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

Abstract

Metal-containing films, such as molybdenum and molybdenum carbide films, are deposited on semiconductor substrates by a deposition process modulated by the addition of halogen-containing activator molecules (e.g., alkyl halides, halosilanes, or I2). In some configurations, the substrate is first contacted with a metal-containing precursor (e.g., MoCl5), followed by a halogen-containing activator (e.g., t-butyl chloride), and then a reducing agent (e.g., H2). This process may be repeated as many times as necessary to form a film of the desired thickness. In some embodiments, the metal film is formed by these methods and deposited inside concave features on the substrate to fill the concave features. In other embodiments, the metal carbide film (e.g., molybdenum carbide film) is deposited by these methods as a liner between the dielectric layer and the metal layer.

Description

[Technical Field]

[0001] Embedding by reference The PCT application is filed concurrently with this application as part of this application. Each application for which this application claims benefit or priority as identified in a concurrently filed PCT application is incorporated herein by reference in its entirety for any purpose.

[0002] This invention relates to a method for manufacturing semiconductor devices. Specifically, embodiments of this invention relate to the deposition of metal-containing layers, such as molybdenum and molybdenum carbide layers, in semiconductor processing. [Background technology]

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

[0004] Chemical vapor deposition (CVD) is another deposition method widely used in semiconductor processing. In CVD, the reaction takes place within the volume of the process chamber and is not limited by the amount of reactants adsorbed on the substrate. As a result, CVD-deposited films are often less conformal than ALD-deposited films. CVD is typically used in applications where step coverage is not critical.

[0005] ALD and CVD can use plasma to accelerate the reaction of deposition precursors, resulting in the formation of the desired film. Methods utilizing plasma are known as plasma-enhanced ALD (PEALD) and plasma-enhanced CVD (PECVD). Methods that do not use plasma are called thermal ALD and thermal CVD.

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

[0007] The background art provided herein is for the purpose of generally presenting the context of this disclosure. The inventors' research, to the extent described in this background art section, is not expressly or implicitly considered prior art to this disclosure, as is the case with any description that may not be considered prior art at the time of filing. [Overview of the project] [Problems that the invention aims to solve]

[0008] A method is provided for depositing a metal-containing layer (such as a molybdenum and molybdenum carbide layer) on a semiconductor substrate using halogen-containing activator molecules. The halogen-containing activator is typically used together with the metal precursor and a reducing agent after the substrate has been first 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., by at least about 20%, e.g., at least about 100%) by first contacting the semiconductor substrate with the metal precursor and then contacting the substrate with halogen-containing activator molecules (e.g., alkyl halides, dihalogens, halosilanes, or any combination thereof). [Means for solving the problem]

[0009] In one embodiment, a method is provided for forming a metal-containing layer (e.g., a metal layer, a metal carbide layer, a metal nitride layer). In some embodiments, the method includes (a) contacting a semiconductor substrate with a metal precursor in a process 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 flowing any two components selected from the group consisting of a metal precursor, a halogen-containing deposition activator, and a reducing agent into the process chamber. In some embodiments, the method includes performing at least two, for example, at least 50, deposition cycles, each cycle comprising steps (a), (b), and (c) performed sequentially. In some embodiments, steps (b) and (c) are performed simultaneously (i.e., with at least some temporal overlap).

[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., t-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), t-butyl iodide (C4H9I), allyl iodide (C3H5I), iodosilane (SiH3I), diiodosilane (SiH2I2), triiodosilane (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), t-butyl bromide, bromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (SiHBr3), and silicon tetrabromide (SiBr4). In some embodiments, halogen-containing deposition activators are selected from the group consisting of titanium tetrabromide, tungsten pentabromide, tungsten hexabromide, boron tribromide, and aluminum tribromide. In some embodiments, halogen-containing deposition activators are selected from the group consisting of titanium tetraiodide, boron triiodide, and aluminum triiodide.

[0011] Metal-containing layers deposited by the provided method include, but are not limited to, metal layers, metal carbide layers, and metal nitride layers. Molybdenum-containing layers, cobalt-containing layers, ruthenium-containing layers, tungsten-containing layers, titanium-containing layers, or any combination thereof can be deposited by the provided method. 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 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 one embodiment, the deposited metal-containing layer is a molybdenum-containing layer, and the metal precursor is a molybdenum precursor containing a molybdenum-halogen bond. For example, the molybdenum precursor is MoCl5, Mo2Cl 10 This may include MoO2Cl2, MoOCl4, or MoF6, or any combination thereof. Other examples include, but are not limited to, Mo(PF3)6, Mo(CO)6, (iPrCp)2MoH2, Mo(hfac)3, MoO(OiPr)4, bis(ethylbenzene)Mo, or Mo2(TFA)4 (wherein iPrCp = isopropylcyclopentadiene and hfac = hexafluoroacetylacetonate).

[0013] In some embodiments, the metal precursor includes a metal-chlorine bond, and the halogen-containing deposition activator includes at least one of bromine and iodine. Examples of bromine-containing deposition activators include hydrogen bromide (HBr), bromine (Br2), t-butyl bromide, bromosilane (SiH3Br), dibromosilane (SiH2Br2), tribromosilane (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), diiodosilane (SiH2I2), triiodosilane (SiHI3), and silicon tetraiodide (SiI4).

[0014] In some embodiments, the deposited metal-containing layer is a molybdenum carbide (MoC or MoCN) layer deposited as a liner on a semiconductor substrate containing a plurality of concave features, the concave features containing a dielectric on their 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 is deposited as a liner, the concave features can be filled with metal.

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

[0016] In some embodiments, the deposit of the metal-containing layer is carried out at a temperature of about 250°C to about 600°C and a pressure of less than about 300 Torre.

[0017] In another embodiment, a method is provided, which includes (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 layer.

[0018] In some embodiments, the provided method is integrated with a photolithography patterning sequence and further includes the steps of applying a photoresist to a 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 may be performed to form concave features on the semiconductor substrate before depositing a metal-containing layer.

[0019] In another embodiment, an apparatus is provided which includes a controller having program instructions configured to cause the execution of any method step of the methods provided herein. For example, in some embodiments, an apparatus is provided for processing a substrate, which includes (a) a process chamber having a substrate holder for holding a semiconductor substrate and one or more inlets for introducing reactants into the process chamber, and (b) a controller which includes program instructions for causing (i) the semiconductor substrate to come into contact with a metal precursor in the process chamber, (ii) the semiconductor substrate to come into contact with a halogen-containing deposition activator, the halogen-containing deposition activator being different from the metal precursor, and (iii) the semiconductor substrate to come into contact with a reducing agent to form a metal-containing layer on the semiconductor substrate. In some embodiments, a system is provided for processing a substrate, which includes (a) one or more process chambers, and (b) a controller which includes program instructions for causing (i) the semiconductor substrate to be exposed to a molybdenum precursor, an alkyl halide, and a reducing agent to deposit a molybdenum carbide liner on a semiconductor substrate having an exposed dielectric layer, and (ii) the molybdenum carbide liner to deposit a metal layer on the molybdenum carbide liner.

[0020] In another embodiment, a non-transient machine-readable medium is provided, which includes a code for causing the execution of any step of the method provided herein. For example, the code may include a code for (i) contacting a semiconductor substrate with a metal precursor in a process chamber, (ii) contacting the semiconductor substrate with a halogen-containing deposition activator, the halogen-containing deposition activator being 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-transient machine-readable medium may include a code for (i) depositing a molybdenum carbide liner on a semiconductor substrate having an exposed dielectric 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 liner.

[0021] These and other embodiments of the implementation of the subject matter described herein are shown in the accompanying drawings and the following description. [Brief explanation of the drawing]

[0022] [Figure 1A] This shows a schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to embodiments provided herein. [Figure 1B] This shows a schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to embodiments provided herein. [Figure 1C] This shows a schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to embodiments provided herein. [Figure 2A] A schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to another embodiment provided herein is shown. [Figure 2B] A schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to another embodiment provided herein is shown. [Figure 2C] A schematic cross-sectional view of a substrate during the deposition of a metal-containing film according to another embodiment provided herein is shown. [Figure 3A] This is a process flow diagram of a method for forming a metal-containing film according to embodiments provided herein. [Figure 3B] This is a process flow diagram of a method for forming a metal-containing film according to embodiments provided herein. [Figure 4] Examples of ligands that can be used in molybdenum precursors according to embodiments provided herein are provided. [Figure 5] Examples of sulfur-containing ligands that can be used in molybdenum precursors according to embodiments provided herein are provided. [Figure 6A] Examples of molybdenum precursors according to embodiments provided herein are listed below. [Figure 6B] Examples of molybdenum precursors according to embodiments provided herein are listed below. [Figure 6C] Examples of molybdenum precursors according to embodiments provided herein are listed below. [Figure 7] This is a schematic diagram of an apparatus suitable for depositing metal-containing films, according to embodiments provided herein. [Figure 8] This is a schematic diagram of a multi-station processing system according to embodiments provided herein. [Figure 9] This is a schematic diagram of a multi-station processing system according to embodiments provided herein. [Figure 10] This experimental plot shows the thickness of molybdenum deposited on titanium nitride as a function of temperature, with and without the use of a halogen-containing activator. [Modes for carrying out the invention]

[0023] A method is provided for depositing metal-containing layers (such as metal, metal carbide, and metal nitride layers) on a semiconductor substrate using vapor deposition such as CVD or ALD. The method generally includes, but is not limited to, a process sequence in which the use of plasma activation is not required and all steps are performed in the absence of plasma (in some embodiments, one or more steps may be plasma-assisted). The method can be used to deposit metals such as molybdenum, ruthenium, tungsten, titanium, and cobalt, as well as metal carbides (including oxide carbides 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 carried out at high deposition rates at low temperatures below about 600°C, for example below about 500°C.

[0024] The method involves increasing the deposition rate on a substrate using a halogen-containing deposition activator. In some embodiments, the halogen-containing deposition activator is brought into contact with the substrate after the substrate first comes into contact with a metal precursor, and the halogen-containing activator molecules are different from those of the metal precursor. In some configurations, the substrate is brought into contact with the halogen-containing activator, and then with a reducing agent. In other configurations, the substrate is brought into contact with both the halogen-containing activator and the reducing agent simultaneously.

[0025] In some implementations, halogen-containing activators increase the deposition rate by at least about 20%, for example, at least 50%, or at least about 100%, compared to processes carried out under the same deposition conditions in the absence of the activator. For example, the metal deposition rate can be increased from about 20 Å per 100 deposition cycles to about 90 Å per 100 deposition cycles.

[0026] The provided method can be used to deposit a metal (e.g., molybdenum, ruthenium, titanium, cobalt, or tungsten) to fill concave features on a semiconductor substrate. The concave features can be filled via conformal or bottom-up mechanisms. The thickness of the metal layer deposited within the concave features ranges from about 0.1 μm to about 500 μm in some examples. In other embodiments, the deposited film is used as a liner at the interface between, for example, a dielectric layer and a metal layer (e.g., a film having a thickness of about 0.5 nm to about 200 nm, e.g., about 1 nm to 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 concave features formed in a dielectric layer using the provided method. After the liner is deposited by the method provided herein, the concave features can be filled with metal (e.g., molybdenum, tungsten, or ruthenium) using the method provided herein or by other deposition methods (e.g., CVD without halogen-containing activator molecules).

[0027] The provided method can be used to deposit metal-containing films on a variety of surfaces, including but not limited to deposits 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, polycrystalline silicon, 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, the deposition is carried out on substrates having different exposed materials. For example, the metal-containing film provided herein can be deposited on a substrate having a concave feature, in which the dielectric is exposed within the field region and on the sidewalls of the concave feature, and the metal is exposed at the bottom of the concave feature.

[0028] The provided method can be used for a variety of applications, including, but is not limited to, the deposition of metals (e.g., molybdenum) in gap-filling applications and the formation of conformal metal films. Examples of semiconductor device structures that can be manufactured using the provided method 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 the range of about 0.5 nm to about 4 nm and can be used to deposit molybdenum metal on various concave features, such as features with a width of about 1 nm to about 25 nm, a depth of about 30 nm to about 200 nm or more, and various aspect ratios, including high aspect ratios of at least 10:1 such as 30:1.

[0029] As used herein, “metal” refers to a material that essentially consists of a metal in a zero-oxide state. Other elements (e.g., C, N, or O) may be present in small amounts in the metal (e.g., total content less than about 15 atomic percent, or less than about 10 percent, and hydrogen is not included in the calculation). In some embodiments, metal films having less than 3 atomic percent carbon can be obtained by the methods provided. Examples of metal films that can be obtained by the methods provided include 97% pure molybdenum, 97% pure cobalt, 97% pure tungsten, and 97% pure ruthenium, where % refers to weight percent.

[0030] As used herein, “metal carbide” refers to a material containing metal and carbon. In some embodiments, the carbon content is greater than about 10 atomic percent, for example, greater than 20 atomic percent, or greater than 40 atomic percent (hydrogen is not included in the calculation). As used herein, metal carbides may also contain other elements such as N, O, and B. For example, as used herein, “molybdenum carbide” encompasses MoC, MoOC, and MoCN (also called molybdenum carbonitride or molybdenum carbide nitride), and the formula does not indicate a specific stoichiometry. For example, MoC has a carbon content of about 40–60 atomic percent in some embodiments, and not necessarily 50 atomic percent.

[0031] As used herein, the term “semiconductor substrate” refers to a substrate at any stage in the fabrication of a semiconductor device that contains semiconductor material somewhere within its structure. It is understood that the semiconductor material within the semiconductor substrate does not need to be exposed. A semiconductor wafer having multiple layers of other material (e.g., dielectric) covering the semiconductor material is an example of a semiconductor substrate. In the detailed description below, the disclosed mounting configurations are assumed to be mounted on a semiconductor wafer, such as a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed mounting configurations are not limited in this way. Workpieces may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that may utilize the disclosed mounting configurations include various articles such as printed circuit boards.

[0032] As used herein, the term “halogen-containing deposition activator” refers to a species (e.g., a compound) containing one or more halogen atoms (e.g., F, Cl, Br, I, or any combination thereof), and the use of an activator in the deposition of metal-containing materials results in a higher deposition rate of the metal-containing material compared to the same deposition process carried out 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.

[0033] As used herein, the term “reducing agent” refers to a species that is oxidized (loses one or more electrons) during the deposition process. For example, H2 (a reducing agent) with hydrogen in a zero-oxidation state can be oxidized to HCl during a deposition process where hydrogen is in a +1 oxidation state.

[0034] As used herein, the term “approximately” means + / - 10% of the listed values ​​unless otherwise specified. As used herein, this term qualifies any listed value, range of values, or endpoint of one or more ranges.

[0035] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be located in a specific place within the apparatus.

[0036] As used herein, the phrase "at least one of A, B, and C" should be interpreted as meaning (A OR B OR C) using the non-exclusive logic OR, and not as meaning "at least one of A, at least one of B, and at least one of C."

[0037] As used herein, "A" should be interpreted as "one or more". For example, "surface of the substrate" should be interpreted as "one or more surfaces of the substrate", which may include concave feature sidewall surfaces, field surfaces, concave feature bottom surfaces, and combinations thereof.

[0038] As used herein, "reducing agent" refers to a reactant that loses one or more electrons in a reaction.

[0039] As used herein, "heteroreptic complex" refers to a compound containing at least two different ligands bonded to a metal center.

[0040] As used herein, "homoreptic complex" refers to a compound containing all identical ligands bonded to a metal center.

[0041] The term "activator-free deposition cycle" refers to the continuous exposure of a substrate to metal precursors and reducing agents without the use of deposition activators.

[0042] The term "activator-assisted deposition cycle" refers to the exposure of a semiconductor substrate to deposition activators, metal precursors, and reducing agents, at least a portion of which are performed sequentially.

[0043] The terms “acyl” or “alkanoyl,” as used interchangeably herein, refer to groups having one, two, three, four, five, six, seven, or eight or more saturated, unsaturated, or aromatic carbon atoms, or combinations thereof, or hydrogen atoms, having linear, branched, or cyclic structures, which are bonded to a parent group via a carbonyl group as defined herein. Examples of such groups include formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, and butanoyl. 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.

[0044] "Alkanoyloxy" means an alkanoyl group as defined herein, bonded to a parent group via an oxy group as defined herein. Examples of this group include acetoxy (-OAc or -OC(O)Me). In some embodiments, the alkanoyloxy group is -OC(O)-R, where R is a hydrogen, aliphatic group, or aromatic group as defined herein.

[0045] "Aliphatic" refers to a group of carbon atoms with 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 This refers to hydrocarbon groups having ), including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), their cyclic versions, and further including linear and branched configurations, as well as all stereoisomers and positional isomers. Aliphatic groups are either unsubstituted or substituted with functional groups as described herein, for example. For example, an aliphatic group can be substituted with one or more substituents, as described herein for alkyls.

[0046] "Aliphatic-carbonyl" means an aliphatic group that is or can be bonded to a compound disclosed herein, the aliphatic group being or becoming bonded via a carbonyl group (-C(O)-). In some embodiments, the aliphatic carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0047] "Aliphatic-carbonyloxy" means an aliphatic group that is or can be bonded to a compound disclosed herein, the aliphatic group being or becoming bonded via a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0048] "Aliphatic-oxy" means an aliphatic group that is or can be bonded to a compound disclosed herein, the aliphatic group being or becoming bonded via an oxy group (-C(O)-). In some embodiments, the aliphatic-oxy ​​group is -OR, where R is an optionally substituted aliphatic group as defined herein.

[0049] "Aliphatic-oxycarbonyl" means an aliphatic group that is or can be bonded to a compound disclosed herein, the aliphatic group being or becoming bonded 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.

[0050] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" each mean an alkyl, alkenyl, or alkynyl group as defined herein, which can be attached to a parent molecular group via an aryl group as defined herein. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups can be substituted with one or more substituents as described herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkyl-aryl), as well as those having an alkyl group having 1 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 1-6 alkyl-C 4-18 aryl). Exemplary unsubstituted alkenyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkenyl-aryl), as well as those having an alkenyl group having 2 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 2-6 alkenyl-C 4-18 aryl). Exemplary unsubstituted alkynyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkynyl-aryl), as well as those having an alkynyl group having 2 to 6 carbons and an aryl group having 4 to 18 carbons (i.e., C 2-6 alkynyl-C 4-18 aryl). In some embodiments, the alkyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl group is -L-R, where L is an aryl group or an arylene group as defined herein and R is an alkynyl group as defined herein.

[0051] "Alkenyl" refers to a molecule containing at least 2 to 50 carbon atoms (C) 2-50 ), for example, 2 carbon atoms to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, where the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of the parent alkene. The alkenyl group can be branched, linear, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). An exemplary alkenyl is an optionally substituted C having one or more double bonds. 2-24 Alkenyl groups include alkyl groups. Alkenyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogen atoms to form a suitable bond to the parent group or a suitable bond between the parent group and another substitution. Alkenyl groups can also be substituted or unsubstituted. For example, an alkenyl group 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.

[0052] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, trihaloalkoxys such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, and trifluoromethoxy. Alkoxy groups may be substituted or unsubstituted. For example, an alkoxy group may be substituted with one or more substituents, as described herein for alkyls. 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 An example is an alkoxy group.

[0053] "Alkoxyalkyl" means an alkyl group as defined herein that is substituted with an alkoxy group as defined herein. Exemplary unsubstituted alkoxyalkyl groups have 2 to 12 carbon atoms (C 2-12 Alkoxyalkyl groups, as well as groups having an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms (i.e., C 1-6 Alkoxy-C 1-6 It is an alkyl group. In some embodiments, the alkoxyalkyl group is -LOR, where L and R are each independently alkyl groups as defined herein.

[0054] "Alkoxycarbonyl" means -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group may be substituted or unsubstituted. For example, the alkoxycarbonyl group may be substituted with one or more substituents as described herein for alkyl groups. An example of an unsubstituted alkoxycarbonyl group is 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 Contains an alkoxycarbonyl group.

[0055] "Alkyl" refers to a group of carbon atoms (C) with at least 1 to 50 carbon atoms. 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10This refers to saturated monovalent hydrocarbons having ) such that saturated monovalent hydrocarbons can be derived by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, linear, or cyclic (e.g., cycloalkyl). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, and tetracosyl. Alkyl groups can also be substituted or unsubstituted. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogen atoms to form a suitable bond to the parent group or a suitable bond between the parent group and another substitution. For example, if an alkyl group has one, two, three, or two or more carbon atoms, (1)C 1-6 alkoxy(for example, -OR(where R is C) 1-6 (1) Alkyl)), (2)C 1-6 Alkyl sulfinyl (for example, -S(O)-R(where R is C) 1-6 (3)C 1-6 Alkyl sulfonyl (for example, -SO2-R(where R is C)) 1-6 (4) Alkyl (for example, -NR) 1 R 2 (In the formula, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2(1) These can, together with the nitrogen atom to which they are bonded, form a heterocyclyl group as defined herein.) (5) Aryl, (6) Arylalkoxy (e.g., -OLR (wherein L is alkyl and R is aryl)), (7) Aryloyl (e.g., -C(O)-R (wherein R is aryl)), (8) Azide (e.g., -N3), (9) Cyano (e.g., -CN), (10) Aldehyde (e.g., -C(O)H), (11) C 3-8 (12) Cycloalkyl, (13) Halo, (14) Heterocyclyl (e.g., a 5, 6, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein), (15) Heterocyclyloxy (e.g., -OR (wherein R is a heterocyclyl as defined herein)), (16) Heterocycliroyl (e.g., -C(O)-R (wherein R is a heterocyclyl as defined herein)), (17) Hydroxyl (e.g., -OH), (18) N-protected amino, (19) Nitro (e.g., -NO2), (10) Oxo (e.g., =O), (11) C 1-6 Thioalkyls (e.g., -SR (where R is alkyl)), (21) thiols (e.g., -SH), (22) -CO2R 1 , where R 1 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 Alkyl, and R is C 4-18 (Selected from the group consisting of aryls), (23)-C(O)NR 1 R 2 , where R 1 and R 2 Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 Alkyl, and R is C 4-18selected from the group consisting of aryl)), (24)-SO2R 1 , wherein R 1 is (a) C 1-6 alkyl, (b) C 4-18 aryl, and (c) C 4-18 aryl-C 1-6 alkyl (for example, -L-R (where L is C 1-6 alkyl, and R is C 4-18 aryl)), (25)-SO2NR 1 R 2 , wherein R 1 and R 2 each are independently (a) hydrogen, (b) C 1-6 alkyl, (c) C 4-18 aryl, and (d) C 4-18 aryl-C 1-6 alkyl (for example, -L-R (where L is C 1-6 alkyl, and R is C 4-18 aryl)), (26)-NR 1 R 2 , wherein R 1 and R 2 each are independently (a) hydrogen, (b) an N-protecting group, (c) C 1-6 alkyl, (d) C 2-6 alkenyl, (e) C 2-6 alkynyl, (f) C 4-18 aryl, (g) C 4-18 aryl-C 1-6 alkyl (for example, -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 (for example, -L-R (where L is C 1-6 alkyl, and R is C 3-8The alkyl group can be substituted with four substituents independently selected from the group consisting of cycloalkyl groups, and in one embodiment, two groups are not bonded to the nitrogen atom via carbonyl or sulfonyl groups. The alkyl group may be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo 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 It is an alkyl group.

[0056] As used herein, “alkyl halides” refers to compounds containing one or more carbon-halogen bonds. Alkyl halides as used herein may be saturated compounds without double or triple carbon-carbon bonds, or unsaturated compounds (which may contain double and triple carbon-carbon 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.

[0057] "Alkylene," "alkenylene," or "alkynylene" respectively refer to the polyvalent (e.g., divalent) forms of alkyl, alkenyl, or alkynyl groups as described herein. Examples of alkylene groups include methylene, ethylene, propylene, and butylene. 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 2-24In 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 The group is an alkenylene or alkynylene group. The alkylene, alkenylene, or alkynylene group may be branched or unbranched. The alkylene, alkenylene, or alkynylene group may also be substituted or unsubstituted. For example, the alkylene, alkenylene, or alkynylene group may be substituted with one or more substituents, as described herein for alkyl groups.

[0058] "Alkyl sulfinyl" means an alkyl group as defined herein, bonded to a parent molecule via an -S(O)- group. In some embodiments, the unsubstituted alkyl sulfinyl group is C 1-6 or C 1-12 It is an alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group as defined herein.

[0059] "Alkylsulfinylalkyl" means an alkyl group as defined herein, substituted with an alkylsulfinyl group. In some embodiments, the unsubstituted alkylsulfinylalkyl group is C 2-12 or C 2-24 Alkylsulfinylalkyl groups (for example, C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In other embodiments, the alkylsulfinylalkyl group is -LS(O)-R, where L and R are each independently alkyl groups as defined herein.

[0060] "Alkylsulfonyl" means an alkyl group as defined herein, bonded to a parent molecule via a -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is C 1-6 or C 1-12 It is an alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is optionally substituted alkyl (e.g., optionally substituted C as described herein). 1-12 (This includes alkyl, haloalkyl, or perfluoroalkyl elements.)

[0061] "Alkylsulfonylalkyl" means an alkyl group as defined herein, substituted with an alkylsulfonyl group. In some embodiments, the unsubstituted alkylsulfonylalkyl group is C 2-12 or C 2-24 Alkylsulfonylalkyl groups (for example, C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In other embodiments, the alkylsulfonylalkyl group is -L-SO2-R, where L and R are each independently alkyl groups as defined herein.

[0062] "Alkynyl" refers to a molecule with at least 2 carbon atoms to 50 carbon atoms (C) 2-50 ), for example, 2 carbon atoms to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, where the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of the parent alkyne. The alkynyl group can be branched, linear, or cyclic (e.g., cycloalkynyl). An exemplary “alkynyl” is an optionally substituted C having one or more triple bonds. 2-24Alkynyl groups include alkyl groups. Alkynyl groups can be cyclic or acyclic, with examples including ethynyl and 1-propynyl. Alkynyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent group or a suitable bond between the parent group and another substitution. Alkynyl groups can also be substituted or unsubstituted. For example, an alkynyl group can be substituted with one or more substituents, as described herein for alkyl groups.

[0063] "Ambient temperature" refers to temperatures within the range of 16°C to 26°C, for example, 19°C to 25°C or 20°C to 25°C.

[0064] "Amide" is -C(O)NR 1 R 2 or -NHCOR 1 This means that in the formula, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 These can, together with the nitrogen atoms to which they are bonded, form a heterocyclyl group as defined herein.

[0065] "Amino" means -NR 1 R 2 This means that in the formula, R 1 and R 2 Each of these is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or in formula R 1 and R 2 These, together with the nitrogen atoms to which they are bonded, can form a heterocyclyl group as defined herein. In certain embodiments, R 1 , R 2Each of these is 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 silyloxy. In certain embodiments, R 1 and R 2 These can combine with the nitrogen atoms to which they are bonded to form optionally substituted heterocyclines.

[0066] "Aminoalkyl" means 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 L is an alkyl group as defined herein, and R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 These can, together with the nitrogen atom to which they are bonded, form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic as defined herein, or any combination thereof, or R 1 and R 2 Each of these can, together with the nitrogen atom to which it is bonded, form a heterocyclyl group as defined herein, R 3 and R 4 Each of these is independently an H or alkyl as defined herein.

[0067] "Amino-oxy" means an oxy group as defined herein, substituted with an amino group as defined herein. In some embodiments, the amino-oxy group is -O-NR 1 R 2 And in the formula, R 1 and R 2 Each of these can be independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as described herein, or R 1 and R 2 These, together with the nitrogen atoms to which they are bonded, can form a heterocyclyl group as defined herein. In certain embodiments, R 1 , R 2 Each of these is 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 silyloxy.

[0068] "Aromatic" means a cyclic conjugated group or moiety of 5 to 15 ring atoms having a monocycle (e.g., phenyl) or a plurality of fused rings (e.g., naphthyl, indolyl, or pyrazolopyridinyl) in which at least one ring is aromatic. That is, at least one ring, and optionally the plurality of fused rings, have a continuous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Huckel's rule (4n+2). Bonding to the parent structure is typically via the aromatic moiety of the fused ring system. The aromatic group is either unsubstituted or substituted with functional groups, for example, as described herein. For example, the aromatic group may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

[0069] "Aromatic-carbonyl" means an aromatic group that is or can be bonded to a compound disclosed herein, the aromatic group being or becoming bonded via a carbonyl group (-C(O)-). In some embodiments, the aromatic carbonyl group is -C(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0070] "Aromatic carbonyloxy" means an aromatic group that is or can be bonded to a compound disclosed herein, the aromatic group being or becoming bonded via a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0071] "Aromatic-oxy" means an aromatic group that is or can be bonded to a compound disclosed herein, the aromatic group being or becoming bonded via an oxy group (-O-). In some embodiments, the aromatic-oxy ​​group is -OR, where R is an optionally substituted aromatic group as defined herein.

[0072] "Aromatic-oxycarbonyl" means an aromatic group that is or can be bonded to a compound disclosed herein, the aromatic group being or becoming bonded via an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic carbonyl group is -C(O)OR, where R is an optionally substituted aromatic group as defined herein.

[0073] "Aryl" refers to a compound having a single ring or multiple fused rings, with at least 5 to 15 carbon atoms (C) 5-15 ), for example, 5 to 10 carbon atoms (C 5-10The term aryl means an aromatic carbocyclic group containing aryl atoms, and the fused ring may be aromatic or non-aromatic, provided that the bonding sites to the rest of the compounds disclosed herein are via atoms of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, and phenoxybenzene. The term aryl also includes heteroaryls, which are defined as groups 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. Similarly, the term nonheteroaryl is also included in the term aryl and defines groups containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (for example, -C(O)-R (where R is C) 1-6 (1) Alkyl)), (2)C 1-6 Alkyl, (3)C 1-6 alkoxy(for example, -OR(where R is C) 1-6 (4)C 1-6 Alkoxy-C 1-6 Alkyl (for example, -LOR(wherein L and R are independently C) 1-6 (5)C 1-6 Alkyl sulfinyl (for example, -S(O)-R(where R is C) 1-6 (6)C 1-6 Alkylsulfinyl-C 1-6 Alkyl (for example, -LS(O)-R(wherein L and R are independently C) 1-6 (7)C 1-6 Alkyl sulfonyl (for example, -SO2-R(where R is C)) 1-6 (8)C 1-6 Alkylsulfonyl-C 1-6Alkyl (for example, -L-SO2-R(wherein L and R are independently C) 1-6 (9) alkyl, (10) amino (e.g., -NR) 1 R 2 (In the formula, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 (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 (In the formula, L 1 is C 1-6 It is alkyl, L 2 is covalent or C 1-6 It is alkyl, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein, or R 1 and R 2 Each of these can, together with the nitrogen atom to which it is bonded, form a heterocyclyl group as defined herein, R 3 and R 4 Each of these is independently H or C 1-6 (12) Alkyl, (13) Heteroaryl, (14) C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 4-18(14) Aryl oil (e.g., -C(O)-R (where R is aryl)), (15) Azide (e.g., -N3), (16) Cyano (e.g., -CN), (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C) 1-6 (18) Aldehydes (e.g., -C(O)H), (19) Aldehydes -C 1-6 Alkyl (for example, -LC(O)H (where L is C) 1-6 (It is alkyl)), (20)C 3-8 Cycloalkyl, (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 3-8 (22) Halo, (23) C 1-6 Haloalkyl (e.g., -L) 1 -X or -L 2 -C(X)(R 1 )-R 2 (L in the formula 1 is C 1-6 It is alkyl, L 2 is covalent or C 1-6 It is alkyl, where X is fluoro, bromo, chloro or iodo, and R 1 and R 2 Each of these is independently H or C 1-6 (1) alkyl), (24) heterocyclyl (e.g., a 5, 6, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms as defined herein), (25) heterocyclyloxy (e.g., -OR (wherein R is a heterocyclyl as defined herein)), (26) heterocycliroyl (e.g., -C(O)-R (wherein R is a 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 (In the formula, L 1 is C 1-6 It is alkyl, L2 R is covalent or alkyl, 1 and R 2 Each of these independently refers to hydrogen or C as defined herein. 1-6 (Alkyl), (29) Nitro, (30) C 1-6 Nitroalkyl (e.g., -L) 1 -NO or -L 2 -C(NO)(R 1 )-R 2 (In the formula, L 1 is C 1-6 It is alkyl, L 2 R is covalent or alkyl, 1 and R 2 Each of these independently refers to hydrogen or C as defined herein. 1-6 (Alkyl), (31)N-protected amino, (32)N-protected amino-C 1-6 Alkyl, (33)oxo (e.g., =O), (34)C 1-6 Thioalkyl (for example, -SR (where R is C) 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (for example, -LSR(wherein L and R are independently C)) 1-6 (It is alkyl)), (36)-(CH2) r CO2R 1 (In the formula, r is an integer from 0 to 4, R 1 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 4-18 (Selected from the group consisting of aryls), (37)-(CH2) r CONR 1 R 2 (In the formula, r is an integer from 0 to 4, R 1 and R 2 Each of these independently, (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)C 4-18Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 4-18 (Selected from the group consisting of aryls), (38)-(CH2) r SO2R 1 (In the formula, r is an integer from 0 to 4, R 1 (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 4-18 (Selected from the group consisting of aryls), (39)-(CH2) r SO2NR 1 R 2 (In the formula, r is an integer from 0 to 4, R 1 and R 2 Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 4-18 Aryl-C 1-6 Alkyl (for example, -LR(where L is C) 1-6 It is alkyl, and R is C 4-18 (Selected from the group consisting of aryls), (40)-(CH2) r NR 1 R 2 (In the formula, r is an integer from 0 to 4, R 1 and R 2 Each of these independently consists of (a) hydrogen, (b) an N-protecting group, and (c) C 1-6 Alkyl, (d)C 2-6 Alkenil, (e)C 2-6 Alkinyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR(where L is C)) 1-6 It is alkyl, and R is C 4-18 (It is an aryl compound), (h)C 3-8 Cycloalkyl, and (i)C 3-8 Cycloalkyl-C 1-6Alkyl (e.g., -LR(where L is C)) 1-6 It is alkyl, and R is C 3-8 Selected from the group consisting of (cycloalkyl), in one embodiment, two groups are not bonded to the nitrogen atom via a carbonyl or sulfonyl group, (41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2) n CF3 (wherein n is an integer from 0 to 10)), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3 (wherein n is an integer from 0 to 10), (44) aryloxy (e.g., -OR (wherein R is aryl)), (45) cycloalkoxy (e.g., -OR (wherein R is cycloalkyl)), (46) cycloalkylalkoxy (e.g., -OLR (wherein L is alkyl and R is cycloalkyl)), (47) arylalkoxy (e.g., -OLR (wherein L is alkyl and R is aryl)). In certain embodiments, 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 It is an aryl group.

[0074] "Aryl-alkyl," "aryl-alkenyl," and "aryl-alkynyl" mean aryl groups as defined herein that can be bonded to a parent molecule via an alkyl, alkenyl, or alkynyl group, as defined herein, respectively. Aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl groups may be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl, and / or aryl-alkynyl groups may be substituted with one or more substituents, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbon atoms (C 7-16Arylalkyl groups, as well as those having an aryl group having 4 to 18 carbon atoms and an alkyl group having 1 to 6 carbon atoms (i.e., C 4-18 Aryl-C 1-6 It is an alkyl group. An example of an unsubstituted aryl-alkenyl group is one having 7 to 16 carbon atoms (C 7-16 (aryl-alkenyl), as well as those having an aryl group having 4 to 18 carbon atoms and an alkenyl group having 2 to 6 carbon atoms (i.e., C 4-18 Aryl-C 2-6 It is an alkenyl. An example of an unsubstituted aryl-alkynyl group is one having 7 to 16 carbon atoms (C 7-16 (aryl-alkynyl), as well as those having an aryl group having 4 to 18 carbon atoms and an alkynyl group having 2 to 6 carbon atoms (i.e., C 4-18 Aryl-C 2-6 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 alkenylene 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 alkynylene group as defined herein, and R is an aryl group as defined herein.

[0075] "Arylene" means the polyvalent (e.g., divalent) form of the aryl group described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10The arylene group may be branched or unbranched. The arylene group may also be substituted or unsubstituted. For example, the arylene group may be substituted with one or more substituents, as described herein for aryl groups.

[0076] "Arylalkoxy" means an aryl-alkyl group as defined herein, bonded to a parent molecular 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.

[0077] "Aryloxy" means -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 It is an aryloxy group. In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, etc.

[0078] "Aryloxycarbonyl" means an aryloxy group as defined herein, bonded to a parent group via a carbonyl group. In some embodiments, the unsubstituted aryloxycarbonyl group is C 5-19 It is an aryloxycarbonyl group. In other embodiments, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group as defined herein.

[0079] "Aryl oil" refers to an aryl group bonded to a parent group via a carbonyl group. In some embodiments, the unsubstituted aryl oil group is C 7-11 Aryl oil or C 5-19 It is an aryl oil group. In other embodiments, the aryl oil group is -C(O)-R, where R is an aryl group as defined herein.

[0080] "Aryl oil oxy" means an aryl oil group as defined herein, bonded to a parent group via an oxy group. In some embodiments, the unsubstituted aryl oil oxy group is C 5-19 It is an aryl oil oxy group. In other embodiments, the aryl oil oxy group is -OC(O)-R, where R is an aryl group as defined herein.

[0081] "Azide" refers to the -N3 group.

[0082] "Azidoalkyl" means an azide group bonded to a parent molecule via an alkyl group as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group as defined herein.

[0083] "Azo" means -N=N- group.

[0084] "Carbamoyl" means an amino group bonded to a parent molecule via a carbonyl group as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 It is a base, R 1 and R 2 Each of them is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 These can, together with the nitrogen atoms to which they are bonded, form a heterocyclyl group as defined herein.

[0085] "Carbamoyloxy" means a carbamoyl group as defined herein, bonded to a parent group via an n-oxy group, as defined herein. In some embodiments, the carbamoyl is -OC(O)NR 1 R 2It is a base, R 1 and R 2 Each of these is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 These can, together with the nitrogen atoms to which they are bonded, form a heterocyclyl group as defined herein.

[0086] "Carbonimidoyl" means a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein.

[0087] "Carbonyl" refers to a -C(O)- group, which can also be represented as >C=O.

[0088] "Carboxyl" refers to the -CO2H group or its anion.

[0089] A "catalyst," as readily understood by those skilled in the art, means a compound that can catalyze a synthesis reaction and is typically present in small amounts relative to the reactants. In some embodiments, the catalyst may include a transition metal coordination complex.

[0090] "Cyanat" refers to the -OCN group.

[0091] "Cyano" refers to the -CN group.

[0092] "Aliphatic" means a cyclic aliphatic group as defined herein.

[0093] "Cycloalkoxy" means a cycloalkyl group as defined herein, bonded to a parent molecular group via an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group as defined herein.

[0094] "Cycloalkylalkoxy" means an -OLR group, where L is an alkyl or alkylene group as defined herein, and R is a cycloalkyl group as defined herein.

[0095] Unless otherwise specified, "cycloalkyl" means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group with 3 to 8 carbon atoms, with examples including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and bicyclo[2.2.1heptyl]. 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. Furthermore, a cycloalkyl group may contain one or more double and / or triple bonds.

[0096] "Cycloheteroaliphatic" means a cyclic heteroaliphatic group as defined herein.

[0097] "Disilanil" refers to a group containing a Si-Si bond. In some embodiments, the disilanil group is -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - It is a base, and in the formula, R S1 , R S2 , R S3 , R S4 , and R S5Each of these is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino.

[0098] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0099] An "electron-donating group" refers to a functional group that can donate at least a portion of its electron density to a directly bonded ring through resonance or other means.

[0100] An "electron-withdrawing group" refers to a functional group that can accept electron density from the ring to which it is directly bonded through means such as induced electron withdrawal.

[0101] "Halo" means F, Cl, Br, or I.

[0102] "Chalcogen" means O, S, Se, or Te.

[0103] "Haloaliphatic" means an aliphatic group as defined herein in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodine.

[0104] "Haloalkyl" means an alkyl group as defined herein in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodine. In independent embodiments, the haloalkyl group may be a -CX3 group, where each X can be independently selected from fluoro, bromo, chloro, or iodine. In some embodiments, the haloalkyl group is -LX, where L is an alkyl group as defined herein and X is fluoro, bromo, chloro, or iodine. In other embodiments, the haloalkyl group is -LC(X)(R 1 )-R 2 (wherein L is a covalent bond or an alkyl group as defined herein), X is fluoro, bromo, chloro or iodine, and R 1 and R 2 Each of these is independently an H or alkyl as defined herein.

[0105] "Haloheteroaliphatic" means a heteroaliphatic as defined herein, in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by halogen atoms such as fluoro, bromo, chloro, or iodine.

[0106] "Heteroaliphatic" means an aliphatic group as defined herein, comprising at least one to twenty heteroatoms, for example, one to fifteen heteroatoms, or one to five heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms. Heteroaliphatic groups are either unsubstituted or substituted with functional groups as described herein, for example. For example, heteroaliphatic groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0107] "Heteroaliphatic-carbonyl" means a heteroaliphatic group that is or can be bonded to a compound disclosed herein, the heteroaliphatic group being or becoming bonded via a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0108] "Heteroaliphatic-carbonyloxy" means a heteroaliphatic group that is or can be bonded to a compound disclosed herein, the heteroaliphatic group being or becoming bonded via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0109] "Heteroaliphatic-oxy" means a heteroaliphatic group that is or can be bonded to a compound disclosed herein, the heteroaliphatic group being or becoming bonded via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0110] "Heteroaliphatic-oxycarbonyl" means a heteroaliphatic group that is or can be bonded to a compound disclosed herein, the heteroaliphatic group being or becoming bonded via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0111] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" mean an alkyl, alkenyl, or alkynyl group (which may be branched, linear, or cyclic) as defined herein, comprising at least one to twenty heteroatoms, for example, one to fifteen heteroatoms or one to five heteroatoms, and which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group.

[0112] "Heteroalkylene," "heteroalkenylene," and "heteroalkylynylene" respectively refer to the polyvalent (e.g., divalent) form of the heteroalkyl, heteroalkenyl, or heteroalkynyl group as described herein.

[0113] "Heteroaromatic" means an aromatic group as defined herein, comprising at least one to twenty heteroatoms, for example, one to fifteen heteroatoms, or one to five heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the group. Heteroaromatic groups are either unsubstituted or substituted with functional groups, for example, those described herein. For example, heteroaromatic groups may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

[0114] "Heteroaromatic-carbonyl" means a heteroaromatic group that is or can be bonded to a compound disclosed herein, the heteroaromatic group being or becoming bonded via a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0115] "Heteroaromatic-carbonyloxy" means a heteroaromatic group that is or can be bonded to a compound disclosed herein, the heteroaromatic group being or becoming bonded via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0116] "Heteroaromatic-oxy" means a heteroaromatic group that is or can be bonded to a compound disclosed herein, the heteroaromatic group being or becoming bonded via an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​group is -OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0117] "Heteroaromatic-oxycarbonyl" means a heteroaromatic group that is or can be bonded to a compound disclosed herein, the heteroaromatic group being or becoming bonded via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic carbonyl group is -C(O)OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0118] "Heteroaryl" means an aryl group containing at least 1 to 6 heteroatoms, for example 1 to 4 heteroatoms, which can be selected from oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and their oxidized forms within the ring, but are not limited thereto. Such heteroaryl groups can have a monocyclic or multiple condensed rings, the condensed rings may or may not be aromatic, and / or may contain heteroatoms as long as the bonding point is through an atom of an aromatic heteroaryl group. The heteroaryl group may be substituted with one or more groups other than hydrogen, for example aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl includes a subset of heterocyclyl groups as defined herein that are aromatic, i.e., contain 4n + 2 π electrons within a monocyclic or polycyclic ring system.

[0119] "Heteroarylene" means the polyvalent (e.g., divalent) form of a heteroaryl group as described herein.

[0120] "Heteroatom" means an atom other than carbon such as oxygen, nitrogen, sulfur, silicon, boron, selenium or phosphorus. In certain disclosed embodiments, for example, when valence constraints do not permit, the heteroatom does not include a halogen atom.

[0121] "Heterocyclyl", unless otherwise specified, means a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (independently selected from the group consisting of, for example, nitrogen, oxygen, phosphorus, sulfur, or halogen). The 5-membered ring has 0 to 2 double bonds, and the 6- and 7-membered rings have 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 to 1, 2, or 3 rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocycle, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc. Examples of heterocycles include thianyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uracil, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuryl, benzothienyl, etc.

[0122] "Heterocyclyloxy" means a heterocyclyl group as defined herein, bonded to a parent molecular group via an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is the heterocyclyl group as defined herein.

[0123] "Heterocyclyl" means a heterocyclyl group as defined herein, bonded to a parent molecule via a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group as defined herein.

[0124] "Hydrazino" is -NR 1 -NR 2 R 3 This means that in the formula, R 1 , R 2 and R 3 Each of these is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or in formula R 1 and R 2 A combination of or R 2 and R 3 The combination with the nitrogen atom to which each is bonded can form a heterocyclyl group as defined herein. In certain embodiments, R 1 , R 2 , or R 3 Each of these is independently H, an optionally substituted alkyl, an optionally substituted aryl, an optionally substituted alkyl-aryl, or an optionally substituted aryl-alkyl. In certain embodiments, R 2 and R 3 These can combine with the nitrogen atoms to which they are bonded to form optionally substituted heterocyclines.

[0125] "Hydroxyl" means -OH.

[0126] "Hydroxyalkyl" means an alkyl group as defined herein that is substituted with 1 to 3 hydroxyl groups, however, one or fewer hydroxyl groups may be bonded to a single carbon atom of the alkyl group, such as hydroxymethyl and dihydroxypropyl. 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 In the formula, L is a covalent bond or alkyl group as defined herein, and R 1 and R 2 Each of these is independently an H or alkyl as defined herein.

[0127] "Idomidoyl" refers to the portion containing the carbonimidoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2- And in the formula, R 1 and R 2 Each of these is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein. In other embodiments, the imidoyl group is -C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar And in the formula, R 1R 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, optionally substituted aryl-alkyl, or optionally substituted silyloxy. Ak R is an optionally substituted alkyl or optionally substituted aliphatic, Ar is an optionally substituted aryl or optionally substituted aromatic.

[0128] "Imino" means -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0129] "Isocyanate" refers to the -NCO group.

[0130] "Isocyano" refers to the -NC group.

[0131] "Ketone" means a compound containing -C(O)R or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof as defined herein. An example of a ketone is R 1 C(O)R can be included in the formula, where R and R 1 Each of these is independently selected from the aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0132] "Nitro" refers to the -NO2 group.

[0133] "Nitroalkyl" means an alkyl group as defined herein, substituted with 1 to 3 nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group as defined herein. In other embodiments, the nitroalkyl group is -LC(NO)(R 1 )-R 2 In the formula, L is a covalent bond or alkyl group as defined herein, and R 1 and R 2 Each of these is independently an H or alkyl as defined herein.

[0134] "Oxo" means an oxygen group.

[0135] "Oxy" means -O-.

[0136] "Perfluoroalkyl" means an alkyl group as defined herein, in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl and pentafluoroethyl. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer between 0 and 10.

[0137] "Perfluoroalkoxy" means an alkoxy group as defined herein, in which each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group as defined herein.

[0138] "Salt" means the ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that includes a cationic or anionic compound that forms an electrically neutral compound or structure. Salts can be prepared in situ during the final isolation and purification of the compounds of the present invention, or separately by reacting a free base group with a suitable organic acid (to produce an anionic salt), or by reacting an acidic group with a suitable metal or organic salt (to produce a cationic salt). Typical anionic salts include acetate, adipine, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, tartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptoneate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthate, iodide, lactate, lactobio This includes nitrates, laurates, lauryl sulfates, malates, maleates, malons, mandelates, mesylates, methanesulfons, methyl bromide, methylnitrates, methyl sulfates, mucates, 2-naphthalenesulfons, nicotinates, nitrates, oleates, oxalates, palmitates, pamoates, pectins, persulfates, 3-phenylpropionates, phosphates, picrinates, pivaphosphates, polygalacturonates, propions, salicylates, stearates, basic acetates, succinates, sulfates, tannates, tartrates, theophyllines, thiocyans, triiodides, toluenesulfons, undecanoates, valersates, and others.Typical cationic salts include metal salts, such as alkali salts or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, and sodium; other metal salts such as aluminum, bismuth, iron, and zinc; and, not limited to these, non-toxic ammonium, quaternary ammonium, and amino cations, including ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphadinium, phosphazenium, pyridinium, and other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrorium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazorium, optionally substituted isothiazorium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted fluzanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridinium Dazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperadinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted in This includes dorium, optionally substituted isoindrium, optionally substituted indridinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolidinium, optionally substituted dehydroquinolidinium, optionally substituted quinolinium, optionally substituted isoindrium, optionally substituted benzimidazolinium, and optionally substituted prium.

[0139] "Cyril" is -SiR 1 R 2 R 3 or -SiR 1R 2 - means base. In some embodiments, R 1 , R 2 , and R 3 Each of these is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino. In certain embodiments, R 1 , R 2 , and R 3 Each of these is 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, or an optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) c The formula is such that each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, where a, b, and c are each ≥ 0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0140] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 And in the formula, R 1 , R 2 , and R 3 Each of these is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino. In certain embodiments, R 1 , R2 and R 3 Each of which is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is ≧0 and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0141] "Sulfinyl" means a -S(O)- group.

[0142] [[ID=*********]] "Sulfo" means a -S(O)2OH group.

[0143] "Sulfonyl" or "sulfonate" means 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.

[0144] "Thioalkyl" means an alkyl group as defined herein bonded to the parent molecular group through a sulfur atom. An exemplary unsubstituted thioalkyl group is C 1-6 contains thioalkyl. In some embodiments, the thioalkyl group is -S-R, where R is an alkyl group as defined herein.

[0145] "Thiol" means a -SH group.

[0146] As used herein, "halosilane" refers to a compound containing one or more silicon-halogen bonds. Halosilanes include difluorosilane (SiH2F2), dichlorosilane (SiH2Cl2), dibromosilane (SiH2Br2), diiodosilane (SiH2I2), dimethyldifluorosilane (Si(CH3)2F2), dimethyldichlorosilane, dimethyldieobromosilane, and dimethyldiiodosilane.

[0147] As used herein, "dihalogen" refers to a diatomic molecule containing two halogen atoms, such as F2, Cl2, Br2, and I2.

[0148] Those skilled in the art will recognize that the definitions provided above are not intended to include unacceptable substitution patterns (e.g., a methyl group substituted with five different groups). Such unacceptable substitution patterns are readily recognizable to those skilled in the art. Any functional groups disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise specified.

[0149] The term "independently selected" means, when referring to the selection of R substituents in a molecule containing multiple R groups, that the selection of R substituents on different atoms of the molecule is independent, as is the selection of R substituents on a single atom that has multiple R substituents.

[0150] method In some embodiments, the deposition method provided herein includes the steps of providing a semiconductor substrate (e.g., a semiconductor substrate having one or more concave features), exposing the substrate to a metal precursor in vapor form, exposing the semiconductor substrate to a halogen-containing deposition activator (the halogen-containing deposition activator being different from the metal precursor), and exposing the semiconductor to a reducing agent. In some embodiments, the exposures are performed sequentially so that the two components do not flow into the process chamber simultaneously. In other embodiments, the reducing agent and the halogen-containing activator flow into the process chamber containing the semiconductor substrate simultaneously. In some examples, if the substrate is exposed to halogen-containing molecules before contact with the metal precursor, the deposition process may be inhibited rather than activated. Therefore, in some configurations, the substrate is first brought into contact with the metal precursor, and then with the halogen-containing activator.

[0151] The methods provided are used in some embodiments to deposit metals (e.g., molybdenum, tungsten, titanium, ruthenium, or cobalt) to fill concave features on a semiconductor substrate. Figures 1A–1C show schematic cross-sectional views of a semiconductor substrate undergoing metal deposition by the methods provided herein. Figure 1A shows a substrate having concave features 101 formed within a material layer 103, which may be a dielectric layer containing silicon and oxygen. A layer 105, which may contain metal silicide and silicon or metal (e.g., tungsten), is present at the bottom of the concave features 101. The substrate is backed with a metal nitride layer (e.g., a titanium nitride layer) 107 exposed within the field region, on the sidewalls of the concave features, and at the bottom of the concave features. According to one embodiment of the methods provided herein, the substrate is exposed to a metal precursor, followed by exposure to a halogen-containing activator and reducing agent to deposit a metal layer 109 as shown in Figure 1B. Next, exposure to the metal precursor, halogen-containing activator, and reducing agent is repeated as needed to deposit a metal film of the desired thickness and fill the concave features (completely or partially). Figure 1C shows the concave features after they have been completely filled with metal.

[0152] In another embodiment, a metal-containing layer (e.g., a metal carbide layer) is deposited as a liner between the dielectric layer and the metal layer using a method provided herein. For example, molybdenum carbide may be deposited as the liner instead of titanium nitride. This is shown in Figures 2A-2C. Figure 2A shows a semiconductor substrate having a concave feature 201 formed in a dielectric layer 203, the dielectric layer 203 can be, for example, a silicon oxide-based dielectric. In the illustrated example, the sidewalls of the concave feature 201 contain the exposed dielectric, and the bottom of the concave feature 201 contains a different material 205 (e.g., metal, metal silicide, or silicon). The metal carbide liner is deposited conformally using a method 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 activator), and a reducing agent (e.g., H2). The resulting structure is shown in Figure 2B, which shows a conformally deposited layer of molybdenum carbide 207 backing the substrate. Next, as shown in Figure 2C, a metal such as tungsten, molybdenum, cobalt, ruthenium, copper, tin, or an alloy containing any of these metals is deposited to fill the concave features, where 209 is the deposited metal layer filling the concave features. 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, and boron-containing films can be obtained by using reagents (metal precursors, halogen-containing activators, or reducing agents) of the desired element (e.g., N, O, or B).

[0153] Deposition in the illustrated examples can be carried out at temperatures of approximately 250°C to approximately 600°C (e.g., between approximately 300°C and 450°C) and pressures typically less than 300 Torr, e.g., approximately 0.1 to approximately 100 Torr. Metal precursors, reducing agents, and halogen-containing deposition activators are selected so that they can be introduced in vapor form under deposition conditions. In some embodiments, both the activation and reduction steps are performed in the same process chamber or process station of the deposition apparatus. The reactants (activator, metal precursor, and reducing agent) can be flowed into the process chamber with or without an inert carrier gas at a flow rate ranging, for example, 0.5 to 10,000 sccm, depending on the implementation. In some embodiments, deposition involves sequentially exposing the substrate to the metal precursor, deposition activator, and reducing agent, with each exposure lasting approximately 1 to approximately 500 seconds, e.g., approximately 5 to 50 seconds. In one exemplary implementation, the deposition process utilizes t-butyl chloride as the activator, MoCl5 as the metal precursor for depositing molybdenum carbide, and H2 as the reducing agent. Such depositions can be used to deposit molybdenum carbide or molybdenum metal. In some embodiments, the obtained molybdenum carbide or carbon-rich molybdenum is treated with an alkyl halide activator to increase the molybdenum content and decrease the carbon content in the film.

[0154] Figures 3A and 3B show some exemplary process flows of deposition methods using halogen-containing activators. These methods can be used to fill concave features with metal and to form metal-containing liners (such as for forming conformal MoC liners).

[0155] In some embodiments, activation with a halogen-containing activator is incorporated into the ALD process, as shown by the process flow diagram in Figure 3A. The process is initiated in step 301 by bringing the substrate into contact with a metal precursor. The substrate may be any of the substrates described herein, such as a substrate having an exposed metal layer, a metal nitride layer, a metal oxide layer, a silicon layer, or a silicon-containing dielectric layer. For example, the substrate may have the structure shown in Figure 1A, where an exposed titanium nitride layer backs the substrate surface within the field region, on the feature sidewalls, and at the bottom of the features. In another embodiment, the substrate has the structure shown in Figure 2A. Once the substrate is exposed to the metal precursor, the metal precursor is adsorbed onto the surface of the substrate. In some embodiments, the metal precursor is flowed into the process chamber in the absence of any co-current gas. In other embodiments, the metal precursor is flowed into the process chamber with an inert carrier gas such as nitrogen, argon, or helium. The flow of the metal precursor is then stopped, and in step 303, the substrate is brought into contact with a halogen-containing activator. The activator can be introduced into the process chamber with or without a carrier gas and can be adsorbed onto the surface of the substrate. After the flow of the activator stops, the process proceeds to step 305, in which the substrate is exposed to a reducing agent to form a metal-containing layer. After the flow of the reducing agent stops, in step 307, the process can be continued by repeating steps 301 to 305 until the metal-containing film is deposited to a desired thickness. For example, at least two deposition cycles can be performed, such as 2 to 2,000 cycles (e.g., 200 to 2,000), each cycle comprising each of steps 301, 303, and 305 once. Optionally, the deposition cycle may also include a purge step after one or more of steps 301, 303, and 305. In some embodiments, after each of steps 301, 303, and 305, the process chamber is purged with a purge gas (e.g., nitrogen or argon) to remove any unadsorbed reactants from the process chamber.

[0156] Next, following step 309, the semiconductor substrate may be treated to increase the metal content in the deposited film. This step is optional and may be used in embodiments where the content of other elements (e.g., carbon, nitrogen, oxygen, or boron) in the deposited metal-containing film is too high for the desired application. For example, if a low-carbon metal film is desired to fill concave features and the formed film has a higher carbon content than required (e.g., due to the incorporation of carbon from alkyl halide activators), the film may be treated to increase its metal content. In some embodiments, the treatment is hydrogen annealing. The substrate with the exposed film is in contact with hydrogen at a higher temperature and / or for a longer time than in step 305. For example, the formed metal-containing film may be deposited at a temperature of about 250°C to about 450°C and then annealed in a hydrogen atmosphere at a temperature of at least about 500°C, for example, at least about 650°C (e.g., at a temperature of about 700°C to 800°C). In some embodiments, the hydrogen annealing step is at least twice as long as step 305 of the deposition process.

[0157] In another embodiment, the metal content in the formed film can be increased by using prolonged exposure of the formed film to a metal halide. For example, the molybdenum content in the film can be increased by treating a deposited carbon-rich molybdenum film or molybdenum carbide film with MoCl5. This treatment is typically longer (e.g., at least twice as long) than the exposure of the molybdenum precursor during deposition and can be used to reduce the carbon content by converting the carbon to volatile carbon tetrachloride and removing it from the process chamber.

[0158] Halogen-containing activators can increase the deposition rate even when introduced simultaneously with a reducing agent. Furthermore, in some embodiments, such simultaneous exposure can result in a higher metal content in the formed metal-containing film. An example of a process flow in which a reducing agent is flowed into a process chamber together with a halogen-containing activator is shown in Figure 3B. The process is initiated in step 311 by bringing the semiconductor substrate into contact with a metal precursor. This step is performed without a simultaneous flow of the halogen-containing activator, although it may optionally include a simultaneous flow of the reducing agent. Next, the flow of the metal precursor is stopped and the process chamber is optionally purged (e.g., using an inert gas or hydrogen), and in step 313, the semiconductor substrate is brought into contact with the reducing agent and the halogen-containing activator. In this embodiment, the reducing agent and the halogen-containing activator flow into the process chamber simultaneously, without a flow of the metal-containing precursor. In some embodiments, the flow rate of the halogen-containing activator is about 10 to 40 sccm. Then, after the first portion of the metal-containing layer is formed, the process is optionally continued in step 315 by repeating steps 311 and 313. This process may include the number of deposition cycles required to form a metal-containing layer of the desired thickness. For example, at least two deposition cycles can be performed, such as 2 to 2,000 cycles (e.g., 200 to 2,000), with each cycle having one step 311 and one step 313. The process can then proceed to step 317, if necessary, where the substrate can be treated to increase the metal content in the deposited film. The treatment can be performed as described above for step 309.

[0159] Halogen-containing deposition activator Halogen-containing deposition activators include, but are not limited to, alkyl halides, halosilanes, dihalogens, halides of Group 13 elements, halides of Group 15 elements, and metal halides.

[0160] Alkyl halides that can be used in any of the methods provided herein include alkyl fluorides, alkyl chlorides, alkyl bromides, and alkyl iodides, and may contain one or more halogen atoms. Primary alkyl halides, secondary alkyl halides, and tertiary alkyl halides can be used. Primary alkyl halides include, for example, methyl fluoride, methyl chloride, methyl bromide, methyl iodide, ethyl fluoride, ethyl chloride, ethyl bromide, ethyl iodide, 1-fluoropropane, 1-chloropropane, 1-bromopropane, 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 t-butyl fluoride (also known as 2-fluoro-2-methylpropane), t-butyl chloride (also known as 2-chloro-2-methylpropane), t-butyl bromide (also known as 2-bromo-2-methylpropane), and t-butyl iodide (also known as 2-iodo-2-methylpropane).

[0161] In some embodiments, an alkyl halide having the following formula: Hal-C(R')2-CH(R")2 The formula used is 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 t-butyl chloride, 2-chloro-2-methylbutane, 2-chloro-2-methylpentane, and 2-chloro-2-methylhexane.

[0162] Halosilanes refer to molecules that contain a silicon-halogen bond. Examples of halosilanes include SiH2F2, SiH2Cl2, SiH2Br2, and SiH2I2.

[0163] Examples of dihalogens are F2, Cl2, Br2, and I2.

[0164] Examples of halides of Group 13 elements include boron halides such as boron trichloride (BCl3) and boron tribromide (BBr3), aluminum halides such as aluminum trichloride and aluminum tribromide, and gallium halides. Examples of halides of Group 15 elements include nitrogen halides, phosphorus halides, and antimony halides.

[0165] In some embodiments, the metal precursor and halogen-containing activator used for deposition contain the same halogen (e.g., chlorine). For example, the metal precursor may contain a metal-chlorine bond, and the activator may be an alkyl chloride. In other embodiments, the metal precursor and halogen-containing activator may have different halogens. For example, the metal precursor may contain a metal-chlorine bond, and the halogen-containing activator may contain a halogen different from chlorine (e.g., I or Br).

[0166] In some embodiments, chlorine-containing deposition activators are used. Examples of chlorine-containing deposition activators include, but are not limited to, hydrogen chloride (HCl), chlorine (Cl2), t-butyl chloride, chlorosilane (SiH3Cl), dichlorosilane (SiH2Cl2), trichlorosilane (SiHCl3), and silicon tetrachloride (SiCl4). 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.

[0167] 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.

[0168] Metal precursors The methods provided allow the use of various metal precursors for metal deposition according to the embodiments provided herein. The precursors are selected so that they can be delivered to the process chamber alone or with an inert carrier gas in gaseous form (e.g., vapor). For example, an inert gas flowing over a solid or liquid precursor can deliver the precursor to the process chamber. Examples of metals that can be deposited using vapor phase deposition, e.g., ALD and CVD deposition, include molybdenum, tungsten, cobalt, and ruthenium.

[0169] Molybdenum precursor Generally, molybdenum-containing precursors can contain molybdenum in a wide range of oxidation states from 0 to +6. In some embodiments, molybdenum compounds having molybdenum in low oxidation states of +3, +4, and +5 are preferred. The method provided is particularly useful for depositing molybdenum-containing materials from halogen-containing molybdenum-containing compounds, because silicon-containing reactants can assist in halogen capture, but halogen-free molybdenum-containing precursors can also be used. Suitable molybdenum-containing precursors include halide molybdenum and halide oxymolybdenum, such as fluoride, chloride, bromide, oxyfluoride, oxychloride, and oxybromide, where molybdenum may be in any oxidation state from +2 to +6.

[0170] To maintain appropriate volatility, in many embodiments discussed herein, precursors having a molecular weight of less than about 450 g / mol, for example less than about 400 g / mol, are selected.

[0171] In some embodiments, the molybdenum-containing precursor is of formula MoX n Y m The formula has the following characteristics, 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 MoCl5 and Mo2Cl 10 Examples include, but are not limited to, MoO2Cl2 and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6.

[0172] In some embodiments, the molybdenum-containing precursor includes a carbonyl ligand.

[0173] Halide-containing heteroreptic molybdenum compounds In one embodiment, a halide-containing heteroreptic molybdenum compound is used as a precursor for the deposition of molybdenum-containing films, such as for the deposition of molybdenum metal. In one embodiment, the precursor is a compound comprising molybdenum, at least one halide that forms a bond with molybdenum, and at least one organic ligand having one of the elements N, O, and S, wherein an atom of any of these elements forms a bond with molybdenum. Suitable organic ligands that provide a nitrogen or oxygen bond include amidinates, amidates, iminopyrrolidineates, diazadienes, beta-iminoamides, alpha-iminoalkoxides, beta-aminoalkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates. Suitable organic ligands that provide a sulfur bond include thioethers, thiolates, dithiolenes, dithiolates, and alpha-iminothiolenes. These ligands may 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 substituents. The organic ligand may be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum may be in various oxidation states such as +1, +2, +3, +4, +5, and +6.

[0174] The structures of exemplary suitable N and / or O-containing organic ligands 1-17 are shown in Figure 4, and the structures of exemplary suitable S-containing organic ligands 18-25 are shown in Figure 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, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, and cyclobutylethyl. In some embodiments, each R is an independently selected alkyl. In some embodiments, ligands having branched alkyl substituents, such as isopropyl and isobutyl, are preferred because such ligands provide a more volatile molybdenum precursor.

[0175] 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., unsubstituted or N-alkyl-substituted ethylenediamines), and higher dentate amines (e.g., substituted or unsubstituted diethylenetriamines). An example of a monodentate amine is amine 1 shown in Figure 4, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments, at least one R is alkyl, and each R is independently selected from H and alkyl. In some embodiments, at least one organic ligand is an amide, such as monoanionic amide 16, where at least one R is alkyl or fluoroalkyl, and each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, at least one organic ligand is an imide, such as dianionic imide 17, where R is alkyl or fluoroalkyl. In general, imide-containing precursors can be used for the deposition of various molybdenum-containing films (including molybdenum metal), but in some embodiments, they are preferred for the deposition of molybdenum nitride and molybdenum carbonitride because they can form strong molybdenum-nitrogen bonds and function 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 Figure 4, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidinate 2 is a monoanionic ligand capable of forming two molybdenum-nitrogen bonds and functions as a bidentate ligand.

[0176] In some embodiments, at least one organic ligand in the precursor is an amidate. An example of an amidate is amidate 3 shown in Figure 4, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidate 3 is a monoanionic ligand that can form one molybdenum-nitrogen and one molybdenum-oxygen bond and functions as a bidentate ligand.

[0177] In some embodiments, at least one organic ligand in the precursor is a diazadiene. Examples of diazadienes are 1,4-diazabuta-1,3-diene (DAD) 5, 6, and 7, where each R is independently selected from H, alkyl, and fluoroalkyl. An interesting property of this ligand is that it can exist in neutral form 5, monoanionic radical form 6, and dianionic form 7. Due to the redox activity of the monoanionic (radical) form 6, it can be removed relatively easily during deposition, making complexes of DAD 6 particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal. DAD ligands 5, 6, and 7 can each function as bidentate ligands forming two molybdenum-nitrogen bonds. In some embodiments, the molybdenum precursor contains DAD ligand 5, 6, or 7 as the organic ligand, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and t-butyl.

[0178] In some embodiments, at least one organic precursor is an iminopyrrolidinate (e.g., iminopyrrolidinate 4 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), a beta-iminoamide (e.g., beta-iminoamide 8, etc., where each R is independently selected from H, alkyl, and fluoroalkyl), an alpha-iminoalkoxide (e.g., alpha-iminoalkoxide 9 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), a beta-dikethyminate (e.g., beta-dikethyminate 10 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), a beta-ketoiminate (e.g., These include ketoimminate 11 (wherein each R is independently selected from H, alkyl, and fluoroalkyl), beta-diketonate 12 (e.g., beta-diketonate 12 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), pyrazolate (e.g., pyrazolate 13 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), beta-aminoalkoxide (e.g., beta-aminoalkoxide 14 (wherein each R is independently selected from H, alkyl, and fluoroalkyl)), or guazinidate 15 (e.g., guazinidate 15, where each R is independently selected from H, alkyl, and fluoroalkyl). These are monoanionic ligands that can bond to molybdenum in a bidentate manner.

[0179] In some embodiments, at least one organic precursor is a sulfur-containing ligand capable of forming a molybdenum-sulfur bond. In some embodiments, at least one organic ligand in the precursor is a thioether. The term “thioether” is used herein to broadly include both monodentate and polydentate (e.g., bidentate or tridentate) thioethers, as well as ligands containing both thioether and thiolate (or other) moieties. An example of a monodentate thioether is a dialkyl sulfide R2S, where each R is an alkyl such as dimethyl sulfide, diethyl sulfide, or diisobutyl sulfide. An example of a polydentate thioether ligand that also contains a thiolate moiety is (SCH2CH2SCH2CH2S). 2 - An example of a monodentate thioether is thioether 18 shown in Figure 5, where each R is independently selected from the group consisting of alkyl and fluoroalkyl. In some embodiments, each R is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl.

[0180] In some embodiments, at least one organic ligand is a thiolate, such as a monoanionic thiolate 19, where R is alkyl or fluoroalkyl. For example, R may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. In some embodiments, the thiolate is a dithiolate, for example, a dianionic alpha-dithiolate 24 (wherein each R is independently selected from H, alkyl, and fluoroalkyl), or a dianionic beta-dithiolate 25 (wherein each R is independently selected from H, alkyl, and fluoroalkyl). The dithiolate can form two molybdenum-sulfur bonds with molybdenum.

[0181] In some embodiments, at least one organic ligand in the precursor is dithiolene. Examples of dithiolene 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 neutral form 20, monoanionic radical form 21, and dianionic form 22. Due to the redox activity of the monoanionic radical form 21, it can be removed relatively easily during the deposition and reduction of the molybdenum precursor, making complexes of dithiolene 21 particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal. The dithiolene ligands 20, 21, and 22 can function as bidentate ligands, each capable of forming two molybdenum-sulfur bonds. In some embodiments, the molybdenum precursor comprises dithiolene ligands 20, 21, and / or 22 as organic ligands, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl.

[0182] In some embodiments, at least one organic ligand in the precursor is an alpha-iminothiolene, such as in 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 H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, and the R substituent at the nitrogen is independently selected from alkyl and fluoroalkyl. In some embodiments, the R substituent at the nitrogen is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and t-butyl. This ligand (similar to DAD and dithiolene) has a monoanionic radical form, as shown in structure 23, is redox active, and is readily removable during the reduction process.

[0183] In some embodiments, the precursor is of the formula Mo(X) m (L) nThe compound is having the formula, where m is selected from 1 to 4, n is selected from 1 to 3, each X is a halide independently selected from F, Cl, Br, and I, and each L is a ligand independently selected from the above organic ligands, such as amidinates, amidates, iminopyrrolidineates, diazadienes, betaiminoamides, alphaiminoalkoxides, betaaminoalkoxides, beta-diketiminates, beta-ketoimminates, beta-diketonates, amines, and pyrazolates, thioethers, thioates, dithiolenes, dithioates, and α-iminothiolenes. In some embodiments, in the named ligands, each R is independently selected from H, alkyls, and fluoroalkyls.

[0184] In some embodiments, L is a bidentate ligand. Examples of suitable molybdenum-containing precursors of formula Mo(L)Cl4 utilizing a bidentate ligand are shown in Figure 6A. These are Mo(V) compounds and include amidinate molybdenum complex 27, DAD complex 28, beta-diketiminate complex 29, pyrazolate complex 30, amidate complex 31, beta-iminoamide complex 32, beta-ketoimiminate complex 33, beta-aminoalkoxide complex 34, iminopyrrolidinenate complex 35, alpha-iminoalkoxide complex 36, and beta-diketonate complex 37.

[0185] The heteroreptic complexes having molybdenum-halide bonds and organic ligands described herein can be synthesized by reacting a molybdenum halide starting material with a compound containing an organic ligand in a neutral or anionic form. For example, a molybdenum(V) precursor can be prepared using MoCl5 as a starting material. A Mo(III) precursor can be prepared using MoX3(THF)3 as a starting material, where X is selected from chloride, bromide, and iodide, and THF is tetrahydrofuran. The starting materials can be treated with a ligand in a neutral or anionic form (e.g., a salt such as a lithium salt or a sodium salt) to form the heteroreptic complexes described herein.

[0186] The heteroreptic molybdenum compounds containing molybdenum-halide bonds and organic ligands described herein can advantageously provide high-purity molybdenum metal in CVD and ALD deposition methods provided herein. Furthermore, the use of these compounds may be associated with a reduction in substrate material etching compared to conventional homoreptic molybdenum halides. These advantages are described for illustrative purposes only and the use of these compounds is not limited to molybdenum metal deposition or deposition on etching-sensitive substrates.

[0187] In some embodiments, when deposition is carried out on a fluorine-sensitive material (e.g., a silicon-containing material), the precursor is selected to be fluorine-free, for example, containing one of Cl, Br, or I as a halide in the complex. Furthermore, in these embodiments, the use of compounds having fluoroalkyl substituents can be avoided.

[0188] Sulfur-containing molybdenum compounds In one embodiment, a sulfur-containing molybdenum compound is used as a molybdenum-containing precursor for the deposition of molybdenum-containing films, such as for the deposition of molybdenum metal and molybdenum silicide. In some embodiments, the molybdenum compound comprises molybdenum and at least one sulfur-containing ligand that provides a molybdenum-sulfur bond. Using a sulfur-containing ligand-based molybdenum precursor, a substantially impurity-free molybdenum-containing film can be deposited because sulfur impurities are easier to remove compared to oxygen, carbon, and nitrogen impurities. In some embodiments, the molybdenum compound does not contain a molybdenum-carbon bond and / or a molybdenum-oxygen double bond. In some embodiments, the molybdenum compound does not contain a molybdenum-nitrogen double bond. In some embodiments of the provided molybdenum precursor, molybdenum forms a bond only with sulfur atoms.

[0189] Suitable sulfur-containing ligands that provide a sulfur bond include thioethers, thiolates, dithiolenes, dithiolates, thiocarbamates, and α-iminothiolenes. The ligand may contain one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The ligand may be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum may be in various oxidation states such as 0, +1, +2, +3, +4, +5, and +6.

[0190] In some embodiments, the sulfur-containing ligands are ligands 18-25 shown in Figure 5, and the R substituents are as described above. Examples of suitable molybdenum precursors include molybdenum thiolate Mo(SR)4, where R is alkyl, e.g., methyl, ethylpropyl, butyl. In one specific example, the precursor is tetrakis(tert-butylthiolate)molybdenum(IV):Mo(SR)4 (where R is t-butyl). Another example of a suitable molybdenum precursor is a molybdenum thiocarbamate such as tetrakis(diethyldithiocarbamate)molybdenum(IV).

[0191] [ka]

[0192] In the formula, 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).

[0193] In some embodiments, dithiolene complexes of molybdenum are provided, where the dithiolene may be one of the neutral form 20, the anionic-radical form 21, and the dianionic form 22, and each R is independently H, alkyl, or fluoroalkyl.

[0194] Dithiolene complexes are redox active and can support molybdenum in various oxidation states. The redox reactions of dithiolene ligands 20, 21, and 22 are shown in Equation 1.

[0195] [ka]

[0196] In one implementation, the precursor is Mo(21)3, where each R in 21 is independently selected from H, alkyl, and fluoroalkyl groups. For example, R may be methyl, ethyl, CF3, etc. This is a homoreptic Mo(III) compound containing only molybdenum-sulfur bonds.

[0197] In some embodiments, the ligand can provide a nitrogen bond in addition to the sulfur bond. An example of such a ligand is alpha-iminothiolene 23, which is a redox-active radical anion ligand that can exhibit behavior similar to that of thiolenes. In some embodiments, the precursor is Mo(III) compound Mo(23)3, where each R in compound 23 is independently selected from H, alkyl, and fluoroalkyl.

[0198] In some embodiments, the precursor is MoL nThe compound is such that n is 2 to 6 and L is a sulfur-containing ligand, for example, one of the sulfur-containing ligands described herein. In some embodiments, each L is the same sulfur-containing ligand. In other embodiments, the precursor may contain 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, and Mo(25)3. The sulfur-containing molybdenum compounds described herein can be synthesized by reacting a molybdenum halide starting material with a compound containing an organosulfur-containing ligand in neutral or anionic form. For example, a molybdenum(V) precursor can be prepared using MoCl5 as a starting material. Mo(III) or Mo(IV) precursors can be prepared using the corresponding halide or MoX3(L)3 or MoX4(L)2 as a starting material, where X is selected from chlorides, bromides, and iodides, and L is a neutral Lewis base such as tetrahydrofuran or diethyl ether. The starting material can be treated with a desired sulfur-containing ligand in neutral or anionic form (e.g., a salt such as a lithium salt or a sodium salt) to form the sulfur-containing complex described herein.

[0199] For example, a Mo(IV) thiolate complex can be prepared by reacting molybdenum tetrachloride with lithium thiolate. For instance, MoCl4 can be reacted with t-BuSLi in a 1,2-dimethoxyethane solvent to form a Mo(t-BuS)4 compound.

[0200] α-iminothiolene ligands can be prepared from the corresponding α-iminoketones by thionation using a suitable reagent such as Lawson's reagent. The radical anion form of α-iminothiolene can then be prepared by subsequent treatment with an alkali metal such as lithium. The resulting ligands and ligand salts can be reacted with molybdenum halides to form α-iminothiolene-containing molybdenum compounds.

[0201] Molybdenum complexes can also be prepared using zero-valent starting materials, such as molybdenum hexacarbonyl. The starting materials can be treated with a neutral ligand, such as a thioether (dialkyl sulfide), to induce redox neutral ligand exchange. The zero-valent starting materials can also be treated with ligand precursors, such as bis(diethylthiocarbamoyl) disulfide or bis(trifluoromethyl)-1,2-dithiate, to induce oxidative addition and form the sulfur-containing complexes described herein.

[0202] The reaction may be carried out in various aprotic solvents. For example, the reaction may be carried out in ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, and 1,2-dimethoxyethane; in hydrocarbon solvents such as toluene, benzene, heptane, hexane, and pentane; or in halocarbon solvents such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, and chloroform. The reaction can be carried out over a wide temperature range, depending on the boiling point of the solvent and the solubility of the product. In some embodiments, the starting materials, reaction intermediates, and desired products are unstable to water and oxygen. Therefore, the reaction process should be carried out using anhydrous and oxygen-free conditions with the use of a protective inert gas such as nitrogen or argon.

[0203] 1,4-Diazabtadiene (DAD)-containing precursor In another embodiment, DAD-containing molybdenum-containing precursors are provided. DAD can be bound to molybdenum in its neutral form 5, its radical anionic form 6, and its dianionic form 7. In some embodiments, homoreptic DAD complexes of formula Mo(DAD)m are provided, where m is 1 to 3, and each DAD is independently selected from neutral DAD 5, radical anionic DAD 6, and dianionic DAD 7. The oxidation state of molybdenum in these complexes may range from 0 to +6. Non-limiting examples of suitable homoreptic DAD complexes include tris-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.

[0204] In some embodiments, homoreptic DAD complexes are prepared using a reaction between a molybdenum halide and a DAD ligand source with the desired electron configuration. For example, the tris-DAD Mo(III) precursor Mo(6)3 can be synthesized by reacting MoCl3 with three equivalents of the radical anion form of the DAD ligand, which can be prepared from the neutral form of the DAD ligand by treatment with an alkali metal such as lithium in a solvent such as THF, as shown in Formula 2.

[0205] [ka]

[0206] In some embodiments, heteroreptic DAD-containing molybdenum compounds are provided. In some implementations, the precursor comprises molybdenum, at least one DAD ligand bonded to the molybdenum, and at least one second ligand, where the DAD may be neutral DAD 6, radical anionic DAD 7, or dianionic DAD 8, and the second ligand is independently selected from anionic and neutral ligands. In some embodiments, the precursor does not contain a CO ligand as the sole second ligand. In some embodiments, the precursor is Mo(DAD) m (L) n (X) p In the formula, L is a neutral Lewis base ligand, each L independently selected from CO, amines, phosphines, thioethers, nitriles, and isonitriles; X is an anionic ligand, each X independently selected from halides, alkyls, allyls, and cyclopentadienyls; m is 1-3, n is 0-4, and p is 0-4. Nitriles are RCN compounds, where R is alkyl. Isonitriles are RNC compounds, where R is alkyl. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligands containing a donor atom selected from C, N, O, B, S, Si, Al, and P.

[0207] Examples of heteroreptic 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), and Mo(6)2(24).

[0208] Heteroreptic DAD-containing precursors can be prepared by a sequential salt metathesis reaction in a single pot or by using multiple steps. Molybdenum halide starting materials, such as Mo(V), Mo(IV), or Mo(III) halides, can be treated with anionic DAD ligands or other anionic ligands. Neutral Lewis base ligands can be replaced using heat treatment or photoexcitation.

[0209] Heteroreptic DAD-containing precursors can also be prepared using zero-valent molybdenum starting materials, such as molybdenum hexacarbonyl, which can undergo oxidative addition with redox-active ligands such as DAD ligands.

[0210] In some embodiments, precursors containing radical anionic DAD ligands 8 are particularly preferred for the deposition of molybdenum metal and high-purity molybdenum metal. In radical anionic form 7, the DAD ligand is thought to electronically bond to the empty molybdenum d orbital and function as an electron source that reduces the molybdenum ion to a zero-valent metallic state. After ligand-metal electron transfer, the volatile neutral DAD ligands 6 can be purged from the molybdenum metal growth surface. Since the DAD ligands can be removed intact from the growth surface, the use of DAD precursors reduces the incorporation of impurity elements such as C and N compared to other organometallic precursors. Therefore, molybdenum precursors containing radical anionic DAD ligands can be used to deposit high-purity molybdenum metal at low temperatures.

[0211] Di-molybdenum precursor In another embodiment, the precursor for the deposition of molybdenum-containing films is a di-molybdenum compound containing molybdenum-molybdenum bonds (e.g., multiple molybdenum-molybdenum bonds such as double bonds, or any multiple bonds having a bond order of 2 to 5). Such precursors are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal because such compounds are easier to reduce to metallic molybdenum than many mononuclear molybdenum compounds.

[0212] In some embodiments, a precursor for depositing a molybdenum-containing film is provided, and the precursor is Mo2L n In some embodiments, each L is independently selected from amidate, amidinate, and guanidinate ligands, n is 2 to 5, and the precursor contains multiple molybdenum-molybdenum bonds. In some embodiments, each L is independently selected from amidinate ligand 2, amidate ligand 3, and guanidinate ligand 15, and each R in amidinate, amidate, and guanidinate is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments, each L is an amidinate, and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is an amidinate, and the precursor has the formula Mo2(L)3 or Mo2(L)4. In some embodiments, each L is a guanidinate, and the precursor has the formula Mo2(L)3 or Mo2(L)4. In these complexes, molybdenum has low oxidation states of 2+ (in Mo2(L)3) and 3+ (in Mo2(L)4), and these complexes are particularly suitable for easy reduction to molybdenum metal.

[0213] Structure 38 shows an example of an exemplary structure of an amidate paddlewheel di-Mo(II) precursor having a quadruple molybdenum-molybdenum bond.

[0214] [ka]

[0215] In some embodiments, each of R and R' is independently selected from alkyl groups such as methyl, ethyl, isopropyl, and t-butyl. In some embodiments, one, two, three, or four amidate ligands in 38 may be substituted with amidinate or guanidinide ligands.

[0216] The dimolybdenum precursors described herein can be synthesized by using dimolybdenum tetraacetate as a starting material and treating it with a ligand salt such as lithium amide.

[0217] Other examples of suitable molybdenum-containing precursors 39–54 are shown in Figure 6B, where each L is a carbon-containing ligand that does not form a metal-carbon bond, m is an integer from 1 to 4, and n is an integer from 1 to 4. Each R and R1 is independently selected from the group consisting of alkyl, fluoroalkyl, and alkylsilyl. In some embodiments, each R1 is selected so that it does not provide a beta hydrogen atom. Examples of such R1 substituents include t-butyl and trialkylsilyl substituents. It should be noted that in some embodiments, R substituents of O and S atoms may provide beta hydrogen atoms, since beta hydrogens are not readily removed at these positions and are not expected to result in carbon contamination of the resulting film. In some embodiments, neither R nor R1 provides 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 Figure 6C, showing structures 55–58.

[0218] Cobalt precursor Cobalt metal can be deposited using various cobalt precursors, and cobalt can be in an oxidation state of +1, +2, or +3. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., cobalt(III) bis(acetylacetonate)), cobalt amidinate (e.g., bis(Nt-butyl-N'-ethylpropanimidoamidate)cobalt(II), cobaltocene), and carbonyl-containing cobalt precursors (e.g., cobalt tricarbonyl nitrosyl and cyclopentadienylcobalt dicarbonyl). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine.

[0219] Ruthenium precursor Ruthenium metal can be deposited using vaporizable ruthenium precursors such as bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenium cene, and cyclopentadienyl-propylcyclopentadienylruthenium(II).

[0220] Tungsten precursor The tungsten-containing layer can be deposited using various volatile precursors. In some embodiments, halogen-containing tungsten precursors, such as WHa x (wherein Hal is a halogen (e.g., F, Cl, Br, and / or I), and x is 2 to 6) is used. In some embodiments, tungsten chloride is used. Tungsten chloride includes tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In other examples, tungsten fluoride, such as tungsten hexafluoride, may be used.

[0221] Titanium precursor Titanium-containing layers can be deposited using several suitable volatile precursors, such as TiHal x These include titanium halides such as Hal, where Hal is a halogen (e.g., F, Cl, Br, and / or I) and x is 1 to 4. Other titanium precursors include titanium alkoxides, e.g., Ti(OR)4 (where R is alkyl), and titanium alkylamides, e.g., Ti(NR2)4 (where R is alkyl). Examples of titanium precursors include titanium tetrachloride (TiCl4), titanium dichloride (TiCl2), titanium tetraisopropoxide (Ti(OiPr)4), titanium tetraethoxide (Ti(OEt)4), tetrakis(dimethylamide)titanium (Ti(NMe2)4), and tetrakis(diethylamide)titanium (Ti(NEt2)4).

[0222] Reducing agent Several reducing agents can be used for depositing metal-containing films provided herein. Suitable reducing agents include hydrogen (H2), ammonia (NH3), hydrazine (N2H4), amines, diborane (B2H6), silane (SiH4), disilane (Si2H6), alcohols, hydrogen sulfide (H2S), or thiols. In some embodiments, the reducing agent is hydrogen (H2).

[0223] 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 deposited layer can be selected by choosing an appropriate combination of metal precursors, halogen-containing activators, and reducing agents, such that at least one of these reagents provides the required elements (in addition to the metal elements). For example, metal carbides can be deposited by selecting reagents such that at least one of the metal precursors, halogen-containing activators, and reducing agents contains carbon. In some embodiments, alkyl halide activators can supply the carbon necessary for depositing metal carbides. Similarly, metal nitrides can be deposited by selecting reagents such that at least one of the metal precursors, halogen-containing activators, and reducing agents contains nitrogen. For example, nitrogen-containing metal precursors and / or nitrogen-containing reducing agents (e.g., NH3) can be used to provide nitrogen for the deposition of metal nitrides and nitrogen-containing metal carbides (e.g., carbonitrides). Alternatively, additional volatile reagents may be added to supply the necessary elements. For example, H2 may function as a reducing agent, and NH3 may be an additional reagent to provide nitrogen in the deposition of metal nitrides.

[0224] Device The deposition methods described herein can be carried out using a variety of apparatuses. A suitable apparatus includes a process chamber having one or more inlets for introducing reactants, a substrate holder within the process chamber configured to hold the substrate in place during deposition, and optionally, a plasma generation mechanism configured to generate plasma in the process gas. Generally, the methods provided herein do not require plasma activation of the reactants and can be carried out in the absence of plasma treatment. The apparatus may include a controller having program instructions configured to perform any of the steps described herein. The deposition methods described herein can be carried out using corresponding ALD and CVD apparatuses available from Lam Research Corp. in Fremont, California, such as the Halo, Altus®, Vector®, and Striker® tools.

[0225] For example, in some embodiments, the apparatus includes a controller having program instructions, the instructions including instructions to cause contact between a semiconductor substrate and a metal precursor, instructions to cause contact between the semiconductor substrate and a halogen-containing deposition activator, wherein the halogen-containing deposition activator is different from the metal precursor, and instructions to cause contact between the semiconductor substrate and a reducing agent to form a layer of metal-containing material (e.g., molybdenum or molybdenum carbide). The controller may also include program instructions for performing any of the methods described herein.

[0226] Figure 7 shows an example of a suitable deposition apparatus for depositing metal-containing films using the provided method. Figure 7 schematically illustrates an embodiment of a process station 700 that may be used to deposit materials using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), both of which may be plasma-enhanced. For simplicity, the process station 700 is shown as a standalone process station having a process chamber body 702 for maintaining a low-pressure environment. However, it will be understood that multiple process stations 700 may be included in a common process tool environment. Furthermore, it will be understood that in some embodiments, one or more hardware parameters of the process station 700, including those discussed in detail below, may be programmed by one or more computer controllers.

[0227] The process station 700 is in fluid communication with a reactant delivery system 701 to deliver process gas to a distribution showerhead 706. The reactant delivery system 701 includes a mixing vessel 704 for blending and / or adjusting the process gas for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 may control the introduction of process gas into the mixing vessel 704. Similarly, a showerhead inlet valve 705 may control the introduction of process gas into the showerhead 706.

[0228] Several metal precursors may be stored in solid or liquid form before vaporization and subsequent delivery to the process station. For example, the embodiment in Figure 7 includes a vaporization point 703 for vaporizing solid reactants supplied to a mixing vessel 704. In some embodiments, the vaporization point 703 may be a heated vaporizer. In some embodiments, a flow of inert gas is bubbling through a heated solid metal precursor or a heated liquid metal precursor at near-atmospheric pressure to deliver precursor vapor to the process chamber. The precursor vapor produced from such a vaporizer may condense in the downstream delivery piping. Exposure of the condensed reactants to unsuitable gases may generate small particles. These small particles can clog piping, interfere with valve operation, and contaminate substrates, among other things. Some techniques to address these problems involve sweeping and / or exhausting the delivery piping to remove residual reactants. However, sweeping the delivery piping can increase process station cycle time and reduce process station throughput. Therefore, in some embodiments, the delivery piping downstream of the vaporization point 703 may be thermally tracked. In some examples, the mixing vessel 704 may also be thermally tracked. In one non-limiting example, the piping downstream of the vaporization point 703 has an increasing temperature profile in the mixing vessel 704, extending from approximately 100°C to approximately 200°C.

[0229] The showerhead 706 distributes the process gas toward the substrate 712. In the embodiment shown in Figure 7, the substrate 712 is located below the showerhead 706 and is shown resting on the pedestal 708. It will be understood that the showerhead 706 may have any preferred shape and may have any preferred number and arrangement of ports for distributing the process gas toward the substrate 712. Although not explicitly shown, in some embodiments, the showerhead 706 is a dual plenum showerhead including at least two types of conduits, the first type of conduit dedicated to the delivery of molybdenum-containing precursor vapor, and the second type of conduit dedicated to the delivery of a second (or other) reactant. In these embodiments, the molybdenum-containing precursor and reactant cannot be mixed in the conduit before entering the process chamber and do not share the conduit when delivered continuously into the chamber.

[0230] In some embodiments, the microvolume 707 is located below the showerhead 706. By performing the ALD and / or CVD processes within a microvolume rather than the entire volume of the process station, the exposure and sweeping times of reactants can be reduced, the time required to change process conditions (e.g., pressure, temperature, etc.) can be reduced, and the exposure of the process station robot to the process gas can be limited, etc. Exemplary microvolume sizes include, but are not limited to, volumes of 0.1 liters to 2 liters. This microvolume also affects productivity throughput. The deposition rate per cycle is reduced, but the cycle time is also reduced. In some cases, the latter effect is dramatic enough to improve the overall throughput of the module for a given target film thickness.

[0231] In some embodiments, the pedestal 708 may be raised or lowered to expose the substrate 712 to a minute volume 707 and / or vary the volume of the minute volume 707. For example, during the substrate transfer phase, the pedestal 708 may be lowered to load the substrate 712 onto the pedestal 708. During the deposition process phase, the pedestal 708 may be raised to position the substrate 712 within the minute volume 707. In some embodiments, the minute volume 707 may completely enclose a portion of the substrate 712 and the pedestal 708 to create a region of high flow impedance during the deposition process.

[0232] Optionally, the pedestal 708 may be lowered and / or raised during parts of the deposition process to modulate the process pressure, reactant concentration, etc., within the microvolume 707. In one scenario where the process chamber body 702 remains at base pressure during the deposition process, lowering the pedestal 708 may allow for the exhaust of the microvolume 707. Exemplary ratios of microvolume to process chamber volume include, but are not limited to, a volume ratio of 1:700 to 1:10. In some embodiments, it will be understood that the height of the pedestal may be programmed to adjust by a suitable computer controller.

[0233] While the exemplary microvolume variations described herein refer to a height-adjustable pedestal, it will be understood that in some embodiments, the volume of the microvolume 707 may be varied by adjusting the position of the showerhead 706 relative to the pedestal 708. Furthermore, it will be understood that the vertical position of the pedestal 708 and / or the showerhead 706 may be varied by any suitable mechanism within the scope of this disclosure. In some embodiments, the pedestal 708 may include a pivot axis for rotating the orientation of the substrate 712. In some embodiments, it will be understood that one or more of these exemplary adjustments may be performed programmatically by one or more suitable computer controllers.

[0234] Returning to the embodiment shown in Figure 7, the showerhead 706 and pedestal 708 electrically communicate with the RF power supply 714 and matching network 716 to power the plasma. In other embodiments, a device without a plasma generator is used to deposit a molybdenum-containing film using the provided method. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, radio frequency (RF) source power, RF source frequency, and plasma power pulse timing. For example, the RF power supply 714 and matching network 716 may operate at any preferred power to form a plasma having a desired composition of radical species. Similarly, the RF power supply 714 may supply RF power at any preferred frequency. In some embodiments, the RF power supply 714 may be configured to control the high-frequency RF power and the low-frequency RF power independently of each other. Exemplary low-frequency RF frequencies may range from 50 kHz to 700 kHz, but are not limited to these. Exemplary high-frequency RF frequencies may range from 1.8 MHz to 2.45 GHz, but are not limited to these. It will be understood that any suitable parameters may be discretely or continuously modulated to provide plasma energy for surface reactions. In a non-limiting example, the plasma power may be intermittently pulsed to reduce ion collisions with the substrate surface compared to the case of a continuously powered plasma.

[0235] In some embodiments, the plasma may be monitored in situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage-current sensors (e.g., VI probes). In another scenario, plasma density and / or process gas concentration may be measured by one or more emission spectroscopic sensors (OES). In some embodiments, one or more plasma parameters may be programmed to adjust based on measurements from such in situ plasma monitors. For example, an OES sensor may be used in a feedback loop to provide programmed control of plasma power. In some embodiments, it will be understood that other monitors may be used to monitor plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0236] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. For example, instructions for setting the plasma conditions of a plasma process stage may be included in the corresponding plasma activation recipe stage of the deposition process recipe. In some cases, process recipe stages may be arranged sequentially so that all instructions for the deposition process stage are executed concurrently with that process stage. In some embodiments, instructions for setting one or more plasma parameters may be included in recipe stages preceding the plasma process stage. For example, a first recipe stage may include instructions for setting the flow rates of the inert gas and / or reactant gas, instructions for setting the plasma generator to a power setpoint, and a time delay instruction for the first recipe stage. A second subsequent recipe stage may include instructions for enabling the plasma generator and a time delay instruction for the second recipe stage. A third recipe stage may include instructions for deactivating the plasma generator and a time delay instruction for the third recipe stage. It will be understood that these recipe stages may be further subdivided and / or repeated in any preferred manner within the scope of this disclosure.

[0237] In some embodiments, the pedestal 708 may be temperature-controlled via a heater 710. Furthermore, in some embodiments, pressure control of the deposition process station 700 may be provided by a butterfly valve 718. As shown in the embodiment of Figure 7, the butterfly valve 718 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the process station 700 may also be regulated by varying the flow rate of one or more gases introduced into the process station 700.

[0238] Figure 8 shows a schematic diagram of an embodiment of a multi-station process tool 800 having an inbound load lock 802 and an outbound load lock 804, one or both of which may be equipped with a remote plasma source. Such a tool may be used to process a substrate using the method provided herein. An atmospheric robot 806 is configured to move a wafer from a cassette loaded through a pod 808 to the inbound load lock 802 via an atmospheric port 810. 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. If the inbound load lock 802 is equipped with a remote plasma source, the wafer may be exposed to remote plasma processing in the load lock before being introduced into the processing chamber 814. Furthermore, the wafer may also be heated in the inbound load lock 802, for example, to remove moisture and adsorbed gases. Next, the chamber transport port 816 to the processing chamber 814 is opened, and another robot (not shown) places the wafer into the reactor on the pedestal of the first station, which is located inside the reactor for processing. The embodiment shown in Figure 8 includes a load lock, but it will be understood that in some embodiments, direct entry of the wafer into the process station may be provided.

[0239] The illustrated processing chamber 814 comprises four process stations numbered 1 to 4 in the embodiment shown in Figure 8. Each station has a heated pedestal (station 1 is shown as 818) and a gas line inlet. In some embodiments, it will be understood that each process station may have different or more purposes. Although the illustrated processing chamber 814 comprises four stations, it will be understood that the processing chamber according to this disclosure may have any preferred number of stations. For example, in some embodiments, the processing chamber may have five or more stations, and in other embodiments, the processing chamber may have three or fewer stations.

[0240] Figure 8 also shows an embodiment of a wafer handling system 890 for transferring wafers within the processing chamber 814. In some embodiments, the wafer handling system 890 may transfer wafers between various process stations and / or between process stations and load locks. It will be understood that any suitable wafer handling system may be used. Non-limiting examples include wafer carousels and wafer handling robots. Figure 8 also shows an embodiment of a system controller 850 used to control the processing conditions and hardware state of the process tool 800. The system controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. The processors 852 may include a CPU or computer, analog and / or digital input / output connections, a stepping motor controller board, etc.

[0241] In some embodiments, the system controller 850 controls all activities of the process tool 800. The system controller 850 is stored in a mass storage device 854, loaded into a memory device 856, and runs system control software 858 on a processor 852. The system control software 858 may include instructions for controlling timing, gas mixing, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power level, RF frequency, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by the process tool 800. The system control software 858 may be configured in any preferred manner. For example, various process tool component subroutines or control objects may be written to control the operation of process tool components necessary to perform various process tool processes according to the disclosed method. The system control software 858 may be coded in any preferred computer-readable programming language.

[0242] In some embodiments, the system control software 858 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each stage of the ALD process may include one or more instructions for execution by the system controller 850. Instructions for setting process conditions for an ALD process stage may be included in the corresponding ALD recipe stage. In some embodiments, the stages of the ALD recipe may be arranged sequentially such that all instructions in an ALD process stage are executed simultaneously with that process stage.

[0243] In some embodiments, other computer software and / or programs may be used, stored in a mass storage device 854 and / or memory device 856 associated with the system controller 850. Examples of such programs or sections of programs include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0244] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 818 and control the spacing between the substrate and other parts of the process tool 800.

[0245] The process gas control program may include code to control the gas composition and flow rate, and optionally to flow gas to one or more process stations before deposition in order to stabilize the pressure within the process stations. The process gas control program may include code to control the gas composition and flow rate within any of the disclosed ranges. The pressure control program may include code to control the pressure within the process stations by, for example, regulating throttle valves in the exhaust systems of the process stations, gas flow to the process stations, etc. The pressure control program may include code to maintain the pressure within the process stations within any of the disclosed pressure ranges.

[0246] The heater control program may include code for controlling the current to the heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions for maintaining the substrate temperature within any of the disclosed ranges.

[0247] The plasma control program may include code for setting the RF power level and frequency applied to process electrodes in one or more process stations, for example, using one of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0248] In some embodiments, there may be a user interface associated with the system controller 850. The user interface may include a display screen, a graphical software display and / or processing conditions for the device, as well as user input devices such as a pointing device, keyboard, touch screen, and microphone.

[0249] In some embodiments, parameters adjusted by the system controller 850 may relate to processing conditions. Non-limiting examples include the composition and flow rate of the process gas, temperature, pressure, and plasma conditions (such as RF power level, frequency, and exposure time). These parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

[0250] Signals for monitoring the process may be provided by analog and / or digital input connections to the system controller 850 from various process tool sensors. Signals for controlling the process may be output to analog and digital output connections of the process tool 800. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (such as manometers), and thermocouples. Appropriately programmed feedback and control algorithms may be used in conjunction with data from these sensors to maintain processing conditions.

[0251] Any suitable chamber may be used to implement the disclosed embodiments. Examples of deposition apparatus include, but are not limited to, apparatus from the Halo® product family available from Lam Research Corp. of Fremont, California, or various other commercially available processing systems. Two or more stations may perform the same function. Similarly, two or more stations may perform different functions. Each station can be designed / configured to perform a specific function / method as desired.

[0252] Figure 9 is a block diagram of a processing system suitable for carrying out a thin film deposition process according to a particular embodiment. System 900 includes a transfer module 903. The transfer module 903 provides a clean pressurized environment to minimize the risk of contamination of the substrate being processed as it moves between various reactor modules. The transfer module 903 is equipped with two multi-station reactors 909 and 910, each capable of carrying out atomic layer deposition (ALD) and / or chemical vapor deposition (CVD) according to a particular embodiment. Reactors 909 and 910 may include a number of stations 911, 913, 915, and 917 that can carry out the operations according to the disclosed embodiment sequentially or non-sequentially. The stations may include heated pedestals or substrate supports, one or more gas inlets or showerheads, or dispersion plates.

[0253] The transfer module 903 may also contain one or more single or multi-station modules 907 capable of performing plasma or chemical (non-plasma) pre-cleaning, or any other processes described in relation to the disclosed methods. Modules 907 may optionally be used for various processes, for example, to prepare substrates for deposition processes. Modules 907 may also be designed / configured to perform various other processes, such as etching or polishing. The system 900 also includes one or more wafer source modules 901, in which wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 919 may first retrieve the wafer from the source module 901 to the load lock 921. A wafer transfer device (typically a robotic arm unit) in the transfer module 903 moves the wafer from the load lock 921 between modules mounted in the transfer module 903.

[0254] In various embodiments, the system controller 929 is used to control process conditions during deposition. The controller 929 typically includes one or more memory devices and one or more processors. The processor may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, and the like.

[0255] The controller 929 may control all activities of the deposition apparatus. The system controller 929 runs system control software that includes a set of instructions for controlling timing, gas mixing, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power level, wafer chuck or pedestal position, and other parameters of a particular process. In some embodiments, other computer programs stored in a memory device associated with the controller 929 may be used.

[0256] Typically, a user interface is associated with the controller 929. The user interface may include a display screen, a graphical software display and / or processing conditions for the device, as well as user input devices such as a pointing device, keyboard, touch screen, or microphone.

[0257] System control logic may be configured in any preferred manner. Generally, logic can be designed or configured in hardware and / or software. Instructions for controlling drive circuits may be hardcoded or provided as software. Instructions may be provided by “programming.” Such programming is understood to include any form of logic, including hardcoded logic in digital signal processors, application-specific integrated circuits, and other devices with specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that can be executed on a general-purpose processor. System control software may be coded in any preferred computer-readable programming language.

[0258] Computer program code for controlling the flow of reducing agents, halogen-containing activators, metal precursors, and other processes in the process sequence can be written in any conventional computer-readable programming language, such as assembly language, C, C++, Pascal, Fortran, etc. The compiled object code or script is executed by the processor to perform the tasks identified within the program. Alternatively, as shown, the program code may be hardcoded.

[0259] Controller parameters relate to process conditions such as process gas composition and flow rate, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters may be provided to the user in the form of a recipe and may be entered using a user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 929. Signals for controlling the process are output to analog and digital output connections of the deposition apparatus 900.

[0260] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control the operation of the chamber components necessary to perform the deposition process (and possibly other processes) according to the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0261] In some implementations, the controller 929 is part of a system which may be part of the examples described above. Such a system may include a semiconductor processing apparatus which includes one or more process tools, one or more chambers, one or more platforms for processing, and / or specific processing components (such as wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling pre-processing, in-processing, and post-processing operations of semiconductor wafers or substrates. The electronics may be referred to as “controllers” which can control various components or sub-components of one or more systems. Depending on the processing requirements and / or the type of system, the controller 929 may be programmed to control any of the processes disclosed herein, including the delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, transfer of wafers to and from tools and other transfer tools, and / or load locks connected to or interfaced with specific systems.

[0262] Broadly speaking, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive and issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in the form of firmware that store program instructions, chips defined as digital signal processors (DSPs), application-specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers (e.g., software) that execute program instructions. Program instructions may also be instructions communicated to the controller in the form of various individual settings (or program files) that define operating parameters for performing a particular process on a semiconductor wafer or system. In some embodiments, operating parameters may be part of a recipe defined by a process engineer to achieve one or more processing steps during the manufacturing of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0263] In some implementations, the controller may be part of, or coupled to, a computer integrated with, coupled to, networked to, or in some way networked to, the system, or a combination thereof. For example, the controller may be all or part of a “cloud” or fab-host computer system, and may also enable remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, examine trends or performance metrics from multiple manufacturing operations, modify parameters of the current process, set processing steps to follow the current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network that may include a local network or the internet. The remote computer may include a user interface that allows input or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data specifying the parameters of each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the controller is configured to interface with or control. Therefore, as described above, the controllers may be distributed, for example, by comprising one or more separate controllers that are networked together and operate toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes is one or more integrated circuits on a chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) which are combined to control the processes on the chamber.

[0264] Exemplary systems may include, but are not limited to, plasma etching chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, clean chambers or modules, bevel edge etching chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etching (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing systems related to or usable in the fabrication and / or manufacture of semiconductor wafers.

[0265] As described above, depending on one or more process steps performed by the tool, the controller may communicate with one or more of the following: other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, the main computer, another controller, or tools used for material transport that carry wafer containers to and from tool locations and / or load ports in the semiconductor manufacturing plant.

[0266] Further implementation forms The apparatus and processes described herein may be used in conjunction with lithography patterning tools or processes for, for example, the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, but not necessarily, such apparatus and processes are used or performed together in a common fabrication facility. Lithography patterning of films typically includes some or all of the following steps, each step made possible with several possible tools: (1) coating 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 a UV curing tool; (3) exposing the photoresist to visible light, UV light, or X-ray light using a tool such as a wafer stepper; (4) selectively removing the resist and thereby developing the resist for patterning using a tool such as a wet bench; (5) transferring the resist pattern to a substrate film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0267] Experimental example Molybdenum was deposited on a TiN surface with and without the use of an alkyl halide activator. MoCl5 was used as the molybdenum precursor, H2 as 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, each cycle including continuous exposure to MoCl5 and H2. When the t-butyl chloride activator was used, each cycle included substrate exposure to MoCl5, followed by exposure to t-butyl chloride, followed by exposure to H2 (as a reducing agent). Reagents were introduced sequentially into the process chamber without mixing within the process chamber. After each step of the cycle, purging was used to remove unadsorbed reagents from the process chamber. The molybdenum film was deposited at temperatures in the range of 350°C to 450°C. Figure 10 is a plot showing the thickness of the molybdenum layer deposited on the TiN surface as a function of temperature in the absence of a halogen-containing activator (circle) and with the use of a halogen-containing activator (triangle). It can be seen that the molybdenum thickness increases by more than four times at 400°C when using the t-butyl chloride activator. [Explanation of Symbols]

[0268] 101 Concave Features 103 Material layer 105 layers 109 Metal layer 201 Concave Features 203 Dielectric layer 205 Material 207 Molybdenum Carbide 700 Deposit Processing Station 700 processing stations 700 Process Stations 701 Reactant Delivery System 702 Processing Chamber Body 703 Vaporization point 704 Mixing container 705 Shower head inlet valve 706 Shower Head 706 Splitter Shower Head 707 Microvolume 708 Pedestal 710 Heater 712 circuit board 714 RF power supply 716 harmonized network 718 Butterfly Valve 720 Mixing container inlet valve 800 Multi-Station Processing Tools 800 Process Tools 802 Inbound Road Rock 804 Outbound Road Lock 806 Robot 808 Pod 810 Atmospheric Port 812 Pedestal 814 Processing Chamber 816 Chamber transport port 818 Pedestal 850 System Controller 852 processors 854 Mass storage devices 856 memory devices 858 System Control Software 890 Wafer Handling System 900 System 900 Deposition device 901 Wafer Source Module 901 Source Module 903 Transport Module 907 module 907 Multi-Station Module 909 Multi-station reactor 909 Reactor 911 Station 913 Station 915 Station 919 Atmospheric transfer chamber 921 Roadrock 929 System Controller 929 Controller

Claims

1. A method for forming a metal-containing layer, wherein the method is (a) A step of bringing a semiconductor substrate into contact with a metal precursor in a process chamber, (b) A step of bringing the semiconductor substrate into contact with a halogen-containing deposition activator, wherein the halogen-containing deposition activator is different from the metal precursor, (c) The step of bringing the semiconductor substrate into contact with a reducing agent to form the metal-containing layer on the semiconductor substrate, A method for forming a metal-containing layer, including [a specific component].

2. The method according to claim 1, wherein steps (a), (b), and (c) are performed sequentially without simultaneously flowing any two components selected from the group consisting of the metal precursor, the halogen-containing deposition activator, and the reducing agent into the process 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, halosilanes, 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 t-butyl chloride.

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

8. The halogen-containing deposition activator is hydrogen bromide (HBr), bromine (Br) ２ ), t-butyl bromide, bromosilane (SiH ３ Br), dibromosilane (SiH ２ Br ２ ), tribromosilane (SiHBr ３ ), and silicon tetrabromide (SiBr ４ The method according to claim 1, selected from the group consisting of ).

9. The halogen-containing deposition activator is hydrogen iodide (HI), iodine (I ２ ), t-butyl iodide (C ４ H ９ I), allyl iodide (C ３ H ５ I), iodosilane (SiH ３ I), diiodosilane (SiH ２ I ２ ), triiodosilane (SiHI ３ ), and silicon tetraiodide (SiI ４ ), and the method according to claim 1, which is selected from the group consisting of.

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 according to 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 to 11, wherein the metal-containing layer includes a molybdenum-containing layer, a cobalt-containing layer, a ruthenium-containing layer, a tungsten-containing layer, a titanium-containing layer, or any combination thereof.

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

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

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

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

17. The metal-containing layer is a molybdenum layer, and the metal precursor is MoCl ５ Mo ２ Cl １０ MoO ２ Cl ２ MoOCl ４ Mo(PF) ３ ) ６ Mo(CO) ６ (iPrCp) ２ MoH ２ Mo(hfac) ３ ,MoO(OiPr) ４ , bis(ethylbenzene) Mo, Mo ２ (TFA) ４ , or MoF ６ The method according to any one of claims 1 to 11, including, or any combination thereof.

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

19. The method according to claim 1, further comprising the step of performing at least two deposition cycles, each cycle comprising 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 according to claim 1, wherein the metal-containing layer is a molybdenum carbide layer deposited as a liner on a semiconductor substrate having a plurality of concave features, and the concave features have a dielectric material on their sidewalls.

22. The method according to claim 1, wherein the metal-containing layer is a molybdenum carbonitride layer deposited as a liner on a semiconductor substrate having a plurality of concave features, and the concave features have a dielectric material in their sidewalls.

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

24. The method according to claim 1, wherein the metal-containing layer is a metal layer deposited within the concave features of the semiconductor substrate to at least partially fill the concave features.

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

26. The method according to claim 1, wherein the metal-containing layer is deposited at a temperature of about 250°C to about 600°C and a pressure of less than about 300 Torre.

27. (a) The step of providing a semiconductor substrate having an exposed dielectric layer, (b) The step of 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, (c) The step of depositing a metal layer on the molybdenum carbide liner, A method for depositing a metal layer, including [a specific component].

28. An apparatus for processing substrates, wherein the apparatus is (a) A process chamber having a substrate holder for holding a semiconductor substrate and one or more inlets for introducing reactants into the process chamber, (b) A controller, (i) The semiconductor substrate is brought into contact with a metal precursor in the process chamber. (ii) The semiconductor substrate is brought into contact with a halogen-containing deposition activator, and the halogen-containing deposition activator differs from the metal precursor, (iii) A controller including a program instruction for bringing the semiconductor substrate into contact with a reducing agent to form a metal-containing layer on the semiconductor substrate, An apparatus for processing substrates, equipped with the following features.

29. A system for processing substrates, wherein the system is (a) One or more process chambers, (b) A controller, (i) By exposing the semiconductor substrate to a molybdenum precursor, an alkyl halide, and a reducing agent, a molybdenum carbide liner is deposited on the semiconductor substrate having an exposed dielectric layer. (ii) A controller including program instructions for depositing a metal layer on the molybdenum carbide liner, A system for processing substrates, including the following:

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