituted silyl group, or an optionally substituted siloxy group. In specific embodiments, R 1 and R 2 together with the nitrogen atom to which each is attached can form an optionally substituted heterocyclyl group.

[0078] "aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 wherein L is an alkyl group, as defined herein, and R 1 and R 2 are each independently selected from hydrogen, an aliphatic group, a heteroaliphatic group, or an aromatic group, as defined herein, or any combination thereof; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR 1 R 2 )(R 3 )-R4 wherein L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic, or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein; and R 3 and R 4 are each independently H or an alkyl group as defined herein.

[0079] "Aminooxy" refers to an oxy group as defined herein 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 are each independently selected from hydrogen, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl, or an optionally substituted siloxy group as defined herein, or any combination thereof; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein. In specific embodiments, R 1 and R 2 are each independently H, an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted aryloxy, an optionally substituted alkyl-aryl, an optionally substituted aryl-alkyl, an optionally substituted silyl, or an optionally substituted siloxy group.

[0080] Unless otherwise specified, "aromatic group" refers to a cyclic, conjugated group or moiety (e.g., naphthyl, indolyl, or pyrazolopyridinyl) of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings of which at least one is aromatic; that is, at least one ring and optionally multiple condensed rings have a continuous delocalized pi electron system. Typically, the number of out-of-plane pi electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the condensed ring system. The aromatic group is unsubstituted or substituted, for example, with functional groups described herein. For example, the aromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl groups.

[0081] "Aryl-carbonyl" refers to an aryl group coupled to or that can be coupled to a compound disclosed herein, wherein the aryl group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, the aryl-carbonyl is -C(O)-R, wherein R is an optionally substituted aryl group as defined herein.

[0082] "Aryl-carbonyloxy" refers to an aryl group coupled to or that can be coupled to a compound disclosed herein, wherein the aryl group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, the aryl carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aryl group as defined herein.

[0083] "Aryl-oxy" refers to an aryl group coupled to or that can be coupled to a compound disclosed herein, wherein the aryl group is coupled or becomes coupled through an oxy (-O-). In some embodiments, the aryl-oxy is -O-R, wherein R is an optionally substituted aryl group as defined herein.

[0084] "Aryl-oxycarbonyl" refers to an aryl group coupled to or that can be coupled to a compound disclosed herein, wherein the aryl group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aryl-carbonyl is -C(O)O-R, wherein R is an optionally substituted aryl group as defined herein.

[0085] "Aryl" refers to an aromatic carbocyclic group including at least 5 carbon atoms to 15 carbon atoms (C 5-15 ), for example, 5 to 10 carbon atoms (C 5-10 ), having a single ring or multiple condensed rings, which condensed rings can or can not be aromatic, provided that the point of attachment to the remainder of the compound disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group can be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl is also included in the term aryl, which defines a group containing an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, wherein R is C1-6 alkyl); (2) C 1-6 alkyl; (3) C 1-6 alkoxy (e.g., -O-R, where R is C 1-6 alkyl); (4) C 1-6 alkoxy-C 1-6 alkyl (e.g., -L-O-R, where L and R are each independently C 1-6 alkyl); (5) C 1-6 alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 alkyl); (6) C 1-6 alkylsulfinyl-C 1-6 alkyl (e.g., -L-S(O)-R, where L and R are each independently C 1-6 alkyl); (7) C 1-6 alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl); (8) C 1-6 alkylsulfonyl-C 1-6 alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein); (11) C 1-6 aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or C 1-6 alkyl; R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl, as defined herein; and R 3and R 4 each independently H or C 1-6 alkyl); (12) heteroaryl; (13) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (14) aroyl (e.g., C(O)-R, where R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-C 1-6 alkyl (e.g., -L-C(O)H, where L is C 1-6 alkyl); (20) C 3-8 cycloalkyl; (21) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl); (22) 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 alkyl; L 2 is a covalent bond or C 1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and R 1 and R 2 each independently H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, where R is heterocyclyl as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein); (27) hydroxyl (-OH); (28) C 1-6 hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 is C 1-6 alkyl; L 2 is a covalent bond or alkyl; and R 1 and R 2 each independently H or C1-6 (29) Alkyl group (as defined herein); (30) Nitro group; 1-6 Nitroalkyl (e.g., -L) 1 -NO or -L 2 -C(NO)(R 1 )-R 2 L 1 It is C 1-6 Alkyl; L 2 It is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 Alkyl groups, as defined herein; (31) N - Protected amino group; (32) N -Protected amino-C 1-6 Alkyl; (33) Oxyl (e.g., =O); (34) C 1-6 Thioalkyl groups (e.g., -SR, where R is C) 1-6 Alkyl); (35) Thio-C 1-6 Alkoxy-C 1-6 Alkyl groups (e.g., -LSR, where L and R are each independently C). 1-6 Alkyl); (36)-(CH2) r CO2R 1 , where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (37)-(CH2) r CONR 1 R 2 , where r is an integer from 0 to 4 and R 1 and R 2 Each is independently selected from: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl groups (e.g., -LR, where L is C) 1-6 Alkyl and R is C 4-18 (Aryl); (38)-(CH2) r SO2R 1 , where r is an integer from 0 to 4, and R 1 Choose from the following groups: (a) C1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (39) -(CH2) r SO2NR 1 R 2 where r is an integer from 0 to 4, and where R 1 and R 2 each independently is selected from the group consisting of (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl); (40) -(CH2) r NR 1 R 2 where r is an integer from 0 to 4, and where R 1 and R 2 each independently is selected from the group consisting of (a) hydrogen, (b) N -protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 cycloalkyl-C 1-6 alkyl (e.g., -L-R, where L is C 1-6 alkyl and R is C 3-8 cycloalkyl), where in one embodiment no two radicals are bound to the nitrogen atom through a carbonyl or sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2) n CF3, where n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2) nCF3, where n is an integer from 0 to 10; (44) aryloxy (e.g., -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 a specific embodiment, the unsubstituted aryl 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 6-10 Aryl.

[0086] "Aryl-alkyl," "aryl-alkenyl," and "aryl-ynyl" refer to an aryl group as defined herein, which is coupled (or linked) to a parent molecule group via an alkyl, alkenyl, or ynyl group as defined herein. Aryl-alkyl, aryl-alkenyl, and / or aryl-ynyl groups may be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl, and / or aryl-ynyl groups may be substituted with one or more substituents, as described herein with respect to aryl and / or alkyl groups. An exemplary unsubstituted aryl-alkyl group has 7 to 16 carbons (C60-C60). 7-16 Aryl-alkyl), and those having 4 to 18 carbons of aryl and 1 to 6 carbons of alkyl (i.e., C10, C20, C30, C40, C50, C6 ... 4-18 Aryl-C 1-6 Alkyl groups. Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbons (C60-162). 7-16 Aryl-alkenyl), and those having an aryl group with 4 to 18 carbons and an alkenyl group with 2 to 6 carbons (i.e., C). 4-18 Aryl-C 2-6 Alkenyl). Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbons (C). 7-16 Aryl-alkynyl), and those having an aryl group with 4 to 18 carbons and an alkynyl group with 2 to 6 carbons (i.e., C). 4-18 Aryl-C 2-6 (Alkynyl). In some embodiments, the aryl-alkyl 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, the aryl-alkenyl group is -LR, where L is an alkenyl or alkenyl group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -LR, where L is an alkynyl or alynylene group as defined herein, and R is an aryl group as defined herein.

[0087] "Arylidene" refers to the polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylidene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthracene, or phenanthrene. In some embodiments, the arylidene is C1. 4-18 C 4-14 C 4-12 C 4-10 C 6-18 C 6-14 C 6-12 Or C 6-10 Arylenes. Arylenes can be branched or unbranched. Arylenes can also be substituted or unsubstituted. For example, arylenes can be substituted by one or more substituents, as described herein with respect to aryl groups.

[0088] "Arylalkoxy" refers to an aryl-alkyl group as defined herein, which is attached to a parent molecule group via 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.

[0089] "Aryloxy group" refers to -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C. 4-18 Or C 6-18 Aryloxy group. In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, etc.

[0090] "Aryloxycarbonyl" refers to an aryloxy group as defined herein, which is attached to a parent molecule group via a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C10. 5-19 Aryloxycarbonyl. In other embodiments, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group as defined herein.

[0091] "Aromatic acyl" refers to an aryl group linked to a parent molecule group via a carbonyl group. In some embodiments, the unsubstituted aromatic acyl group is C10. 7-11 Aromatic acyl or C 5-19 Aromatic acyl group. In other embodiments, the aromatic acyl group is -C(O)-R, where R is an aryl group as defined herein.

[0092] "Aryloxy group" refers to an aryl group as defined herein, which is attached to a parent molecule group via an oxygen group. In some embodiments, the unsubstituted aryloxy group is C 5-19 Aromatic acyloxy group. In other embodiments, the aromatic acyloxy group is -OC(O)-R, where R is an aryl group as defined herein.

[0093] "Azide group" refers to the -N3 group.

[0094] "Aryloxy" means an aryloxy group as defined herein linked through an oxygen atom to the parent molecular moiety. In some embodiments, the aryloxy group is -O-aryl, wherein aryl is as defined herein.

[0095] "Azo" means a -N=N- group.

[0096] "Carbamoyl" means an amino group as defined herein linked through a carbonyl group as defined herein to the parent molecular moiety. In some embodiments, the carbamoyl group is -C(O)NR 1 R 2 group, wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic as defined herein, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein.

[0097] "Carbamoyloxy" means a carbamoyl group as defined herein linked through n oxy groups as defined herein to the parent molecular moiety. In some embodiments, the carbamoyloxy group is -OC(O)NR 1 R 2 group, wherein R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic as defined herein, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy, or any combination thereof; or wherein R 1 and R 2 together with the nitrogen atom to which each is attached can form a heterocyclyl group as defined herein.

[0098] "Carbonylimino" means a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic as defined herein, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof.

[0099] "Carbonyl" means a -C(O)- group, which can also be represented as >C=0.

[0100] "Carboxyl" means a -CO2H group or its anion.

[0101] "Catalyst" means a compound, typically present in small amounts relative to the reactants, that is capable of catalyzing a synthetic reaction, as would be readily understood by one of ordinary skill in the art. In some embodiments, a catalyst can include a transition metal coordination complex.

[0102] "Cyano" means a -CN group.

[0103] "Cyano" means a -CN group.

[0104] "Alicyclyl" means a cyclic aliphatic group, as defined herein.

[0105] "Cycloalkoxy" means a cyclic alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, a cycloalkoxy group is -O-R, wherein R is a cycloalkyl group, as defined herein.

[0106] "Cycloalkylalkoxy" means an -O-L-R group, wherein L is an alkyl or alkylene group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0107] Unless otherwise indicated, "cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of 3 to 8 carbons, and examples of which are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1. heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group can be substituted with one or more groups including those described herein for alkyl groups. In addition, a cycloalkyl group can include one or more double and / or triple bonds.

[0108] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group, as defined herein.

[0109] "Disilyl" means a group containing a Si-Si bond. In some embodiments, a disilyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - group, wherein R S1 , R S2 , R S3 , R S4 and R S5 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0110] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic as defined herein, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof.

[0111] "Electron donating group" refers to a functional group capable of donating at least a portion of its electron density, e.g., by resonance, into a ring to which it is directly attached.

[0112] "Electron withdrawing group" refers to a functional group capable of accepting electron density from a ring to which it is directly attached, e.g., by inductive electron withdrawal.

[0113] "Halo" means F, CI, Br, or I.

[0114] "Heteroaliphatic" refers to an aliphatic group as defined herein that contains at least one heteroatom within the group, such as one to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, the heteroatoms optionally selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. The heteroaliphatic group is unsubstituted or substituted, e.g., with a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substituents as described herein for aliphatic groups.

[0115] "Haloaliphatic" refers to an aliphatic group as defined herein, wherein one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluorine, bromine, chlorine, or iodine.

[0116] "Haloalkyl" refers to an alkyl group as defined herein, wherein one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluorine, bromine, chlorine, or iodine. In independent embodiments, the haloalkyl group can be a -CX3 group, where each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, the haloalkyl group is -L-X, where L is an alkyl group as defined herein, and X is fluorine, bromine, chlorine, or iodine. In other embodiments, the haloalkyl group is -L-C(X)(R 1 -R 2 where L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine, or iodine; and R 1 and R 2 are each independently H or an alkyl group as defined herein.

[0117] "Heteroaliphatic" refers to an aliphatic group as defined herein that contains at least one heteroatom within the group, such as one to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, the heteroatoms optionally selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. The heteroaliphatic group is unsubstituted or substituted, e.g., with a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substituents as described herein for aliphatic groups.

[0118] "Heteroaliphatic" refers to an aliphatic group as defined herein that contains at least one heteroatom within the group, such as one to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, the heteroatoms optionally selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. The heteroaliphatic group is unsubstituted or substituted, e.g., with a functional group described herein. For example, the heteroaliphatic group can be substituted with one or more substituents as described herein for aliphatic groups.

[0119] "Heteroaliphatic- carbonyl" refers to a heteroaliphatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, a heteroaliphatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0120] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, a heteroaliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0121] "Heteroaliphatic-oxy" refers to a heteroaliphatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxy (-C(O)-). In some embodiments, a heteroaliphatic-oxy is -O-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0122] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, a heteroaliphatic-oxycarbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0123] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" refer to alkyl, alkenyl, or alkynyl groups as defined herein (which can be branched, straight-chain or cyclic), containing within the group at least one heteroatom up to 20 heteroatoms, for example, one to 15 heteroatoms or one to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof.

[0124] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to the polyvalent (e.g., divalent) versions of heteroalkyl, heteroalkenyl, or heteroalkynyl groups as described herein.

[0125] "Heteroaromatic" refers to an aromatic group as defined herein, containing within the group at least one heteroatom up to 20 heteroatoms, for example, one to 15 heteroatoms or one to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. The heteroaromatic group is unsubstituted or substituted, for example, with a functional group described herein. For example, the heteroaromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl groups.

[0126] “Heteroaromatic- carbonyl” refers to a heteroaromatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl (-C(O)-). In some embodiments, a heteroaromatic- carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0127] “Heteroaromatic- carbonyloxy” refers to a heteroaromatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy (-OC(O)-). In some embodiments, a heteroaromatic- carbonyloxy is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0128] “Heteroaromatic- oxy” refers to a heteroaromatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy (-O-). In some embodiments, a heteroaromatic- oxy is -O-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0129] “Heteroaromatic- oxycarbonyl” refers to a heteroaromatic group coupled to or that can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, a heteroaromatic- carbonyl is -C(O)O-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0130] “Heteroaryl” refers to an aryl group comprising at least one heteroatom up to six heteroatoms (e.g., one to four heteroatoms) within the ring, the heteroatoms optionally selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups can have a single ring or multiple condensed rings, which condensed rings can or can not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. A heteroaryl group can be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclyl groups as defined herein that are aromatic, i.e., they contain 4n+2 pi electrons within a single or multiple ring ring system.

[0131] “Heteroarylene” refers to a polyvalent (e.g., divalent) version of a heteroaryl group as described herein.

[0132] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, such as when valence considerations do not permit, a heteroatom does not include a halogen atom.

[0133] Unless otherwise indicated, "heterocyclyl" means a 5-, 6-, or 7-membered ring containing one, two, three, or four heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). A 5-membered ring has 0 to 2 double bonds, and a 6-membered and 7-membered ring has 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings is fused with one, two, or three rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothiophenyl, and the like. Heterocyclyl includes thiolanyl, thietanyl, tetrahydrothiophenyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidinonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolyl, isoquinolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furanyl, thiophenyl, thiazolidinyl, isothiazolyl, isoindolyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxathiolanyl, triazinyl, benzofuranyl, benzothiophenyl, and the like.

[0134] "Heterocyclyloxy" means a heterocyclyl group as defined herein attached through an oxygen atom to the parent molecular group. In some embodiments, a heterocyclyloxy group is -O-R, wherein R is a heterocyclyl group as defined herein.

[0135] "Heterocyclylcarbonyl" means a heterocyclyl group as defined herein attached to the parent molecular group through a carbonyl group. In some embodiments, a heterocyclylcarbonyl group is -C(O)-R, wherein R is a heterocyclyl group as defined herein.

[0136] "Hydrazino" means -NR 1 -NR 2 R3 , where R 1 R 2 and R 3 Each is independently selected from hydrogen, optionally substituted aliphatic groups as defined herein, optionally substituted heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaromatic groups, optionally substituted silyl groups, or optionally substituted siloxy groups, or any combination thereof; or wherein R 1 and R 2 Combination or R 2 and R 3 The combination of these atoms, together with their respective attached nitrogen atoms, can form heterocyclic groups as defined herein. In some embodiments, R 1 R 2 Or R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In a specific embodiment, R 2 and R 3 They can form optionally substituted heterocyclic groups together with their respective attached nitrogen atoms.

[0137] "Hydroxy group" refers to -OH.

[0138] "Hydroxyalkyl" means an alkyl group as defined herein that is substituted with one to three hydroxyl groups, provided that no more than one hydroxyl group can be attached to a single carbon atom of the alkyl group, and examples include hydroxymethyl, dihydroxypropyl, etc. 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 is independently H or an alkyl group as defined herein.

[0139] "Imine" refers to the portion containing a carbon-imino group. In some embodiments, the imino group is C(NR) 1 )R 2 , where R 1 and R 2 Each group is independently selected from hydrogen, optionally substituted aliphatic groups as defined herein, optionally substituted heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted heteroaromatic groups, optionally substituted silyl groups, optionally substituted alkyl groups, optionally substituted aryl groups, optionally substituted alkyl-aryl groups or optionally substituted aryl-alkyl groups, optionally substituted siloxy groups, or any combination thereof. In other embodiments, the imino group is -C(NR) 1 )H、-C(NR 1)R Ak or -C(NR N1 )R Ar wherein R 1 is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, or optionally substituted silyloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic; and R Ar is optionally substituted aryl or optionally substituted aromatic.

[0140] "Imino" refers to a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0141] "Isocyanate" refers to a -NCO group.

[0142] "Isothiocyanate" refers to a -NCS group.

[0143] "Ketone" refers to a -C(O)R or a compound comprising such a group, wherein R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. Examples of ketones can include R 1 C(O)R, wherein R and R 1 are each independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0144] "Nitro" refers to a -NO2 group.

[0145] "Nitroalkyl" refers to an alkyl group as defined herein substituted with one to three nitro groups. In some embodiments, the nitroalkyl is -L-NO2, wherein L is an alkyl group as defined herein. In other embodiments, the nitroalkyl is -L-C(NO)(R 1 )-R 2 wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 are each independently H or an alkyl group as defined herein.

[0146] "Oxo" refers to a =O group.

[0147] "Oxy" means -O-.

[0148] "Perfluoroalkyl" means an alkyl group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2)n-CF3, where n is an integer from 0 to 10. n CF3, where n is an integer from 0 to 10.

[0149] "Perfluoroalkoxy" means an alkoxy group as defined herein in which each hydrogen atom has been replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, where R is a perfluoroalkyl group as defined herein.

[0150] “Salt” refers to ionic forms of a compound or structure (e.g., any formula, compound, or composition described herein) that includes cationic or anionic compounds to form an electrically neutral compound or structure. Salts can be prepared in situ during the final isolation and purification of the compounds of the application, or separately by reacting the free base group with a suitable organic acid (to produce an anionic salt) or by reacting the acid group with a suitable metal or organic salt (to produce a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxymethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, laurylsulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethiodide, tosylate, undecanoate, valerate, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth metal salts, for example, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron and zinc; and nontoxic ammonium, quaternary ammonium, and amino cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylene-diamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Other salts include ammonium, sulfonium, oxosulfonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphinium, pyridinium, and others, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolidinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0151] "Silyl" refers to a -SiR 1 R 2 R 3 or -SiR 1 R 2 group. In some embodiments, R 1 , R 2 and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, R 1 , R 2 and R 3 are each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) cwherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each > 0; and a + b + c = 3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0152] "Siloxy" or "siloxy" refers to a -OR group, wherein R is an optionally substituted silyl group as described herein. In some embodiments, the siloxy group is -O-Si(R) 1 R 2 R 3 wherein R 1 , R 2 and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 are each independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the siloxy group is -O-Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each > 0; and a + b + c = 3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0153] "Sulfinyl" or "sulfinyl group" refers to a -S(O)- group.

[0154] "Sulfo" or "sulfo group" refers to a -S(O)2OH group.

[0155] "Sulfonyl" or "sulfonate" refers to a -S(O)2- group or -SO2R, wherein R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0156] "Thioalkyl" refers to an alkyl group as defined herein attached through a sulfur atom to the parent molecular group. Exemplary unsubstituted thioalkyl groups include C 1-6Thioalkyl. In some embodiments, thioalkyl is -S-R, where R is alkyl as defined herein.

[0157] “Thiol” refers to a -SH group.

[0158] “Halosilane” as used herein refers to a compound comprising one or more silicon-halogen bonds. Examples of halosilanes include difluorosilane (SiH2F2), dichlorosilane (SiH2Cl2), dibromosilane (SiH2Br2), diiodosilane (SiH2I2), dimethyldifluorosilane (Si(CH3)2F2), dimethyldichlorosilane, dimethyldibromosilane, and dimethyldiiodosilane.

[0159] “Dihalogen” as used herein refers to a diatomic molecule comprising two halogen atoms, such as F2, Cl2, Br2, and I2.

[0160] One of ordinary skill in the art will recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such impermissible substitution patterns are readily identified by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted, unless otherwise indicated therein.

[0161] The term “independently selected” (when referring to the selection of R substituents in a molecule containing multiple R groups) means that the selection of R substituents at different atoms in the molecule are independent, and the selection of R substituents at one atom having multiple R substituents is also independent.

[0162] Method In some embodiments, the deposition methods provided herein involve providing a semiconductor substrate (e.g., a semiconductor substrate having one or more recessed features), exposing the substrate to a metal precursor in vapor form, exposing the semiconductor substrate to a halogen-containing deposition activator (where the halogen-containing deposition activator is different from the metal precursor), and exposing the semiconductor to a reducing agent. In some embodiments, the exposures are performed sequentially, such that no two components are flowing into the process chamber at the same time. In other embodiments, the reducing agent and the halogen-containing activator are flowed into the process chamber containing the semiconductor substrate at the same time. In some instances, when the substrate is exposed to a halogen-containing molecule prior to contact with the metal precursor, the deposition process can be inhibited rather than activated. Thus, in some implementations, the substrate is first contacted with the metal precursor, and subsequently contacted with the halogen-containing activator.

[0163] The methods provided (in some embodiments) are used to deposit a metal (e.g., molybdenum, tungsten, titanium, ruthenium, or cobalt) to fill a recessed feature on a semiconductor substrate. FIGS. 1A-1C show schematic cross-sectional views of a semiconductor substrate undergoing metal deposition according to the methods provided herein. FIG. 1A shows a substrate having a recessed feature 101 formed in a material layer 103, which can be a dielectric layer comprising silicon and oxygen. A layer 105, which can comprise a metal silicide and silicon or a metal (e.g., tungsten), is at the bottom of the recessed feature 101. The substrate is lined with a metal nitride layer (e.g., a titanium nitride layer) 107, which is exposed in the field region, on the sidewalls of the recessed feature, and at the bottom of the recessed feature. According to embodiments of the methods provided herein, the substrate is exposed to a metal precursor, followed by exposure to a halogen-containing activating agent and a reducing agent, to deposit a metal layer 109, as shown in FIG. 1B. Next, the exposure to the metal precursor, halogen-containing activating agent, and reducing agent is repeated as many times as needed to deposit a metal film of the desired thickness and to fill the recessed feature (completely or partially). FIG. 1C shows the recessed feature after it is completely filled with metal.

[0164] In another embodiment, a metal-containing layer (e.g., a metal carbide layer) is deposited as a liner between a dielectric layer and a metal layer using the methods provided herein. For example, molybdenum carbide can be deposited instead of titanium nitride as a liner. This is illustrated in FIGS. 2A-2C. FIG. 2A shows a semiconductor substrate having a recessed feature 201 formed in a dielectric layer 203, which can be, for example, a silicon oxide-based dielectric. In the example depicted, the sidewalls of the recessed feature 201 comprise exposed dielectric, while the bottom portion of the recessed feature 201 comprises a different material 205 (e.g., a metal, a metal silicide, or silicon). A metal carbide liner is conformally deposited using the methods provided herein. For example, MoC can be deposited by exposing the substrate to a molybdenum precursor (e.g., MoCl5), an alkyl halide as a halogen-containing activating agent, and a reducing agent (e.g., H2). The resulting structure is shown in FIG. 2B, which shows a conformally deposited layer of molybdenum carbide 207 lining the substrate. Next, a metal, such as tungsten, molybdenum, cobalt, ruthenium, copper, tin, or an alloy comprising any of these metals, is deposited to fill the recessed feature, as shown in FIG. 2C, where 209 is a deposited metal layer filling the recessed feature. The metal can be deposited by any suitable method, such as CVD, electrodeposition, or by the methods provided herein. Other metal-containing films, such as nitrogen-containing films, oxygen-containing films, or boron-containing films, can be obtained by using any reagent (metal precursor, halogen-containing activating agent, or reducing agent) with the desired element (e.g., N, O, or B).

[0165] Deposition in the depicted example can be performed at temperatures between about 250 °C and about 600 °C (e.g., between about 300 °C and 450 °C) and pressures typically less than 300 Torr (e.g., between about 0.1 and about 100 Torr). The metal precursor, reducing agent, and halogen-containing deposition activator are selected so that they can be introduced in vapor form under the deposition conditions. In some embodiments, both the activation step and the reduction step are performed in the same processing chamber or processing station of a deposition apparatus. The reactants (activator, metal precursor, and reducing agent) can be flowed into the processing chamber at flow rates ranging, for example, from 0.5 to 10,000 seem, depending on the implementation with or without an inert carrier gas. In some embodiments, the deposition involves sequential exposure of the substrate to the metal precursor, deposition activator, and reducing agent, with each exposure lasting between about 1 second and about 500 seconds, for example, between about 5 and 50 seconds. In an exemplary implementation, the deposition process utilizes t-butyl chloride as the activator, MoCl5as the metal precursor for depositing molybdenum carbide, and H2as the reducing agent. Such deposition can be used to deposit molybdenum carbide or molybdenum metal. In some embodiments, the molybdenum carbide or carbon-rich molybdenum obtained using an alkyl halide activator is treated to increase the molybdenum content and reduce the carbon content in the film.

[0166] Several exemplary process flows for deposition methods using halogen-containing activators are shown in FIGS. 3A and 3B. These methods can be used to fill recessed features with metal and to form metal-containing liners (e.g., to form conformal MoC liners).

[0167] In some embodiments, the activation with a halogen-containing activator will be integrated into the ALD process, as shown in the process flow diagram of Figure 3A. The process begins with contacting the substrate with a metal precursor in step 301. The substrate can be any of the substrates described herein, such as a substrate having an exposed metal layer, metal nitride layer, metal oxide layer, silicon layer, or silicon-containing dielectric layer. For example, the substrate can have the structure shown in Figure 1A, having an exposed titanium nitride layer lined on the surface of the substrate in the field region, on the feature sidewalls, and at the feature bottom. In another embodiment, the substrate has the structure shown in Figure 2A. As the substrate is exposed to the metal precursor, the metal precursor is allowed to adsorb to the surface of the substrate. In some embodiments, the metal precursor is flowed into the process chamber in the absence of any co-flowing gas. In other embodiments, the metal precursor is flowed into the process chamber with an inert carrier gas, such as nitrogen, argon, or helium. Next, the metal precursor flow is stopped, and the substrate is contacted with a halogen-containing activator in step 303. The activator can be introduced into the process chamber with or without a carrier gas, and allowed to adsorb to the surface of the substrate. After stopping the activator flow, the process continues to step 305, in which the substrate is exposed to a reducing agent, and a metal-containing layer is formed. After stopping the reducing agent flow, the process can continue in step 307 by repeating steps 301-305 until the metal-containing film is deposited to the desired thickness. For example, at least 2 deposition cycles can be performed, such as 2-2,000 cycles (e.g., 200-2,000 cycles), where each cycle includes each of steps 301, 303, and 305. Optionally, the deposition cycles can also include a purge step after one or more of steps 301, 303, and 305. In some embodiments, the process chamber is purged with a purge gas, such as nitrogen or argon, after each of steps 301, 303, and 305 to remove any unadsorbed reactants from the process chamber.

[0168] Next, the process can continue in step 309 by treating the semiconductor substrate to increase the metal content in the deposited film. This step is optional, and can be used in embodiments where the content of other elements, such as carbon, nitrogen, oxygen, or boron, in the deposited metal-containing film is too high for its desired use. For example, if a low carbon metal film is needed to fill a recessed feature, and the film formed has a higher than desired carbon content (e.g., due to the carbon incorporated in the alkyl halide activator), the film can be treated to increase its metal content. In some embodiments, the treatment is a hydrogen anneal. The substrate with the exposed film is contacted with hydrogen at a higher temperature and / or for a longer time than step 305. For example, the metal-containing film formed can be deposited at a temperature between about 250 °C and about 450 °C, and then can be annealed in a hydrogen atmosphere at a temperature of at least about 500 °C, such as at a temperature of at least about 650 °C (e.g., a temperature between about 700 °C and 800 °C). In some embodiments, the hydrogen anneal step is at least 2 times longer than step 305 of the deposition process.

[0169] In another embodiment, exposing the formed film to a metal halide for an extended period of time can increase the metal content in the formed film. For example, a deposited carbon-rich molybdenum film or molybdenum carbide film can be treated with MoCl5to increase the molybdenum content in the film. The treatment is typically longer (e.g., at least 2 times longer) than the exposure to the molybdenum precursor during deposition and can be used to reduce the carbon content by converting the carbon to volatile carbon tetrachloride, which can be removed from the processing chamber.

[0170] Halogen-containing activating agents can increase the deposition rate even when they are introduced simultaneously (along with) a reducing agent. Further, in some embodiments, such simultaneous exposure can result in a higher metal content in the formed metal-containing film. An example of a processing sequence in which a reducing agent and a halogen-containing activating agent are co-flowed into a processing chamber is shown in FIG. 3B. The process begins at step 311 by contacting a semiconductor substrate with a metal precursor. This step is performed in the absence of a simultaneous flow of a halogen-containing activating agent, but can optionally include a simultaneous flow of a reducing agent. Next, the flow of the metal precursor is stopped, the processing chamber is optionally purged (e.g., with an inert gas or hydrogen), and the semiconductor substrate is contacted with a reducing agent and a halogen-containing activating agent at step 313. In this embodiment, the reducing agent and the halogen-containing activating agent are co-flowed into the processing chamber, but there is no flow of the metal-containing precursor. In some embodiments, the flow rate of the halogen-containing activating agent is between about 10 seem and 40 seem. Next, after forming a first portion of the metal-containing layer, the process optionally continues at step 315 by repeating steps 311 and 313. The process can include multiple deposition cycles as needed to form a metal-containing layer of a desired thickness. For example, at least 2 deposition cycles, such as 2-2,000 cycles (e.g., 200-2,000 cycles), can be performed, where each cycle has one step 311 and one step 313. Next, if desired, the process can continue to step 317, where the substrate can be treated to increase the metal content in the deposited film. The treatment can be performed as previously described for step 309.

[0171] Halogen-containing deposition activators Halogen-containing deposition activating agents include, but are not limited to, alkyl halides, halosilanes, dihalogens, halides of Group 13 elements, halides of Group 15 elements, and metal halides.

[0172] Alkyl halides that can be used in any of the methods provided herein include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides, and can include one or more halogen atoms. Primary, secondary, and tertiary alkyl halides can be used. Examples of primary alkyl halides include methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, 1-fluoropropane, 1-chloropropane, 1-bromopropane, and 1-iodopropane, 1-fluorobutane, 1-chlorobutane, 1-bromobutane, and 1-iodobutane. Examples of secondary alkyl halides include 2-fluoropropane, 2-chloropropane, 2-bromopropane, 2-iodopropane, 2-fluorobutane, 2-chlorobutane, 2-bromobutane, and 2-iodobutane. In some embodiments, tertiary alkyl halides are preferred. Examples of tertiary alkyl halides include tert-butyl fluoride (also known as 2-fluoro-2-methylpropane), tert-butyl chloride (also known as 2-chloro-2-methylpropane), tert-butyl bromide (also known as 2-bromo-2-methylpropane), and tert-butyl iodide (also known as 2-bromo-2-methylpropane).

[0173] In some embodiments, an alkyl halide having the following formula is used: Hal - C(R’)2 - CH(R’’)2, where Hal is a halogen, each R’ is independently selected from hydrogen and alkyl, and each R” is independently selected from hydrogen and alkyl. In some embodiments, both R” groups are hydrogen. Examples of such alkyl halides include tert-butyl chloride, 2-chloro-2-methylbutane, 2-chloro-2-methylpentane, and 2-chloro-2-methylhexane.

[0174] Halo-silanes refer to molecules having a silicon-halogen bond. Examples of halo-silanes include SiH2F2, SiH2Cl2, SiH2Br2, and SiH2I2.

[0175] Examples of dihalogens are F2, Cl2, Br2, and I2.

[0176] Examples of halides of Group 13 elements include boron halides (e.g., boron trichloride (BCl3) and boron tribromide (BBr3)), aluminum halides (e.g., aluminum trichloride and aluminum tribromide), and gallium halides. Examples of halides of Group 15 elements include nitrogen halides, phosphorus halides, and antimony halides.

[0177] In some embodiments, the metal precursor used for deposition and the halogen-containing activator include the same halogen (e.g., chlorine). For example, the metal precursor can include a metal-chlorine bond, and the activator can be an alkyl chloride. In other embodiments, the metal precursor and the halogen-containing activator can have different halogens. For example, the metal precursor can include a metal-chlorine bond, and the halogen-containing activator can include a halogen different from chlorine (e.g., I or Br).

[0178] In some embodiments, chlorine-containing deposition activators are used. Examples of chlorine-containing deposition activators include, but are not limited to, hydrogen chloride (HC1), chlorine (C12), t-butyl chloride, chlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHC13), and silicon tetrachloride (SiCI4). In some embodiments, bromine-containing deposition activators are used. Examples of bromine-containing deposition activators include, but are not limited to, hydrogen bromide (HBr), bromine (Br2), t-butyl bromide, bromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (SiHBr3), and silicon tetrabromide (SiBr4). Other examples of bromine-containing deposition activators include titanium tetrabromide, tungsten pentabromide, tungsten hexabromide, boron tribromide, and aluminum tribromide.

[0179] In some embodiments, iodine-containing deposition activators are used. Examples of iodine-containing deposition activators include hydrogen iodide (HI), iodine (I2), t-butyl iodide (C4H9I), allyl iodide (C3H5I), iodosilane (SiH3I), diiodosilane (SiH2I2), triiodosilane (SiHI3), and silicon tetraiodide (SiI4). Other examples of iodine-containing deposition activators include titanium tetraiodide, boron triiodide, and aluminum triiodide.

[0180] Metal precursors According to embodiments provided herein, the provided methods can use various metal precursors to deposit a metal. The precursors are selected so that they can be delivered to the processing chamber in a gaseous (e.g., vapor) form, either alone or with an inert carrier gas. For example, an inert gas flowing through a solid or liquid precursor can deliver the precursor to the processing chamber. Examples of metals that can be deposited using vapor deposition (e.g., ALD and CVD deposition) include molybdenum, tungsten, cobalt, and ruthenium.

[0181] Molybdenum precursors In general, the molybdenum-containing precursors can include molybdenum in a wide range of oxidation states from 0 to +6. In some embodiments, it is preferred that the molybdenum compounds have molybdenum in low oxidation states of +3, +4, and +5. The provided methods are particularly useful for depositing molybdenum-containing materials from halogen-containing molybdenum-containing compounds, as silicon-containing reactants can assist in halogen scavenging; however, halogen-free molybdenum-containing precursors can also be used. Suitable molybdenum-containing precursors include halides and oxyhalides of molybdenum, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides, and oxybromides, in which the molybdenum can be in any oxidation state from +2 to +6.

[0182] To maintain suitable volatility, precursors having a molecular weight of less than about 450 g / mol (e.g., less than about 400 g / mol) are selected in many embodiments discussed herein.

[0183] In some embodiments, the molybdenum-containing precursor has the chemical formula of 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.

[0184] In some embodiments, the molybdenum-containing precursor includes a carbonyl ligand.

[0185] Halide-containing heteroleptic molybdenum compounds In one aspect, a halide-containing hetero-ligating molybdenum compound is used as a precursor for deposition of a molybdenum-containing film, for example, as a precursor for deposition of molybdenum metal. In one embodiment, the precursor is a compound that includes molybdenum, at least one halide that forms a bond with molybdenum, and at least one organic ligand having any one of the elements N, O, and S, where an atom of any one of these elements forms a bond with molybdenum. Examples of suitable organic ligands that provide a nitrogen or oxygen bond include amidinates, amidates, iminopyrrolidinates, diazadienes, beta-imino amides, alpha-imino alkoxides, beta-amino alkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates. Examples of suitable organic ligands that provide a sulfur bond include thioethers, thiolates, dithiolenes, dithiolates, and alpha-iminothiolenes. These ligands can be substituted or unsubstituted. In some embodiments, these ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy. These organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in various oxidation states, for example, +1, +2, +3, +4, +5, and +6.

[0186] Suitable exemplary N- and / or O-containing organic ligands 1-17 are shown in FIG. 4, and suitable exemplary S-containing organic ligands 18-25 are shown in FIG. 5, where each 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, i-propyl, i-butyl, 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 having branched alkyl substituents (e.g., i-propyl and i-butyl) are preferred because such ligands provide more volatile molybdenum precursors.

[0187] 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 (e.g., ethylenediamine, unsubstituted or N-alkyl-substituted), and higher dentate amines (e.g., diethylenetriamine, substituted or unsubstituted). 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, the 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, the at least one organic ligand is an imide, such as dianionic imide 17, where R is alkyl or fluoroalkyl. While imide-containing precursors can generally be used to deposit a variety of molybdenum-containing films, including molybdenum metal, in some embodiments they are more suitable for depositing molybdenum nitride and molybdenum carbonitride because they form strong molybdenum-nitrogen bonds and can act as a nitrogen source for the resulting film. 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 monoanionic ligand that can form two molybdenum-nitrogen bonds, acting as a bidentate ligand.

[0188] In some embodiments, at least one organic ligand in the precursor is an amidate. An example of an amidate is amidate 3 shown in FIG. 2, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidate 3 is a monoanionic ligand that can form one molybdenum-nitrogen bond and one molybdenum-oxygen bond, acting as a bidentate ligand.

[0189] In some embodiments, at least one organic ligand in the precursor is a diazadiene. Examples of diazadienes are 1,4-diazine 1,3-butylenes (DADs) 5, 6, and 7, where each R is independently selected from H, alkyl, and fluoroalkyl. The interesting property of this ligand is that it can exist in a neutral form 5, a monoanionic radical form 6, and a dianionic form 7. Due to the redox activity of the monoanionic (radical) form 6, it can be relatively easily removed during deposition, making complexes of DAD 6 particularly suitable 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 includes DAD ligand 5, 6, or 7 as an organic ligand, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0190] In some embodiments, the at least one organic precursor is an imino pyrrolidine salt (e.g., imino pyrrolidine salt 4, where each R is independently selected from H, alkyl, and fluoroalkyl), a β-imino amide (e.g., β-imino amide 8, where each R is independently selected from H, alkyl, and fluoroalkyl), an α-imino alkoxide (e.g., α-imino alkoxide 9, where each R is independently selected from H, alkyl, and fluoroalkyl), a β-diketiminate salt (e.g., β-diketiminate salt 10, where each R is independently selected from H, alkyl, and fluoroalkyl), a β-ketiminate salt (e.g., β-ketiminate salt 11, where each R is independently selected from H, alkyl, and fluoroalkyl), a β-diketonate (e.g., β-diketonate 12, where each R is independently selected from H, alkyl, and fluoroalkyl), a pyrazole salt (e.g., pyrazole salt 13, where each R is independently selected from H, alkyl, and fluoroalkyl), a β-amino alkoxide (e.g., β-amino alkoxide 14, where each R is independently selected from H, alkyl, and fluoroalkyl), or a guadinidate (e.g., guadinidate 15, where each R is independently selected from H, alkyl, and fluoroalkyl). These are all monoanionic ligands that can bind to molybdenum in a bidentate coordination fashion.

[0191] In some embodiments, the at least one organic precursor is a sulfur-containing ligand that is capable of forming a molybdenum-sulfur bond. In some embodiments, at least one organic ligand in the precursor is a sulfide. The term "sulfide" as used broadly herein includes monodentate and polydentate (e.g., bidentate or tridentate) sulfides, as well as ligands containing sulfide and thiolate (or other) moieties. An example of a monodentate sulfide is a dialkyl sulfide R2S, where each R is an alkyl group, such as dimethyl sulfide, diethyl sulfide, diisobutyl sulfide, and the like. An example of a polydentate sulfide ligand that also includes a thiolate moiety is (SCH2CH2SCH2CH2S) 2-Examples of monodentate thioethers are thioethers 18 shown in Figure 5, 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, i-propyl, n-butyl, i-butyl, sec-butyl, and t-butyl.

[0192] In some embodiments, the at least one organic ligand is a thiolate, such as monanionic thiolate 19, where R is alkyl or fluoroalkyl. For example, R can be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, or t-butyl. In some embodiments, the thiolate is a dithiolate, such as dianionic a-dithiolate 24 (where each R is independently selected from H, alkyl, and fluoroalkyl) or dianionic β-dithiolate 25 (where each R is independently selected from H, alkyl, and fluoroalkyl). Dithiolates are capable of forming two molybdenum-sulfur bonds.

[0193] In some embodiments, at least one organic ligand in the precursor is a dithiolene. Examples of dithiolenes are structures 20, 21, and 22, where each R is independently selected from H, alkyl, and fluoroalkyl. This ligand (similar to DAD) can exist in a neutral form 20, a monanionic radical form 21, and a dianionic form 22. Due to the redox activity of the monanionic radical form 21, it can be relatively easy to remove during deposition and reduction of the molybdenum precursor, making complexes of dithiolene 21 particularly suitable for depositing molybdenum metal and high purity molybdenum metal. Dithiolene ligands 20, 21, and 22 can each be capable of forming two molybdenum-sulfur bonds as bidentate ligands. In some embodiments, the molybdenum precursor includes dithiolene ligand 20, 21, and / or 22 as an organic ligand, where each R is independently selected from methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, i-butyl, and t-butyl.

[0194] In some embodiments, at least one organic ligand in the precursor is an a-iminothiolene, such as structure 23, where each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each R substituent at the carbon atom is independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy, while the R substituent at the nitrogen atom is independently selected from alkyl and fluoroalkyl. In some embodiments, the R substituent at the nitrogen is independently selected from methyl, ethyl, propyl, i-propyl, n-butyl, sec-butyl, i-butyl, and t-butyl. This ligand (similar to DAD and dithiolene) has a monanionic radical form, as shown in structure 23, which is redox active and can be easily removed during reduction processing.

[0195] In some embodiments, the precursor is of the formula Mo(X) m (L) ncompounds of formula (I) wherein m is selected from 1-4, n is selected from 1-3, each X is independently selected from halides of F, CI, Br, and I, and each L is an organic ligand as described above, such as a ligand independently selected from amidinate, etimide, imidopyrrolide, diazadiene, beta-iminoamide, alpha-iminoalkoxide, beta-aminoalkoxide, beta-diketiminate, beta-ketiminate, beta-diketone, amine, and pyrazolide, sulfide, thiolate, disulfide, dithiolate, and alpha-iminothiolate. In some embodiments, each R in the nominated ligand is independently selected from H, alkyl, and fluoroalkyl.

[0196] In some embodiments, L is a bidentate ligand. Examples of suitable molybdenum-containing precursors that employ bidentate ligands and have the formula Mo(L)Cl4are shown in FIG. 6. These molybdenum-containing precursors are Mo(V) compounds and include amidinate molybdenum complex 27, DAD complex 28, beta-diketiminate complex 29, pyrazolide complex 30, etimide complex 31, beta-iminoamide complex 32, beta-ketiminate complex 33, beta-aminoalkoxide complex 34, imidopyrrolide complex 35, alpha-iminoalkoxide complex 36, and beta-diketiminate complex 37.

[0197] Heteroleptic complexes having a molybdenum-halide bond and an organic ligand as described herein can be synthesized by using a reaction between a molybdenum halide starting material and a compound comprising the organic ligand in neutral or anionic form. For example, MoCl5can be used as a starting material to prepare molybdenum(V) precursors. MoX3(THF)3, where X is selected from chloride, bromide, and iodide, and THF is tetrahydrofuran, can be used as a starting material to prepare Mo(III) precursors. The starting material can be treated with the ligand in neutral or anionic form (e.g., a salt, such as a lithium salt or a sodium salt) to form the heteroleptic complexes described herein.

[0198] Heteroleptic molybdenum compounds containing a molybdenum-halide bond and an organic ligand as described herein can advantageously provide high purity molybdenum metal in the CVD and ALD type deposition processes provided herein. In addition, the use of these compounds can be associated with reduced etching of the substrate material as 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 to deposition on substrates that are sensitive to etching.

[0199] In some embodiments, fluorine-free precursors are selected when depositing on materials that are sensitive to fluorine, such as silicon-containing materials, for example, including any of CI, Br, and I as the halide in the complex. In addition, the use of compounds having fluoroalkyl substituents can be avoided in these embodiments.

[0200] Sulfur-containing molybdenum compounds In one aspect, sulfur-containing molybdenum compounds are used as molybdenum-containing precursors for deposition of molybdenum-containing films, such as molybdenum metal and molybdenum silicide deposition. In some embodiments, the molybdenum compound includes molybdenum and at least one sulfur-containing ligand that provides a molybdenum-sulfur bond. Molybdenum precursors based on sulfur-containing ligands can be used to deposit molybdenum-containing films that are substantially free of impurities because sulfur impurities are more easily removed than oxygen, carbon, and nitrogen impurities. In some embodiments, the molybdenum compound does not include a molybdenum-carbon bond and / or does not include a molybdenum-oxygen double bond. In some embodiments, the molybdenum compound does not include a molybdenum-nitrogen double bond. In some embodiments, in the provided molybdenum precursors, molybdenum forms bonds only with sulfur atoms.

[0201] Examples of suitable sulfur-containing ligands that provide a sulfur bond include sulfides, thiolates, dithiolenes, dithiolates, thiocarbamates, and a-iminothiolenes. These ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy. These organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in various oxidation states, such as 0, +1, +2, +3, +4, +5, and +6.

[0202] In some embodiments, the sulfur-containing ligand is a ligand 18-25 shown in FIG. 5, where the R substituents are as previously described. An example of a suitable molybdenum precursor includes a thiolate molybdenum Mo(SR)4, where R is an alkyl group, such as methyl, ethyl, propyl, butyl. In one specific example, the precursor is tetrakis(tert-butylthiolate) molybdenum(IV): Mo(SR)4, where R is tert-butyl. Another example of a suitable molybdenum precursor is a thiocarbamate molybdenum, such as tetrakis(diethyldithiocarbamate) molybdenum(IV): where each R is independently selected from alkyl (e.g., ethyl, methyl, propyl, butyl) and fluoroalkyl (e.g., CF3). In one specific example, the precursor is tetrakis(diethyldithiocarbamate) molybdenum(IV).

[0203] In some embodiments, provided are dithiolen complexes of molybdenum, where the dithiolen can be in a neutral form 20, an anion-radical form 21, and a dianion form 22, where each R is independently H, alkyl, or fluoroalkyl.

[0204] Dithiolen complexes are redox active and can complex molybdenum in various oxidation states. The redox reactions of dithiolen ligands 20, 21, and 22 are shown in Reaction 1: In one implementation, the precursor is Mo(21)3, where each R in 21 is independently selected from H, alkyl, and fluoroalkyl. For example, R can be methyl, ethyl, CF3, etc. This is a homoleptic Mo(III) compound containing only molybdenum-sulfur bonds.

[0205] In some embodiments, in addition to sulfur bonding, these ligands can also provide nitrogen bonding. One example of such a ligand is a-thioimino sulfene 23, which can exhibit redox active radical anion behavior similar to that of sulfene. In some embodiments, the precursor is a Mo(III) compound: Mo(23)3, where each R in 23 is independently selected from H, alkyl, and fluoroalkyl.

[0206] In some embodiments, the precursor is a MoLn compound, where n is from 2 to 6, and L is a sulfur-containing ligand, such as any of those described herein. In some embodiments, each L is the same sulfur-containing ligand. In other embodiments, the precursor can 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 by reaction of a molybdenum halide starting material with a compound containing an organic sulfur-containing ligand in neutral or anionic form. For example, Mo(V) precursors can be prepared using MoCl5 as a starting material. Mo(III) or Mo(IV) precursors can be prepared by using a 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 can be treated with the desired sulfur-containing ligand in neutral or anionic form (e.g., a salt, such as a lithium or sodium salt) to form the sulfur-containing complex described herein.

[0207] In one example, a Mo(IV) thiolate complex is prepared by reacting molybdenum tetrachloride with a lithium thiolate. For example, MoCl4 can be reacted with t-BuSLi in a solvent, 1,2-dimethoxyethane, to form a Mo(t-BuS)4 compound.

[0208] The a-imino thiolene ligands can be prepared from the corresponding a- iminoketone by thionation with a suitable reagent (e.g., Lawesson's reagent). The radical anion form of the a-imino thiolene can then be prepared by treatment with an alkali metal (e.g., lithium). The resulting ligand and ligand salts can be reacted with a molybdenum halide to form the a-imino thiolene-containing molybdenum compound.

[0209] Molybdenum complexes can also be prepared by using zerovalent starting materials (e.g., hexacarbonylmolybdenum). The starting material can be treated with a neutral ligand (e.g., a sulfide or a dialkyl sulfide) to initiate a redox- neutral ligand exchange. The zerovalent starting material can also be treated with a ligand precursor such as bis(diethylthioformamidyl)disulfide or bis(trifluoromethyl)- 1,2-dithiete to initiate an oxidative addition reaction and form the sulfur-containing complexes described herein.

[0210] These reactions can be carried out in a variety of aprotic solvents. For example, the reactions can be carried out in an ether solvent (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane), in a hydrocarbon solvent (e.g., toluene, benzene, heptane, hexane, pentane), or a halogenated hydrocarbon solvent (e.g., chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc.). Depending on the boiling point of the solvent and the solubility of the product, these reactions can be carried out over a wide range of temperatures. In some embodiments, the starting materials, reaction intermediates, and desired products are unstable to water vapor and oxygen. Therefore, the reaction work-up should be carried out under anhydrous and air-free conditions, and using an inert gas with protection (e.g., nitrogen or argon).

[0211] 1,4-Diaza-diamantane (DAD)-containing precursors In another aspect, DAD-containing molybdenum precursors are provided. DAD can bind to molybdenum in neutral form 5, radical-anion form 6, and dianion form 7. In some embodiments, homoleptic DAD complexes of the formula Mo(DAD)m are provided, where m is from 1 to 3, and each DAD is independently selected from neutral DAD 5, radical-anion DAD 6, and dianion DAD 7. The oxidation state of molybdenum in these complexes can range from 0 to +6. Non-limiting examples of suitable homoleptic DAD complexes include tri(DAD)Mo(III) precursor Mo(6)3, bis(DAD)Mo(IV) precursor Mo(7)2, bis(DAD)Mo(III) precursor Mo(6)(7), and bis(DAD)Mo(II) precursor Mo(6)2.

[0212] In some embodiments, homoleptic DAD complexes are prepared by using a reaction between a molybdenum halide and a source of DAD ligand in the desired electronic configuration. For example, the tri(DAD)Mo(III) precursor Mo(6)3can be synthesized by reacting MoCl3with three equivalents of the free-radical anion form of the DAD ligand, which can be prepared by treating the neutral form of the DAD ligand with an alkali metal (e.g., lithium) in a solvent (e.g., THF), as shown in Reaction 2: (Reaction 2) In some embodiments, heteroleptic DAD-containing molybdenum compounds are provided. In some implementations, the precursor includes molybdenum, at least one DAD ligand bonded to the molybdenum, and at least one second ligand, where the DAD can be neutral DAD 6, free-radical anion DAD 7, or dianion DAD 8, and the second ligand is independently selected from anionic ligands and neutral ligands. 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, and each L is independently selected from CO, amines, phosphines, sulfides, nitriles, and isonitriles, and X is an anionic ligand, and each X is independently selected from halides, alkyls, allyls, and cyclopentadienyls, and m is 1-3, n is 0-4, and p is 0-4. Nitriles are RCN compounds, where R is an alkyl group. Isonitriles are RNC compounds, where R is an alkyl group. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligand containing donor atoms selected from C, N, O, B, S, Si, Al, and P.

[0213] 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)3, Mo(6)(13)Cl, Mo(6)(18)Cl2, Mo(6)2Cl, Mo(6)2(14), Mo(6)2(19), Mo(6)2(24).

[0214] Heteroleptic DAD-containing precursors can be prepared by one pot or sequential salt metathesis reactions in multiple steps. The molybdenum halide starting material, such as Mo(V), Mo(IV), or Mo(III) halide, can be treated with an anionic form of the DAD ligand or other anionic ligand. The neutral Lewis base ligand can be exchanged using thermal treatment or photoexcitation.

[0215] A zerovalent molybdenum starting material (e.g., molybdenum hexacarbonyl) can also be used to prepare the heteroleptic DAD-containing precursors, where the zerovalent molybdenum starting material can undergo an oxidative addition reaction with a redox-active ligand (e.g., a DAD ligand).

[0216] In some embodiments, precursors containing the radical anion DAD ligand 8 are particularly suitable for the deposition of molybdenum metal and high purity molybdenum metal. In the radical anion form 7, the DAD ligand couples with the empty d orbital electrons of molybdenum and is believed to act as an electron source for the reduction of molybdenum ions to the zerovalent metal state. After the ligand-to-metal electron transfer has occurred, the volatile neutral DAD ligand 6 can be purged from the molybdenum metal growth surface. Since the DAD ligand can be removed from the growth surface without damage, incorporation of impurity elements (e.g., C and N) is reduced when using DAD precursors compared to other metalorganic precursors. Thus, molybdenum precursors containing the radical anion DAD ligand can be used to deposit high purity molybdenum metal at low temperatures.

[0217] Dimolybdenum precursors In another aspect, the precursors for depositing molybdenum-containing films are dimolybdenum compounds containing a molybdenum-molybdenum bond (e.g., a multiple molybdenum-molybdenum bond, such as a double bond; or any multiple bond having a bond order of 2-5). Such precursors are particularly suitable for the deposition of molybdenum metal and high purity molybdenum metal, since it is easier to reduce such compounds to metallic molybdenum than many mononuclear molybdenum compounds.

[0218] In some embodiments, provided are precursors for depositing molybdenum-containing films, where the precursors are Mo2L n where each L is independently selected from the group consisting of an imidazolide, amidinate, and guanidinate ligand, n is 2-5, and the precursor includes a multiple molybdenum-molybdenum bond. In some embodiments, each L is independently selected from the group consisting of amidinate ligand 2, imidazolide ligand 3, and guanidinate ligand 15, where each R in the amidinate, imidazolide, and guanidinate is independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. In some embodiments, each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments, each L is an amidinate, and the precursor has the chemical formula Mo2(L)3or Mo2(L)4. In some embodiments, each L is an amidinate, and the precursor has the chemical formula Mo2(L)3or Mo2(L)4. In some embodiments, each L is a guanidinate, and the precursor has the chemical formula Mo2(L)3or Mo2(L)4. In these complexes, molybdenum has a low oxidation state of 2+ (in Mo2(L)3) and 3+ (in Mo2(L)4), making these complexes particularly suitable for easy reduction to molybdenum metal.

[0219] Structure 38 shows an exemplary structure of an etomidate paddlewheel di-Mo(II) precursor with four molybdenum-molybdenum bonds: In some embodiments, R and R' are each independently selected from alkyl groups, such as methyl, ethyl, isopropyl, and tert-butyl. In some embodiments, one, two, three, or four of the etomidate ligands in 38 can be replaced with amidate or guanidinate ligands.

[0220] Di-molybdenum tetracetate can be used as a starting material and treated with a ligand salt, such as lithium etomidate, to synthesize the di-molybdenum precursors described herein.

[0221] Cobalt precursors Other suitable molybdenum-containing precursors are shown in FIG. 6B, where each L is a carbon-containing ligand that does not form a metal-carbon bond, and where m is an integer between 1-4, and n is an integer between 1-4. Each R and R1is independently selected from the group consisting of alkyl, fluoroalkyl, and alkylsilyl groups. In some embodiments, each R1is selected such that it does not provide a beta hydrogen atom. Examples of such R1substituents include tert-butyl and trialkylsilyl substituents. Note that in some embodiments, R substituents at the O and S atoms can provide beta hydrogen atoms, as beta hydrogens are not readily eliminated at these positions and are not expected to cause carbon contamination of the resulting film. In some embodiments, neither R nor R1provides a beta hydrogen atom. In some embodiments, the precursor does not contain a beta hydrogen atom. More specific examples of molybdenum-containing precursors are shown in FIG. 6C, which depicts structures 55-58.

[0222] Cobalt precursors Cobalt metal can be deposited by using various 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., bis(acetylacetonate) cobalt(III)), cobalt amidinate (e.g., bis(N-tert-butyl-N'-ethylpropionamidinate) cobalt(II)), cobaltocene, and carbonyl-containing cobalt precursors (e.g., tricarbonyl nitrosyl cobalt, and dicarbonyl cyclopentadienyl cobalt). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N , N , N ′, N ′-tetramethylethylenediamine.

[0223] Ruthenium precursors Ruthenium metal can be deposited, for example, by using vaporizable ruthenium precursors, such as bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienyl-propylcyclopentadienyl ruthenium(II).

[0224] Tungsten precursors Tungsten-containing layers can be deposited by using various volatile precursors. In some embodiments, a halogen-containing tungsten precursor is used, such as WHalx, where Hal is a halogen (e.g., F, CI, Br, and / or I) and x is from 2 to 6. In some embodiments, a tungsten chloride is used. Tungsten chlorides include tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In other examples, a tungsten fluoride can be used, such as tungsten hexafluoride.

[0225] Titanium precursors Titanium-containing layers can be deposited using several suitable volatile precursors, including titanium halides, such as TiHal x where Hal is a halogen (e.g., F, CI, Br, and / or I) and x is 1 to 4. Other titanium precursors include titanium alkoxides (e.g., Ti(OR)4, where R is an alkyl group) and titanium alkyl amides (e.g., Ti(NR2)4, where R is an alkyl group). Examples of titanium precursors include titanium tetrachloride (TiCl4), titanium dichloride (TiCl2), titanium tetraisopropoxide (Ti(O i Pr)4), titanium tetraethoxide (Ti(OEt)4), titanium tetra(diethyl)amide (Ti(NMe2)4), and titanium tetra(diethylamido) (Ti(NMe2)4).

[0226] Reduction agents Many reducing agents can be used to deposit the metal-containing films provided herein. Examples of suitable reducing agents include hydrogen (H2), ammonia (NH3), hydrazine (N2H4), amines, diborane (B2H6), silane (SiH4), disilane (Si2H6), alcohols, hydrogen sulfide (H2S), or mercaptans. In some embodiments, the reducing agent is hydrogen (H2).

[0227] Various metal-containing layers can be deposited using the methods provided herein. For example, metal layers (e.g., molybdenum, tungsten, ruthenium, cobalt, and titanium layers), metal carbides (including metal carbonitrides), metal nitrides, and metal borides can be deposited. Examples of metal carbide layers include molybdenum carbide (MoC and MoCN) and tungsten carbide layers. Examples of metal nitride layers include molybdenum nitride layers, titanium nitride layers, and tungsten nitride layers. The type of layer deposited can be selected by choosing an appropriate combination of metal precursor, halogen-containing activating agent, and reducing agent, such that at least one of these agents provides the necessary element (in addition to the metal element). For example, a metal carbide can be deposited by choosing reagents such that at least one of the metal precursor, halogen-containing activating agent, and reducing agent contains carbon. In some embodiments, an alkyl halide activating agent can provide the carbon needed to deposit a metal carbide. Similarly, a metal nitride can be deposited by choosing reagents such that at least one of the metal precursor, halogen-containing activating agent, and reducing agent contains nitrogen. For example, a nitrogen-containing metal precursor and / or a nitrogen-containing reducing agent (e.g., NH3) can be used to provide nitrogen for depositing metal nitrides and nitrogen-containing metal carbides (e.g., carbonitrides). Alternatively, an additional volatile reagent can be added to provide the necessary element. For example, H2may be added as a reducing agent, while NH3may be an additional reagent to provide nitrogen in the deposition of metal nitrides.

[0228] Apparatus The deposition methods described herein can be performed in a variety of apparatuses. Suitable apparatuses include a process chamber having one or more input ports for introducing one or more reactants; a substrate holder located in the process chamber and configured to hold a substrate in place during deposition; and optionally a plasma-generating mechanism configured to generate a plasma in the process gas. In general, the methods provided herein do not require activation of the reactants by a plasma, and can be performed without plasma treatment. The apparatus can include a controller having program instructions to cause performance of any of the method steps described herein. The deposition methods described herein can be performed in corresponding ALD and CVD apparatuses available from Lam Research Corp. (Fremont, CA), such as the Halo, Altus®, Vector®, and Striker® tools.

[0229] For example, in some embodiments, the apparatus includes a controller having program instructions including instructions for contacting a semiconductor substrate with a metal precursor, contacting the semiconductor substrate with a halogen-containing deposition activating agent, where the halogen-containing deposition activating agent is different from the metal precursor, and contacting the semiconductor substrate with a reducing agent to form a metal-containing material (e.g., molybdenum or molybdenum carbide) layer. The controller can include program instructions for causing any of the methods described herein.

[0230] An example of a deposition apparatus suitable for depositing a metal-containing film using the provided methods is shown in FIG. 7. FIG. 7 schematically illustrates an embodiment of a processing station 700 that can be used to deposit materials using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which can be plasma-enhanced. For simplicity, the processing station 700 is depicted as a standalone processing station having a process chamber body 702 for maintaining a low pressure environment. However, it should be appreciated that multiple processing stations 700 can be included in a common processing tool environment. Moreover, it should be appreciated that, in some embodiments, one or more hardware parameters of the processing station 700, including those discussed in detail below, can be adjusted programmatically by one or more computer controllers.

[0231] The processing station 700 is in fluid communication with a reactant delivery system 701 to deliver process gases to a distribution showerhead 706. The reactant delivery system 701 includes a mixing vessel 704 for blending and / or conditioning process gases for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 can control the introduction of process gases to the mixing vessel 704. Similarly, a showerhead inlet valve 705 can control the introduction of process gases to the showerhead 706.

[0232] Some metal-containing precursors can be stored in solid or liquid form prior to vaporization and subsequent delivery to the processing station. For example, the embodiment of FIG. 7 includes a vaporization point 703 for vaporizing solid reactants that will be supplied to the mixing vessel 704. In some embodiments, the vaporization point 703 can be a heated vaporizer. In some embodiments, an inert gas stream is passed over a heated solid metal precursor, or bubbled through a heated liquid metal precursor, at a pressure below atmospheric pressure, and carries the precursor vapor to the processing chamber. Precursor vapor generated from such a vaporizer can condense in the downstream delivery piping. Incompatible gas exposure to the condensed reactant can generate small particles. These small particles can clog the piping, impede valve operation, contaminate substrates, etc. Some methods to address these issues involve purging and / or pumping out the delivery piping to remove residual reactants. However, purging the delivery piping increases processing station cycle time, reducing processing station throughput. Accordingly, in some embodiments, the delivery piping downstream of the vaporization point 703 can be heat traced. In some examples, the mixing vessel 704 can also be heat traced. In one non-limiting example, the piping downstream of the vaporization point 703 has an elevated temperature profile that rises from about 100 °C to about 200 °C at the mixing vessel 704.

[0233] The showerhead 706 distributes process gases toward the substrate 712. In the embodiment shown in FIG. 7, the substrate 712 is positioned below the showerhead 706 and is shown disposed on a susceptor 708. It will be appreciated that the showerhead 706 can have any suitable shape and can have any suitable number and arrangement of ports to distribute process gases to the substrate 712. Although not explicitly shown, in some embodiments, the showerhead 706 is a dual plenum showerhead that includes at least two types of conduits, where a first type of conduit is dedicated to delivering molybdenum-containing precursor vapor and a second type of conduit is dedicated to delivering a second (or other) reactant. In these embodiments, the molybdenum-containing precursor and the reactant are not allowed to mix in the conduits prior to entering the processing chamber and do not share conduits if delivered to the processing chamber consecutively.

[0234] In some embodiments, the micro-volume 707 is positioned below the showerhead 706. Performing ALD and / or CVD processing in a micro-volume rather than in the entire volume of the processing station can reduce reactant exposure and purge times, can reduce the time to change processing conditions (e.g., pressure, temperature, etc.), can limit exposure of the processing station robot to processing gases, etc. Exemplary micro-volume sizes include, but are not limited to, a volume between 0.1 liters and 2 liters. This micro-volume also impacts the throughput of the production. As the deposition rate per cycle is reduced, the cycle time is also reduced. In some cases, the effect of the cycle time reduction is significant enough to increase the overall throughput of the module for a given target film thickness.

[0235] In some embodiments, the susceptor 708 can 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 susceptor 708 can be lowered so that the substrate 712 can be loaded on the susceptor 708. During a deposition processing phase, the susceptor 708 can be raised to position the substrate 712 within the micro-volume 707. In some embodiments, the micro-volume 707 can completely surround the substrate 712 and a portion of the susceptor 708 to form a high flow impedance region during deposition processing.

[0236] Optionally, the susceptor 708 can be lowered and / or raised during portions of the deposition processing to adjust the processing pressure, reactant concentration, etc. within the micro-volume 707. In one case where the processing chamber body 702 is maintained at a base pressure during deposition processing, lowering the susceptor 708 can enable the micro-volume 707 to be pumped down. Exemplary ratios of micro-volume to processing chamber volume include, but are not limited to, a volume ratio between 1 :700 and 1 : 10. It will be appreciated that, in some embodiments, the susceptor height can be adjusted programmatically by a suitable computer controller.

[0237] While the exemplary micro-volume changes described herein involve a highly adjustable pedestal, it should be understood that in some embodiments, the position of the showerhead 706 can be adjusted relative to the pedestal 708 to change the volume of the micro-volume 707. Further, it should be understood that the vertical position of the pedestal 708 and / or the showerhead 706 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 708 can include a rotational axis for rotating the orientation of the substrate 712. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more suitable computer controllers.

[0238] Returning to the embodiment shown in FIG. 7, the showerhead 706 and the 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 device without a plasma generator is used to deposit a molybdenum-containing film using the methods provided. In some embodiments, the energy of the plasma can be controlled by controlling one or more of the pressure of the processing station, the concentration of the gas, the radio frequency (RF) source power, the RF source frequency, and the plasma power pulse timing. For example, the RF power source 714 and the matching network 716 can operate at any suitable power to form a plasma having a desired composition of radical species. Similarly, the RF power source 714 can provide RF power at any suitable frequency. In some embodiments, the RF power source 714 can be configured to control a high frequency RF power source and a low frequency RF power source independently of one another. Exemplary low frequency RF frequencies can include, but are not limited to, frequencies between 50 kHz and 700 kHz. Exemplary high frequency RF frequencies can include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It should be understood that any suitable parameters can be adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power can be pulsed intermittently relative to a continuously powered plasma to reduce ion bombardment of the substrate surface.

[0239] In some embodiments, the plasma can be monitored in situ by one or more plasma monitors. In one case, the plasma power can be monitored by one or more voltage, current sensors (e.g., VI probes). In another case, the plasma density and / or concentration of a process gas can be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on measurements from such in situ plasma monitors. For example, an OES sensor can be used in a feedback loop to provide programmed control of the plasma power. It should be appreciated that in some embodiments, other monitors can be used to monitor the plasma and other process characteristics. Such monitors can include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0240] In some embodiments, the plasma can be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting plasma conditions for a plasma processing phase can be included in a corresponding plasma activation recipe phase of a deposition process recipe. In some cases, the process recipe phases can be arranged in sequence such that all instructions for a deposition process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more plasma parameters can be included in a recipe phase prior to a plasma processing phase. For example, a first recipe phase can include instructions for setting flow rates of an inert gas and / or a reactant gas, instructions for setting a plasma generator to a power setpoint, and a time delay instruction for the first recipe phase. A subsequent second recipe phase can include instructions for enabling the plasma generator and a time delay instruction for the second recipe phase. A third recipe phase can include instructions for disabling the plasma generator and a time delay instruction for the third recipe phase. It should be appreciated that these recipe phases can be further subdivided and / or iterated in any suitable manner within the scope of the present disclosure.

[0241] In some embodiments, the pedestal 708 can be temperature controlled by the heater 710. Further, in some embodiments, pressure control of the deposition processing station 700 can be provided by the butterfly valve 718. As shown in the embodiment of FIG. 7, the butterfly valve 718 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the processing station 700 can also be adjusted by varying a flow rate of one or more gases introduced into the processing station 700.

[0242] Figure 8 shows a schematic view of an embodiment of a multi-station processing tool 800 having an inbound load lock 802 and an outbound load lock 804, either or both of which can include a remote plasma source. Such a tool can be used to process substrates using the methods provided herein. At atmospheric pressure, a robot 806 is configured to move wafers from a cassette loaded through a wafer boat 808 via an atmospheric port 810 into the inbound load lock 802. The wafer is placed by the robot 806 on a pedestal 812 in the inbound load lock 802, the atmospheric port 810 is closed, and the load lock is pumped down. When the inbound load lock 802 includes a remote plasma source, the wafer can be exposed to a remote plasma treatment in the load lock before being introduced into a processing chamber 814. In addition, the wafer can also be heated in the inbound load lock 802, for example, to remove moisture and adsorbed gases. Next, a chamber transfer port 816 to the processing chamber 814 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of the first station shown for processing. Although the embodiment shown in Figure 8 includes load locks, it should be understood that in some embodiments, the wafers can be brought directly into the processing stations.

[0243] The depicted processing chamber 814 includes four processing stations, numbered 1 through 4 in the embodiment shown in Figure 8. Each station has a heated pedestal (shown as 818 for station 1) and gas line inlets. It should be understood that in some embodiments, each processing station can have a different or multiple uses. Although the depicted processing chamber 814 includes four stations, it should be understood that processing chambers according to the present disclosure can have any suitable number of stations. For example, in some embodiments, a processing chamber can have five or more stations, while in other embodiments, a processing chamber can have three or fewer stations.

[0244] Figure 8 also depicts an embodiment of a wafer handling system 890 for transporting wafers within the processing chamber 814. In some embodiments, the wafer handling system 890 can transport wafers between various processing stations and / or between processing stations and load locks. It should be understood that any suitable wafer handling system can be employed. Non-limiting examples include a wafer turntable and a robot that handles wafers. Figure 8 also depicts an embodiment of a system controller 850 for controlling the processing conditions and hardware state of the processing tool 800. The system controller 850 can include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processors 852 can include CPUs or computers, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0245] In some embodiments, system controller 850 controls all of the activities of process tool 800. System controller 850 executes system control software 858 stored in mass storage device 854, loaded into memory device 856, and executed on processor 852. System control software 858 can include instructions for controlling timing, gas mixtures, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck, and / or pedestal position, and other parameters of the particular process performed by process tool 800. System control software 858 can be configured in any suitable manner. For example, various process tool component subroutines or control objects can be written to control the operation of the process tool components necessary to perform the various process tool processes according to the disclosed methods. System control software 858 can be coded in any suitable computer readable programming language.

[0246] In some embodiments, system control software 858 can include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of an ALD process can include one or more instructions executed by system controller 850. Instructions for setting the process conditions for an ALD process stage can be included in the corresponding ALD recipe stage. In some embodiments, the ALD recipe stages can be arranged sequentially, such that all of the instructions for an ALD process stage are executed concurrently with that process stage.

[0247] Other computer software and / or programs stored on mass storage device 854 and / or memory device 856 associated with system controller 850 can be employed in some embodiments. Examples of programs or program segments for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0248] A substrate positioning program can include program code for process tool components for loading a substrate to a pedestal 818 and controlling the spacing between the substrate and other parts of process tool 800.

[0249] A process gas control program can include code for controlling gas composition and flow rates and, optionally, for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. A process gas control program can include code for controlling gas composition and flow rates within any of the disclosed ranges. A pressure control program can include code for controlling the pressure in a process station by adjusting, for example, a throttle valve in an exhaust system of the process station, gas flow into the process station, etc. A pressure control program can include code for maintaining the pressure in a process station within any of the disclosed pressure ranges.

[0250] The heater control program can include code for controlling the current flow to a heating unit for heating the substrate. Alternatively, the heater control program can control the delivery of a heat transfer gas, such as helium, to the substrate. The heater control program can include instructions to maintain the temperature of the substrate within any of the disclosed ranges.

[0251] The plasma control program can include code for setting the RF power level and frequency applied to the processing electrodes in one or more of the processing stations, for example using any of the RF power levels disclosed herein. The plasma control program can also include code for controlling the duration of each plasma exposure.

[0252] In some embodiments, there can be a user interface associated with the system controller 850. The user interface can include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0253] In some embodiments, the parameters adjusted by the system controller 850 can relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF power level, frequency, and exposure time), etc. These parameters can be provided to the user in the form of a recipe, which can be entered using the user interface.

[0254] Signals for monitoring the process can be provided by analog and / or digital input connections of the system controller 850 from various process tool sensors. Signals for controlling the process can be output on analog and / or digital output connections of the process tool 800. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (e.g., manometers), thermocouples, and the like. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0255] Any suitable chamber can be used to implement the disclosed embodiments. Exemplary deposition apparatus include, but are not limited to, the Halo® family of chambers available from Lam Research Corp. of Fremont, California ® The apparatus of the product line, or any of a variety of other commercially available processing systems. Two or more stations can perform the same function. Similarly, two or more stations can perform different functions. Each station can be designed / configured as needed to perform a particular function / method.

[0256] FIG. 9 is a block diagram of a processing system suitable for performing thin film deposition processes, according to certain embodiments. The system 900 includes a transfer module 903. The transfer module 903 provides a clean, pressurized environment to minimize the risk of contamination as substrates being processed are moved between various reactor modules. According to certain embodiments, mounted on 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). The reactors 909 and 910 can include multiple stations 911, 913, 915, and 917, which can perform operations sequentially or non-sequentially according to the disclosed embodiments. These stations can include heated susceptor or substrate supports, one or more gas inlets or showerheads or disperser plates.

[0257] Also mounted on the transfer module 903 can be one or more single- or multi-station modules 907 capable of performing plasma or chemical (non-plasma) pre-cleaning, or any other processing relevant to the disclosed methods. In some cases, the module 907 can be used for various processing to, for example, prepare substrates for deposition processing. The module 907 can also be designed / configured to perform various other processing, such as etching or polishing. The system 900 also includes one or more wafer source modules 901 in which wafers are stored prior to and after processing. Atmospheric robot (not shown) in an atmospheric transfer chamber 919 can first move wafers from the source module 901 to a load lock 921. Wafer transfer devices (typically robotic arm units) in the transfer module 903 move wafers from the load lock 921 to and among the modules mounted on the transfer module 903.

[0258] In various embodiments, a system controller 929 is used to control the processing conditions during deposition. The controller 929 will typically include one or more memory devices and one or more processors. The processors can include CPUs or calculators, analog and / or digital input / output connections, stepper motor controller boards, and the like.

[0259] The controller 929 can control all of the activities of the deposition apparatus. The system controller 929 executes system control software, which includes sets of instructions for controlling timing, mixtures of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or susceptor position, and other parameters of a particular process. Other computer programs stored in memory devices associated with the controller 929 can be employed in some embodiments.

[0260] There will typically be a user interface associated with the controller 929. The user interface can include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0261] The system control logic can be configured in any suitable manner. Generally, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry can be hard coded or provided as software. The instructions can be provided through "programming." Such programming is understood to include any form of logic, including hard coded logic in digital signal processors, application specific integrated circuits, and other devices having specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that can be executed on a general purpose processor. The system control software can be coded in any suitable computer readable programming language.

[0262] The computer program code for controlling the flow of reducing agent, the flow of halogen-containing activating agent, the flow of metal precursor, and other processing in the processing sequence can be written in any of common computer readable programming languages: for example, assembly language, C, C++, Pascal, Fortran or others. Compiled object code or script are executed by a processor to perform the tasks identified in the program. As indicated, the program code can be hard coded.

[0263] The controller parameters relate to processing conditions such as, for example, process gas composition and flow rate, temperature, pressure, chuck pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and can be entered using a user interface. Signals for monitoring the processing can be provided through analog and / or digital input connections of the system controller 929. Signals for controlling the processing are output through analog and digital output connections of the deposition apparatus 900.

[0264] The system software can be designed or configured in many different ways. For example, in accordance with the disclosed embodiments, various chamber component subroutines or control objects can be written to control the operation of the chamber components necessary to perform a deposition process (and in some cases other processes). Examples of programs or program segments for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0265] In some implementations, the controller 929 is part of a system, which can be part of the above-described examples. Such systems can contain semiconductor processing equipment, including one or more of a processing tool, a processing chamber, a platform for processing, and / or a specific processing component (a wafer pedestal, a gas flow system, etc.). These systems can be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics can be referred to as the “controller,” which can control various components or subcomponents of one or more systems. The controller 929, depending on the specific implementation, can be a part of, or communicate with, one or more of the systems. The controller 929 can control various processes run on the systems, including but not limited to, a process gas flow, a temperature setting (e.g., a heating and / or cooling), a pressure setting, a vacuum setting, a power setting, a radio frequency (RF) generator setting, an RF matching circuit setting, a frequency setting, a flow rate setting, a fluid delivery setting, a position and operation setting, wafer transfer into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0266] Broadly speaking, the controller can be defined as electronics designed to receive commands from the processor and send signals to the system in response to the commands associated with the operation of the semiconductor manufacturing system. In some implementations, the controller includes one or more memory, one or more processing units, and / or other components. In some implementations, the controller includes a computer or other computing device. In some implementations, the controller includes one or more integrated circuits, functions, programs and / or software components, which are configured to control the operation of the system.

[0267] In some implementations, a controller can be part of, or coupled to, a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller can be in the "cloud" or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. Computer can enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, make changes to current processing, set-up process steps to follow a current process, or start a new process. In some embodiments, a remote computer (e.g. a server) can provide process recipes to a system over a network, which can include a local network or the Internet. The remote computer can include a user interface that enables a user to retrieve and / or input data, and schedule processing on one or more systems. In some embodiments, a controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters can be specific to a type of process to be performed, and a type of tool that the controller is configured to interface with or control.

[0268] An example system can include, but is not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor

[0269] As described above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of: other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, contiguous tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0270] Further Embodiments The apparatuses and processes described herein can be used in conjunction with lithographic patterning tools or processes, e.g., for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, though not necessarily, these apparatuses and processes will be used or operated together at a common manufacturing facility. Lithographic patterning of a film typically includes some or all of the following steps, each of which enables a number of viable tools: (1) coating a photoresist on a workpiece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hot plate or furnace or ultraviolet curing tool; (3) exposing the photoresist to visible or ultraviolet or X-rays using a tool such as a wafer stepper; (4) developing the resist so as to selectively remove the resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper.

[0271] Experimental examples Molybdenum was deposited on TiN surfaces with and without an alkyl halide activator. MoCl5was used as the molybdenum precursor, H2as the reducing agent, and t-butyl chloride (also known as 2-chloro-2-methylpropane) as the halogen-containing activator. In the absence of t-butyl chloride, molybdenum was deposited on the substrate by performing 100 deposition cycles, where each cycle included sequential MoCl5exposure and H2exposure. When using the t-butyl chloride activator, each cycle included exposing the substrate to MoCl5, followed by exposure to t-butyl chloride, followed by exposure to H2(as a reducing agent). The reagents were introduced into the process chamber sequentially, without mixing in the process chamber. A purge was performed after each step of the cycle to remove unadsorbed reagents from the process chamber. The molybdenum film was deposited at a temperature range of 350 °C to 450 °C. FIG. 10 is a plot showing the molybdenum layer thickness as a function of temperature deposited on a TiN surface in the absence of a halogen-containing activant (circles) and with a halogen-containing activant (triangles). It can be seen that the molybdenum thickness increased by more than a factor of 4 at 400 °C using the t-butyl chloride activant.

Claims

1. A method for forming a metal-containing layer, the method comprising: (a) In a processing chamber, the semiconductor substrate is brought into contact with the metal precursor; (b) Contacting the semiconductor substrate with a halogen-containing deposition activator, wherein the halogen-containing deposition activator is different from the metal precursor; as well as (c) Contact the semiconductor substrate with a reducing agent to form the metal-containing layer on the semiconductor substrate.

2. The method of claim 1, wherein steps (a), (b) and (c) are performed sequentially without allowing any two components selected from the group consisting of the metal precursor, the halogen-containing deposition activator and the reducing agent to simultaneously flow into the processing chamber.

3. The method according to claim 1, wherein steps (b) and (c) are performed simultaneously.

4. The method according to claim 1, wherein the halogen-containing deposition activator is selected from the group consisting of hydrogen halides, alkyl halides, halogenated silanes, dihalogens, halides of group 13 elements, halides of group 15 elements, and metal halides.

5. The method according to claim 1, wherein the halogen-containing deposition activator is a tertiary alkyl halide.

6. The method according to claim 1, wherein the halogen-containing deposition activator is tert-butyl chloride.

7. The method according to claim 1, wherein the halogen-containing deposition activator is an iodine-containing deposition activator.

8. The method according to claim 1, wherein the halogen-containing deposition activator is selected from the group consisting of hydrogen bromide (HBr), bromine (Br2), tert-butyl bromide, bromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (SiHBr3), and silicon tetrabromide (SiBr4).

9. The method according to claim 1, wherein the halogen-containing deposition activator is selected from the group consisting of hydrogen iodide (HI), iodine (I2), tert-butyl iodide (C4H9I), allyl iodide (C3H5I), iodosilane (SiH3I), diiodosilane (SiH2I2), triiodosilane (SiHI3), and silicon tetraiodide (SiI4).

10. The method according to claim 1, wherein the halogen-containing deposition activator is selected from the group consisting of titanium tetrabromide, tungsten pentabromide, tungsten hexabromide, boron tribromide and aluminum tribromide.

11. The method of claim 1, wherein the halogen-containing deposition activator is selected from the group consisting of titanium tetraiodide, boron triiodide and aluminum triiodide.

12. The method according to any one of claims 1-11, wherein the metal-containing layer comprises a molybdenum-containing layer, or a cobalt-containing layer, or a ruthenium-containing layer, or a tungsten-containing layer, or a titanium-containing layer, or any combination thereof.

13. The method according to any one of claims 1-11, wherein the metal-containing layer is a metal nitride layer.

14. The method according to any one of claims 1-11, wherein the metal-containing layer comprises a titanium-containing nitride layer, or a molybdenum-containing nitride layer, or any combination thereof.

15. The method according to any one of claims 1-11, wherein the metal-containing layer is a molybdenum-containing layer.

16. The method according to any one of claims 1-11, wherein the metal-containing layer is a molybdenum-containing layer, and the metal precursor is a molybdenum precursor containing molybdenum-halogen bonds.

17. The method according to any one of claims 1-11, wherein the metal-containing layer is a molybdenum layer, and the metal precursor comprises MoCl5 or Mo2Cl. 10 MoO2Cl2, MoOCl 4、 Mo(PF3)6, Mo(CO)6, ( i PrCp)2MoH2, Mo(hfac)3, MoO(O i Pr)4, bis(ethylbenzene)Mo, Mo2(TFA)4, or MoF6, or any combination thereof.

18. The method of claim 1, wherein the metal precursor comprises a metal-chlorine bond, and wherein the halogen-containing deposition activator comprises at least one of bromine and iodine.

19. The method of claim 1, further comprising performing at least two deposition cycles, wherein each cycle comprises steps (a), (b) and (c).

20. The method according to claim 1, wherein the metal-containing layer is a metal carbide layer.

21. The method of claim 1, wherein the metal-containing layer is a molybdenum carbide layer deposited on a semiconductor substrate comprising a plurality of recessed features as a liner, wherein the recessed features comprise a dielectric at their sidewalls.

22. The method of claim 1, wherein the metal-containing layer is a molybdenum carbonitride layer deposited on a semiconductor substrate comprising a plurality of recessed features as a liner, wherein the recessed features comprise a dielectric at their sidewalls.

23. The method according to any one of claims 21-22, further comprising filling the recessed feature with metal.

24. The method of claim 1, wherein the metal-containing layer is a metal layer deposited into a recessed feature of the semiconductor substrate to at least partially fill the recessed feature.

25. The method of claim 24, wherein the metal-containing layer is a molybdenum layer.

26. The method of claim 1, wherein the metal-containing layer is deposited at a temperature between about 250ºC and about 600ºC and a pressure less than about 300 Torr.

27. A method comprising: (a) Providing a semiconductor substrate with an exposed dielectric layer; (b) A molybdenum carbide liner is formed on the dielectric layer by exposing the semiconductor substrate to a molybdenum precursor, an alkyl halide and a reducing agent; as well as (c) Deposit a metal layer on the molybdenum carbide liner.

28. An apparatus for processing a substrate, the apparatus comprising: (a) A processing chamber having a substrate holder for holding a semiconductor substrate and one or more inlets for introducing reactants into the processing chamber; as well as (b) A controller including program instructions for: (i) causing the semiconductor substrate to come into contact with the metal precursor in the processing chamber; (ii) causing the semiconductor substrate to come into contact with a halogen-containing deposition activator, wherein the halogen-containing deposition activator is different from the metal precursor; as well as (iii) To bring the semiconductor substrate into contact with a reducing agent to form a metal-containing layer on the semiconductor substrate.

29. A system for processing a substrate, the system comprising: (a) One or more processing chambers; as well as (b) A controller, comprising program instructions for: (i) A molybdenum carbide liner is deposited on a semiconductor substrate having an exposed deposition layer by exposing the substrate to a molybdenum precursor, an alkyl halide, and a reducing agent; and (ii) Deposit a metal layer onto the molybdenum carbide substrate.

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