Methods for depositing metallic materials

Abstract

This disclosure relates to methods and components for a cyclic deposition process for depositing Group IV to Group VI transition metals on a substrate. The method includes providing a substrate in a reactor chamber, introducing a gaseous organometallic compound as a metal precursor and a gaseous Lewis acid reactant to react with the metal precursor, thereby forming a transition metal material on the substrate. The method may include introducing a gaseous co-reactant. This disclosure also relates to semiconductor processing components for performing the methods according to this disclosure.

Description

Technical Field

[0001] This disclosure generally relates to methods and components for depositing metallic materials using a cyclic vapor deposition technique. Such methods can be used, for example, to process semiconductor substrates. More specifically, this disclosure relates to methods and components for depositing materials comprising group IV to group VI transition metals having low-carbon impurities. Background Technology

[0002] The deposition of metal carbides and elemental metals with low carbon content is of interest in the fabrication of semiconductor devices.

[0003] Low-resistivity metal carbides, such as molybdenum carbide, hold significant potential in the semiconductor industry due to their excellent electrical properties and thermal stability. These materials can be used in a variety of applications, including metal gate word lines, capacitor electrodes for dynamic random-access memory (DRAM), and work function metals in back-end process (BEOL) interconnects and front-end process (FEOL). The ability of metal carbides to maintain low resistivity even at very thin thicknesses makes them ideal for ever-shrinking semiconductor devices, where reduced resistance is crucial for improving performance and reducing power consumption. Additionally, metal carbides can serve as effective diffusion barrier layers, preventing material mixing in integrated circuits. In particular, controlled deposition of such materials via ALD can find applications in industry, enabling the precise and uniform deposition of metal carbide materials, ensuring their integration into next-generation semiconductor technologies.

[0004] Any discussion set forth in this section (including discussions of problems and solutions) has been included in this disclosure for the purpose of providing context for this disclosure only. Such discussion should not be construed as an admission that any information was known at the time of making this invention or otherwise constitutes prior art. Summary of the Invention

[0005] This invention discloses some concepts in a simplified form, which are described in further detail below. This invention is not intended to necessarily identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Various embodiments of this disclosure relate to methods of depositing metallic materials. Embodiments of this disclosure further relate to methods of manufacturing semiconductor devices and to semiconductor processing components.

[0006] Various embodiments of this disclosure relate to methods for depositing materials comprising Group 4 to Group 6 transition metals on a substrate, materials comprising Group 4 to Group 6 transition metals, and semiconductor processing components for depositing said materials.

[0007] In one aspect, a method is disclosed for depositing a material comprising Group 4 to Group 6 transition metals on a substrate via a cyclic deposition process. The method includes providing a substrate in a reactor chamber and providing a metal precursor comprising an organometallic compound in the gas phase into the reaction chamber. The method further includes providing a Lewis acid reactant in the gas phase into the reaction chamber to react with the metal precursor and form a material comprising any of Group 4 to Group 6 transition metals on the substrate.

[0008] In some embodiments, the method further includes providing the co-reactants in the gas phase into the reaction chamber.

[0009] In some embodiments, the organometallic compound includes a metal selected from the group consisting of vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.

[0010] In some embodiments, the metal precursor comprises a zero-valent organometallic compound. In some embodiments, the metal precursor comprises a diaromatic complex.

[0011] In some embodiments, the Lewis acid reactants include inorganic halides. In some embodiments, the Lewis acid reactants are selected from the group consisting of metal halides and nonmetal halides.

[0012] In some embodiments, the inorganic halide is a chloride. In some embodiments, the inorganic halide is a metal halide selected from the group consisting of aluminum chloride, molybdenum chloride, ferric chloride, and titanium tetrachloride. In some embodiments, the Lewis acid reactant comprises a Group 13 element and one or more ligands selected from halides, alkoxides, alkyl groups, dialkylamides, and combinations thereof.

[0013] In some embodiments, materials comprising Group 4 to Group 6 transition metals include metal carbides.

[0014] In some embodiments, the co-reactants are selected from the group consisting of halosilanes, alkyl halides and acyl halides.

[0015] In some embodiments, the co-reactant includes an alkyl halide, which includes 1,2-diiodoethane or iodobutane.

[0016] In some embodiments, the co-reactant is selected from alkyl chlorides.

[0017] In some embodiments, the co-reactant is an alkyl chloride and is selected from the group consisting of 1,2-dichloroethane, chloromethane, 2-chloro-2-methylpropane, chloroform, 2-methyl-2-chlorobutane, and tert-butyl chloride.

[0018] In some embodiments, materials comprising transition metals from Group 4 to Group 6 include elemental metals from any of Groups 4 to 6 of the periodic table.

[0019] In some embodiments, the metal precursor comprising the organometallic compound, the Lewis acid reactant, and the co-reactant are supplied in a pulsed manner, and the reaction chamber is purged after a series of pulses of the Lewis acid reactant and the co-reactant.

[0020] In some embodiments, the Lewis acid reactant and co-reactant are provided in any order.

[0021] In some embodiments, the process temperature is about 150-400°C.

[0022] In some embodiments, the substrate comprises a pre-cleaned silicon or silicon-germanium substrate.

[0023] In some embodiments, the duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the length for which the metal precursor is provided to the reaction chamber.

[0024] In some embodiments, the semiconductor processing component is configured and arranged to perform the method according to this disclosure.

[0025] As used herein, the term "comprising" means including certain features, but does not exclude the presence of other features, provided they do not render the claim unfeasible. In some embodiments, the term "comprising" includes "consisting of".

[0026] As used herein, the term "composed of" indicates that no other features exist in the apparatus / method / product besides the features following the wording. When the term "composed of" is used to refer to a chemical compound, substance, or composition of substances, it indicates that the chemical compound, substance, or composition of substances contains only the listed components. Similarly, when the term "substantially composed of" is used to refer to a chemical compound, substance, or composition of substances, it indicates that the chemical compound, substance, or composition of substances contains the listed components, but may also contain trace elements and / or impurities that do not substantially affect the properties of the chemical compound, substance, or composition of substances. Nevertheless, in some embodiments, the chemical compound, substance, or composition of substances may also include other components as trace elements or impurities in addition to the listed components.

[0027] Furthermore, in this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and include equivalents, and may refer to an average, median, representative value, multi-value, etc. Furthermore, in this disclosure, the terms “comprising,” “consisting of,” and “having” independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of” in some embodiments. The meaning of any definition in this disclosure does not necessarily exclude the common and customary meaning in some embodiments.

[0028] The term "substantially" applied to compositions, methods, or systems generally refers to a proportion of a value, property, characteristic, etc., or conversely, the absence of such proportion, i.e., at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or more, or any proportion between about 70% and about 100%. In some embodiments, the term "substantially" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0029] The term "essentially" applied to compositions, methods, or systems generally means that the addition of components does not substantially alter the properties and / or functions of the composition, method, or system.

[0030] In this specification, it will be understood that the terms "on" or "above" may be used to describe relative positional relationships. Another element, film, or layer may be directly on the mentioned layer, or another layer (intermediate layer) or element may be inserted between them, or a layer may be disposed on the mentioned layer but not completely cover the surface of the mentioned layer. Therefore, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it will be understood that the terms "below," "subject to," or "under" will be interpreted as relative concepts. Attached Figure Description

[0031] The accompanying drawings are included to provide a further understanding of the present disclosure and form part of this specification. The drawings illustrate exemplary embodiments and, together with the specification, help to explain the principles of the present disclosure.

[0032] In the attached diagram

[0033] Figure 1 This is a block diagram of an exemplary embodiment of a method for depositing a material comprising metal carbides according to the present disclosure.

[0034] Figure 2 This is a block diagram of another exemplary embodiment of the method for depositing elemental metals according to the present disclosure.

[0035] Figure 3 This is a block diagram of another exemplary embodiment of the method for depositing elemental metals according to the present disclosure.

[0036] Figure 4 This is a schematic diagram of an embodiment of a semiconductor processing component according to the present disclosure.

[0037] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. Detailed Implementation

[0038] The following description of exemplary embodiments of methods, materials, layers, and semiconductor processing components is merely illustrative and for purposes of explanation only. The following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having indicative features is not intended to exclude other embodiments having additional features or other embodiments including different combinations of said features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise stated, exemplary embodiments or components thereof may be combined or may be applied separately from each other.

[0039] The headings provided herein (if any) are for convenience only and do not necessarily affect the scope or meaning of the subject matter for which protection is sought.

[0040] In one aspect, a method is disclosed for depositing a material comprising Group 4 to Group 6 transition metals on a substrate via a cyclic deposition process. The method includes providing a substrate in a reactor chamber and providing a metal precursor comprising a metal-organic compound in the gas phase into the reaction chamber. The method further includes providing a Lewis acid reactant in the gas phase into the reaction chamber to react with the metal precursor and form a material comprising any of Group 4 to Group 6 transition metals on the substrate.

[0041] layer

[0042] Materials comprising Group 4 to 6 transition metals (i.e., metallic materials) can be deposited as layers. As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous material, such as materials deposited by the methods disclosed herein. For example, layers and / or films can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers or partially or entirely atomic layers or atomic and / or molecular clusters. Films or layers can include materials or layers having pinholes, which may be at least partially continuous. In some embodiments, the layers according to this disclosure are substantially continuous. In some embodiments, the layers according to this disclosure are continuous.

[0043] Very thin layers with advantageous properties can be deposited using the methods according to this disclosure. In particular, the resistivity of the thin films described herein can be sufficiently low for applications requiring functional layers but with very limited thickness. In some embodiments, the metal-containing layer has a thickness of less than 30 nm. In some embodiments, the metal-containing layer has a thickness of less than 20 nm. In some embodiments, the metal-containing layer has a thickness of less than 10 nm. In some embodiments, the metal-containing layer has a thickness of less than 5 nm. In some embodiments, the metal-containing layer has a thickness of less than 3 nm. However, in some applications, such as back-side power supply networks (BSPDNs) and certain memory applications (particularly DRAM), layers with a thickness of about 100 nm to about 1 μm can be deposited.

[0044] substrate

[0045] The deposition method according to this disclosure includes providing a substrate in a reaction chamber. The substrate can be any one or more underlying materials that can be used to form structures, devices, circuits, or layers, or on which structures, devices, circuits, or layers can be formed. The substrate may include a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or group III-V semiconductor materials), and may include one or more layers overlying or underlying the bulk material. Furthermore, the substrate may include various features formed within or on at least a portion of the layers of the substrate, such as recesses, protrusions, etc. For example, the substrate may include a bulk semiconductor material and an insulating or dielectric material layer overlying at least a portion of the bulk semiconductor material. The substrate may include nitrides (e.g., TiN), oxides, insulating materials, dielectric materials, conductive materials, metals (such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper) or metallic materials, crystalline materials, epitaxy, heteroepitaxial, and / or single-crystal materials. In some embodiments of this disclosure, the substrate includes silicon. In addition to silicon, the substrate may also include other materials as described above. Other materials can form layers. Specifically, the substrate may include partially fabricated semiconductor devices.

[0046] In some embodiments, the substrate surface on which the metallic material according to the present disclosure is deposited comprises silicon-germanium, substantially silicon-germanium, or composed of silicon-germanium. In some embodiments, the substrate surface comprises a metal, substantially metal, or composed of a metal such as copper, cobalt, molybdenum, ruthenium, tungsten, tantalum, niobium, vanadium, or combinations thereof. The metal surface may have a surface oxide.

[0047] In some embodiments, the substrate may be pretreated or cleaned before or at the start of the deposition process. For example, surface oxidation on a metal surface may be removed. In some embodiments, the substrate may undergo a plasma cleaning process before or at the start of the deposition process. Plasma cleaning may include the use of plasma comprising nitrogen, such as NF3 and / or NH3. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some embodiments, the substrate surface may be exposed to plasma, free radicals, excitation materials, and / or atomic materials before or at the start of the deposition process. In some embodiments, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic materials before or at the start of the deposition process. In some embodiments, the pretreatment or cleaning process may be performed in the same reaction chamber as the deposition process. However, in some embodiments, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0048] reaction chamber

[0049] This method includes providing a substrate in a reaction chamber and depositing a material comprising Group 4 to 6 transition metals on the surface of the substrate using a cyclic vapor deposition process. Therefore, the method for depositing metallic materials according to this disclosure includes providing a substrate in a reaction chamber. In other words, the substrate is situated in a space where deposition conditions can be controlled. The reaction chamber may be a single-wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a processing assembly for fabricating semiconductor devices. The processing assembly may include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations within the multi-station processing chamber. The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. The various stages of the method may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chambers of a cluster tool or deposition stations of a multi-station processing chamber.

[0050] In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a nozzle reactor. In some embodiments, the reaction chamber may be a hot-wall reactor. In some embodiments, the reaction chamber may be a spatially partitioned reactor. In some embodiments, the reaction chamber may be a single-wafer atomic layer deposition (ALD) reactor. In some embodiments, the reaction chamber may be a large-scale single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously fabricating multiple substrates.

[0051] The reaction chamber may form part of a semiconductor processing assembly (e.g., an ALD assembly). The reaction chamber may form part of a chemical vapor deposition (CVD) assembly. The deposition assembly may be an ALD or CVD deposition assembly, but molecular layer deposition (MLD) may also be employed in certain process steps or portions of the deposition process flow. In some embodiments, the method is performed in a single reaction chamber of a cluster tool, but other preceding or subsequent fabrication steps of the structure or device are performed in additional reaction chambers of the same cluster tool. Optionally, the assembly including the reaction chamber may be equipped with a heater to activate the reaction by raising the temperature of one or more substrates and / or reactants and / or precursors.

[0052] Cyclic deposition process

[0053] The vapor deposition process according to this disclosure is a cyclic deposition process. Typically, in a cyclic deposition process according to this disclosure, such as in atomic layer deposition (ALD), during each cycle, a precursor (e.g., a metal precursor) is introduced in the gas phase into a reaction chamber and chemisorbed onto a substrate surface (e.g., the substrate surface may include previously deposited material or other material from a previous deposition cycle). In some embodiments, the precursor on the substrate surface does not readily react with another precursor (i.e., the deposition of the precursor may be a partially or completely self-limiting reaction). Subsequently, another precursor or reactant may be introduced into the reaction chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The second precursor (e.g., a reactant) is capable of further reacting with the precursor. During one or more cycles, such as during each step of each cycle, a purging step may be utilized to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber. Therefore, in some embodiments, the cyclic deposition process includes purging the reaction chamber after the precursor has been provided into it. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a first precursor (e.g., a metallic precursor) into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a second precursor or reactant (e.g., a Lewis acid reactant) into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the first precursor into the reaction chamber and after providing the second precursor into the reaction chamber. Without limiting this disclosure to any particular theory, ALD can incorporate self-limiting reactions and slower and more controllable layer growth rates compared to CVD.

[0054] The process may include one or more cyclic stages. In some embodiments, the process includes one or more non-cyclic (i.e., continuous) stages. In some embodiments, the deposition process includes a continuous flow of at least one precursor or reactant. In such embodiments, the process includes a continuous flow of at least a metal precursor or a Lewis acid reactant or co-reactant. In some embodiments, one or more of the precursor and reactant are continuously provided in a reaction chamber.

[0055] The vapor deposition method according to this disclosure includes providing a metal precursor in the gas phase into a reaction chamber and providing a Lewis acid reactant in the gas phase into the reaction chamber. In some embodiments, the method includes providing a co-reactant in the gas phase into the reaction chamber. In some embodiments, at least one of the metal precursor and the Lewis acid reactant and the co-reactant is provided to the reaction chamber in a pulsed manner. In some embodiments, the metal precursor and the Lewis acid reactant are supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses of the metal precursor and the Lewis acid reactant. In some embodiments, the metal precursor, the Lewis acid reactant, and the co-reactant are supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses of the metal precursor, the Lewis acid reactant, and the co-reactant.

[0056] The metal precursor, Lewis acid reactant, and optional co-reactant can be provided in any order. In some embodiments, the deposition cycle includes providing the metal precursor first, followed by the Lewis acid reactant. In some embodiments, the deposition cycle includes providing the Lewis acid reactant first, followed by the metal precursor. In some embodiments, the deposition cycle includes providing the metal precursor first, followed by the Lewis acid reactant, and then the co-reactant. In some embodiments, the deposition cycle includes providing the metal precursor first, followed by the co-reactant, and then the Lewis acid reactant. In some embodiments, the deposition cycle includes providing the Lewis acid reactant first, followed by the metal precursor, and then the co-reactant. In some embodiments, the deposition cycle includes providing the Lewis acid reactant first, followed by the co-reactant, and then the metal precursor. In some embodiments, the deposition cycle includes providing the co-reactant first, followed by the metal precursor, and then the Lewis acid reactant. In some embodiments, the deposition cycle includes providing the co-reactant first, followed by the Lewis acid reactant, and then the metal precursor. In some embodiments, the Lewis acid reactant is provided to the reaction chamber at least partially simultaneously with the co-reactant. Without limiting this disclosure to any particular theory, Lewis acid reactants catalyze the reaction between a metal precursor and a co-reactant, resulting in a faster reaction that favors the formation of pure elemental metals. This can reduce carbon incorporation in the deposited material, leading to a higher elemental metal content and increased conductivity. For a given material quality, the use of Lewis acid reactants allows for lower reaction temperatures and / or faster cycling. Furthermore, the pressure in the reaction chamber can be reduced. These advantages translate into a more economical and environmentally friendly deposition process through reduced energy and process gas consumption during the fabrication of semiconductor devices. Improved material quality can further reduce energy consumption in the final product where materials according to this disclosure are used.

[0057] The duration for which the metal precursor and / or Lewis acid reactant and / or co-reactant are supplied to the reaction chamber (i.e., the pulse time of the metal precursor, the pulse time of the Lewis acid reactant, and the pulse time of the co-reactant, respectively) can be, for example, from about 0.01 s to about 60 s, from about 0.01 s to about 10 s, or from about 0.5 s to about 20 s, or from about 0.5 s to about 10 s, or from about 2 s to about 15 s, or from about 10 s to about 30 s, or from about 10 s to about 60 s, or from about 20 s to about 60 s. The duration of the metal precursor or Lewis acid reactant pulse can be, for example, 0.01 s, 0.02 s, 0.05 s, 0.1 s, 0.5 s, 1 s, 1.5 s, 2 s, 2.5 s, 3 s, 4 s, 5 s, 8 s, 10 s, 12 s, 15 s, 25 s, 30 s, 40 s, 50 s, or 60 s. In some embodiments, the metal precursor pulse time can be at least 3 seconds or at least 5 seconds. In some embodiments, the metal precursor pulse time can be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds. In some embodiments, the Lewis acid reactant pulse time is at least 0.005 seconds, at least 0.01 seconds, at least 0.02 seconds, or at least 0.05 seconds. In some embodiments, the Lewis acid reactant pulse duration may be up to 0.02 seconds, up to 0.05 seconds, up to 0.1 seconds, or up to 0.5 seconds. Controlling the dosage of the Lewis acid reactant is of particular interest because excessively high dosages can lead to degraded performance of the deposited material, and the Lewis acid reactant component may undesirably be incorporated into the deposited material.

[0058] The pulse times of the metal precursor, Lewis acid reactant, and optional co-reactant can vary independently depending on the process under discussion. For example, the flow rate of the precursor or reactant affects the optimal pulse length. The selection of an appropriate pulse time may depend on the substrate topology. For structures with higher aspect ratios, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Furthermore, the selected metal precursor, Lewis acid reactant, and co-reactant chemicals can influence the appropriate pulse time. For process optimization purposes, shorter pulse times may be preferred, provided that appropriate layer properties are achieved. In some embodiments, the metal precursor pulse time is longer than the Lewis acid reactant pulse time. In some embodiments, the Lewis acid reactant pulse time is longer than the metal precursor pulse time. In some embodiments, the metal precursor pulse time is the same as the Lewis acid reactant pulse time. In some embodiments, the co-reactant pulse time is longer than the Lewis acid reactant pulse time. In some embodiments, the Lewis acid reactant pulse time is longer than the co-reactant pulse time. In some embodiments, the co-reactant pulse time is longer than the metal precursor pulse time. In some embodiments, the metal precursor pulse time is longer than the co-reactant pulse time. In some embodiments, the co-reactant pulse time is the same as the metal precursor pulse time. In some embodiments, the co-reactant pulse time is the same as the Lewis acid reactant pulse time.

[0059] In some embodiments, providing the metal precursor and / or Lewis acid reactant and / or co-reactant into the reaction chamber includes pulsed delivery of the metal precursor and Lewis acid reactant, along with optional co-reactant, onto a substrate. In some embodiments, pulse durations in the range of several minutes may be used for the metal precursor and / or Lewis acid reactant. In some embodiments, the metal precursor may be pulsed more than once, e.g., two, three, or four times, before the Lewis acid reactant and optional co-reactant are pulsed into the reaction chamber. Similarly, more than one pulse, such as two, three, or four pulses, may be present for the Lewis acid reactant and / or optional co-reactant before the metal precursor is pulsed (i.e., provided) into the reaction chamber. In some embodiments, the metal precursor, Lewis acid reactant, and co-reactant are supplied in pulsed form, and the reaction chamber is purged after successive pulses of the Lewis acid reactant and co-reactant.

[0060] The pulses of the metal precursor and Lewis acid reactant can form a deposition cycle together. The pulses of the metal precursor, Lewis acid reactant, and co-reactant can form a deposition cycle together. As described above, this process is a cyclic deposition process. Therefore, the precursor is repeatedly supplied (i.e., pulsed) into the reaction chamber. The pulses can be repeated as needed, depending on, for example, the growth rate of the metal-containing material and the desired thickness of the metal-containing material. In some embodiments, the growth rate of the metal-containing material is from about 0.1 Å / cycle to about 10 Å / cycle, for example, from about 4 Å / cycle to about 9 Å / cycle. In some embodiments, the growth rate of the metal-containing material is from about 0.1 Å / cycle to about 5 Å / cycle, for example, from about 3 Å / cycle or about 4 Å / cycle. In some embodiments, the growth rate of the metal-containing material is from about 1 Å / cycle to about 3.5 Å / cycle, for example, from about 2 Å / cycle or about 3 Å / cycle. In some embodiments, the growth rate of the metal-containing material is from about 0.1 Å / cycle to about 1.5 Å / cycle, for example, from about 0.3 Å / cycle or about 0.8 Å / cycle. In some embodiments, the growth rate of the metallic material is from about 0.1 Å / cycle to about 1 Å / cycle, for example, about 0.7 Å / cycle or about 0.9 Å / cycle. In some embodiments, the growth rate of the metallic material is from about 0.5 Å / cycle to about 1 Å / cycle.

[0061] The thickness of the metal-containing material can be selected depending on the application discussed. In some embodiments, the deposited metal-containing material has a thickness of about 0.1 nm to about 30 nm. Therefore, depending on the growth rate of the metal-containing material, deposition cycles can be performed from about 2 to about 800 times. For example, deposition cycles can be performed from about 10, 20, 50, 100, 200, 300, 500, 600, or 700 times.

[0062] In some embodiments, the metallic material according to the present disclosure is deposited at a pressure of at least 0.01 Torr to at most 100 Torr, or at least 0.1 Torr to at most 50 Torr, or at least 0.5 Torr to at most 25 Torr, or at least 0.1 Torr to at most 10 Torr, or at least 0.1 Torr to at most 5 Torr. In some embodiments, the metallic material according to the present disclosure is deposited at a pressure of at least 0.5 Torr to at most 20 Torr, or at least 1 Torr to at most 15 Torr, or at least 1 Torr to at most 10 Torr. For example, the metallic material may be deposited at pressures of about 0.5 Torr, about 1 Torr, about 2 Torr, about 3 Torr, about 6 Torr, about 8 Torr, about 9 Torr, about 12 Torr, or about 18 Torr.

[0063] In some embodiments, the cyclic deposition process according to this disclosure includes a thermal deposition process. In thermal deposition, a chemical reaction is promoted by an increase in temperature related to ambient temperature (process temperature). Typically, in the absence of other external energy sources (e.g., plasma, free radicals, or other forms of radiation), the temperature increase provides the energy required to form the target material. In some embodiments, the method according to this disclosure includes a plasma-enhanced deposition method, such as PEALD or PECVD. For example, in some embodiments, the deposition of metallic materials can be performed by PEALD or PECVD.

[0064] Metal precursor

[0065] In the method according to this disclosure, a metal precursor comprising an organometallic compound is provided in the gas phase into a reaction chamber. The metal precursor according to this disclosure comprises a metal from any of Groups 4, 5, or 6 of the periodic table. The metal precursor also includes an organic ligand that can be bonded to the metal atom via a carbon atom or via another atom (e.g., an oxygen atom or a nitrogen atom). The metal precursor according to this disclosure comprises an organometallic compound.

[0066] In this disclosure, organometallic compounds should be understood as compounds containing carbon and a metal. The metal can be bonded to the rest of the compound via carbon atoms or via atoms of another element such as oxygen or nitrogen.

[0067] In some embodiments, the metal atoms in the organometallic compound have a zero oxidation state. Such a compound may be referred to as a zero-valent compound. In some embodiments, the metal precursor comprises a zero-valent organometallic compound. In some embodiments, the oxidation state of the metal is above zero, but below the highest oxidation state of the metal. Such a compound may be referred to as a low-valent compound. In some embodiments, the metal precursor comprises a low-valent organometallic compound. In some embodiments, the metal in the organometallic compound has an oxidation state lower than its group number. Thus, in some embodiments, the organometallic compound comprises a Group 4 metal, and the metal has an oxidation state below four. In some embodiments, the organometallic compound comprises a Group 5 metal, and the metal has an oxidation state below five. In some embodiments, the organometallic compound comprises a Group 6 metal, and the metal has an oxidation state below six. In some embodiments, the metal precursor comprises a metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. In some embodiments, the metal precursor is selected from one or more of titanium precursors, zirconium precursors, hafnium precursors, vanadium precursors, niobium precursors, tantalum precursors, chromium precursors, molybdenum precursors, and tungsten precursors. In some embodiments, the metal precursor is selected from the group consisting of molybdenum precursor, niobium precursor and tungsten precursor.

[0068] In some embodiments, the organometallic compound comprises a cyclopentadienyl ligand. In some embodiments, the organometallic compound comprises a carbonyl-containing ligand. In some embodiments, the organometallic compound comprises a cycloheptatrienyl (CHT) ligand. In some embodiments, the organometallic compound comprises a diazadiene ligand, such as N,N'-diisopropyldiazadiene or N,N'-di-tert-butyldiazadiene ligand. In some embodiments, the organometallic compound comprises a phosphine ligand. In some embodiments, the organometallic compound comprises an alkyl ligand. In some embodiments, the organometallic compound comprises an aryl ligand. In some embodiments, the organometallic compound comprises an aromatic ligand. In some embodiments, the organometallic compound comprises an n- 6 Coordinated aromatic ligands. In some embodiments, the organometallic compound is a homocoordinated biaromatic compound. In some embodiments, the organometallic compound includes an amidine ligand. In some embodiments, the organometallic compound includes a nitrosyl ligand. In some embodiments, the organometallic compound is a heterocoordinate compound. In some embodiments, the organometallic compound is a zero-valent compound. In some embodiments, the zero-valent compound is selected from compounds including aromatic ligands and compounds including carbonyl ligands.

[0069] Specifically, in some embodiments, the organometallic compound comprises a complex of a bis(aromatic) and a metal selected from the group consisting of V, Cr, Mo, and W. In some embodiments, the organometallic compound comprises a homogeneous carbonyl compound. In some embodiments, the organometallic compound comprises a metal selected from Mo and W, two Cp ligands, and two H ligands. In some embodiments, the organometallic compound comprises a metal selected from Mo and W, one aromatic ligand, and three carbonyl ligands. In some embodiments, the organometallic compound comprises vanadium metal and four amide ligands.

[0070] In some embodiments, the metal precursor is a titanium precursor, and the deposited metal-containing material comprises titanium. In some embodiments, the titanium precursor comprises, is substantially composed of, or is composed of organometallic compounds selected from, such as Ti(NEt2)4, Ti(NEtMe)4, Ti(NMe2)4, TiCp2(… i PrN)2C(NH i Pr)), Ti(Cp)CHT, Ti(CpMe)(O i Pr)3, Ti(CpMe5)(OMe)3, Ti(NEt2)4, Ti(NMe2)3(CpMe) and Ti(NMe2)3(CpN).

[0071] In some embodiments, the metal precursor is a zirconium precursor, and the deposited metal-containing material includes zirconium. In some embodiments, the zirconium precursor comprises, is substantially composed of, or is composed of organometallic compounds selected from, such as ZrCp2Me2, Zn(NMe2)4, Zr(NEt2)4, Zr(NEtMe)4, Zr(NEt2)4, ZrCp2(NMe2)2, Zr(Cp)( t BuDAD)(O i Pr), Zr(Cp2CMe2)Me2, Zr(CpMe)(NMe2)3, Zr(CpMe)2Me2, Zr(CpMe)CHT, Zr(MeAMD)4, Zr(O i Pr)2(dmae)2、Zr(O i Pr)4、Zr(O t Bu)4 and Zr(thd)4.

[0072] In some embodiments, the metal precursor is a hafnium precursor, and the deposited metal-containing material includes hafnium. In some embodiments, the hafnium precursor comprises, is substantially composed of, or is composed of an organometallic compound selected from, the following: for example, Hf(NEtMe)4, Hf(NMe2)4, Hf(NEt2)4, HfCp(NMe2)3, Hf(CpMe)2Me2, Hf(Cp2CMe2)Me(OMe), Hf(CpMe)(NMe2)3, Hf(CpMe)2(mmp)Me, Hf(CpMe)2(O i Pr)Me, Hf(dmap)4, Hf(mmp)4, Hf( i PrFMD)2(NMe2)2、Hf(NO3)4、Hf(O i Pr)4 and Hf(O t Bu)4.

[0073] In some embodiments, the metal precursor is a vanadium precursor, and the deposited metal-containing material includes vanadium. In some embodiments, the vanadium precursor comprises, is substantially composed of, or is composed of: bis(trimethylbenzene)vanadium, bis(toluene)vanadium, and bis(benzene)vanadium, bis(1,3,5-trimethylbenzene)vanadium, bis(ethylbenzene)vanadium, V(CO)6, bis(ethylbenzene)vanadium, V(NMe2)4, V(NEt2)4, V(NEtMe)4, V( i PrAMD)3, VO(acac)2 and VO(O) i Pr)3.

[0074] In some embodiments, the metal precursor is a niobium precursor, and the deposited metal-containing material includes niobium. In some embodiments, the niobium precursor comprises, is substantially composed of, or is composed of an organometallic compound selected from, a group consisting of, or is composed of, an organometallic compound selected from, for example, Nb(N... t Bu)(NMe2)3、Nb(N t Bu)(NEt2)3、Nb(N t Bu)(NEtMe)3、Nb(N t Bu)(NEt2)2(Cp), Nb(N t Bu)(NEtMe)3, Nb(OEt)5, Nb(OEt)5, bis(methylbenzene)niobium, bis(ethylbenzene)niobium, bis(1,3,5-trimethylbenzene)niobium and bis(toluene)niobium.

[0075] In some embodiments, the metal precursor is a tantalum precursor, and the deposited metal-containing material includes tantalum. In some embodiments, the tantalum precursor comprises, is substantially composed of, or is composed of organometallic compounds selected from the group consisting of, for example, Ta(NMe2)5, Ta(NEt2)5, Ta(NEt)(NEt2)3, Ta(N t Bu)( i PrAMD)2(NMe2), Ta(N t Bu)(NEt2)3, Ta(OEt)5, Ta(NEtMe)5, Ta(N i Pr)(NEtMe)3 and TaCp(N t Bu)(NEt2)2.

[0076] In some embodiments, the metal precursor is a chromium precursor, and the deposited metal-containing material includes chromium. In some embodiments, the chromium precursor comprises, is substantially composed of, or is composed of an organometallic compound selected from, such as bis(phenyl)chromium, bis(1,3,5-trimethylphenyl)chromium, tricarbonyl(1,3,5-trimethylphenyl)chromium, Cr(DAD)2, Cr(acac)3, and Cr(thd)3.

[0077] In some embodiments, the metal precursor is a molybdenum precursor, and the deposited metal-containing material includes molybdenum. In some embodiments, the molybdenum precursor comprises, is substantially composed of, or is composed of an organometallic compound selected from, a group consisting of, or is composed of, an organometallic compound selected from: for example, MoCp2Cl2, MoCp2H2, Mo( i PrCp)2Cl2, Mo( iPrCp)2H2, Mo(EtCp)2H2, Mo(CO)6, Mo(1,3,5-cycloheptatriene)(CO)3, Mo(N t Bu)2(NEt2)2、Mo(N t Bu)2(NMe2)2, Mo(NMe2)4, Mo(N t Bu)2( i PrAMD)2, MoCp(CO)2(NO), Mo(MeCp)(CO)2(NO), bis(phenyl)molybdenum, bis(methylphenyl)molybdenum, bis(ethylphenyl)molybdenum, bis(1,3-dimethylphenyl)molybdenum, bis(1,3,5-trimethylphenyl)molybdenum, tricarbonyl(1,3,5-trimethylphenyl)molybdenum, bis(m-xylene)molybdenum, Mo(CO)6, Mo(CO)5P(OMe)3 and Mo(CO)5PEt3.

[0078] In some embodiments, the metal precursor is a tungsten precursor, and the deposited metal-containing material comprises tungsten. In some embodiments, the tungsten precursor comprises, is substantially composed of, or is composed of an organometallic compound selected from, a group consisting of, or is composed of, an organometallic compound selected from: for example, mesitylenetricarbonyltungsten, tricarbonylphenyltungsten, tricarbonyl(1,3,5-trimethylbenzene)tungsten, bis(phenyl)tungsten, bis(methylbenzene)tungsten, bis(ethylbenzene)tungsten, bis(1,3-dimethylbenzene)tungsten, bis(1,3,5-trimethylbenzene)molybdenum, W(CO)(3-hexyne)3, W(N t Bu)2(NMe2)2、W2(NMe2)6、W(CO)6、W(N t Bu)2( i PrAMD)2、WO2( t BuAMD)2、WH2( i PrCp)2, WH2Cp2 and W(N) t Bu)2(Me3SiMe)2.

[0079] In the formula, acac represents acetylacetone, AMD represents acetamidine, CHT represents cycloheptatrienyl, Cp represents cyclopentadienyl, DAD represents diazabutadiene (e.g., N,N'-diisopropyldiazadiene or N,N'-di-tert-butyldiazadiene), dmae represents dimethylaminoethanol, dmap represents 1-dimethylamino-2-propanol, FMD represents formamidinium, mmp represents 1-methoxy-2-methyl-2-propanol, Me represents methyl, and Et represents ethyl. i Pr stands for isopropyl. t Bu stands for tert-butyl. n Bu represents n-butyl, and thd represents 2,2,6,6-tetramethyl-3,5-heptadecane.

[0080] Lewis acid reactants

[0081] In the method according to this disclosure, Lewis acid reactants are provided in the gas phase into a reaction chamber. The Lewis acid reactants react with a metal precursor to form a material comprising a transition metal on a substrate. Optionally or additionally, in some embodiments, the Lewis acid reactants react with a surface-chemisorbed co-reactant or a derivative thereof on the surface.

[0082] In some embodiments, the Lewis acid reactant comprises a Group 13 element and one or more ligands selected from halides, alkoxides, alkyl groups, dialkylamides, and combinations thereof. In some embodiments, the Group 13 element is boron. In some embodiments, the Group 13 element is aluminum. In some embodiments, the Group 13 element is gallium. In some embodiments, the halide is selected from the group consisting of fluorides, chlorides, bromides, iodides, and combinations thereof. In some embodiments, the alkoxide is selected from the group consisting of methanol, ethanol, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, isobutoxide, tert-butoxide, cyclopentyl oxide, cyclohexyl oxide, benzene oxide, and combinations thereof. In some embodiments, the alkyl ligand is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, and combinations thereof. In some embodiments, the dialkylamide group is selected from the group consisting of dimethylamide, diethylamide, ethylmethylamide, bis(trimethylsilyl)amide, diisopropylamide, and combinations thereof.

[0083] In some embodiments, the Lewis acid reactant comprises an inorganic halide. In some embodiments, the Lewis acid reactant is selected from the group consisting of metal halides and nonmetal halides. In some embodiments, the inorganic halide is a chloride. In some embodiments, the inorganic halide is a fluoride. In some embodiments, the inorganic halide is a bromide. In some embodiments, the inorganic halide is an iodide. In some embodiments, the inorganic halide is a metal chloride. In some embodiments, the inorganic halide is a metal fluoride. In some embodiments, the inorganic halide is a metal bromide. In some embodiments, the inorganic halide is a metal iodide. In some embodiments, the inorganic halide is a metal halide selected from the group consisting of: aluminum chloride, molybdenum chloride and titanium tetrachloride, gallium trichloride, zirconium tetrachloride, hafnium tetrachloride, tungsten pentachloride, tungsten heptachloride, boron trifluoride, boron trichloride, boron tribromide, boron triiodide, aluminum tribromide, titanium tetrafluoride, titanium tetrabromide, titanium tetraiodide, tantalum pentachloride, niobium pentafluoride, niobium pentachloride, vanadium tetrachloride, and vanadium trichloride (VOCl3).

[0084] In some embodiments, the Lewis acid reactant is selected from the group consisting of: antimony pentafluoride (SbF5), boron trifluoride (BF3), aluminum chloride (AlCl3), titanium tetrachloride (TiCl4), tin tetrachloride (SnCl4), ferric chloride (III) (FeCl3), zinc chloride (ZnCl2), gallium trichloride (GaCl3), molybdenum pentachloride (MoCl5), vanadium tetrachloride (VCl4), boron trichloride (BCl3), phosphorus pentachloride (PCl5), sulfur hexafluoride (SF6), and iodine pentafluoride (IF5).

[0085] In some embodiments, the Lewis acid reactant is TiCl4. In some embodiments, the Lewis acid reactant is AlCl3. In some embodiments, the Lewis acid reactant is MoCl5. In some embodiments, the Lewis acid reactant is BCl3.

[0086] In some embodiments, a metallic alkyl group may be used as a Lewis acid reactant. For example, a metallic alkyl group comprising a Group 13 metal bonded to the alkyl group may be used. In some embodiments, the Lewis acid reactant comprises, is substantially composed of, or is composed of a trialkylaluminum compound, a trialkylgallium compound, or a trialkylindium compound. In some embodiments, the Lewis acid reactant comprises, is substantially composed of, or is composed of trimethylaluminum, trimethylindium, or trimethylgallium.

[0087] Co-reactants

[0088] In some embodiments, the co-reactant is provided to the reaction chamber in the gas phase. In some embodiments, the deposition cycle includes providing the co-reactant to the reaction chamber. Without limiting the present disclosure to any particular theory, the use of a co-reactant in addition to Lewis acid reactants during the deposition process can result in the deposition of elemental metals with low-carbon impurities. In some embodiments, the co-reactant comprises one halogen atom. In some embodiments, the co-reactant comprises no more than one halogen atom. In some embodiments, the co-reactant comprises two or more halogen atoms. The co-reactant may or may not include Group 14 elements. In some embodiments, the co-reactant consists of carbon, hydrogen, and one or more halogen atoms selected from F, Cl, I, and Br. In some embodiments, the co-reactant consists of carbon, oxygen, hydrogen, and one or more halogen atoms selected from Cl, I, and Br. In some embodiments, the co-reactant consists of silicon, hydrogen, and one or more halogen atoms selected from F, Cl, I, and Br. In some embodiments, the co-reactant consists of silicon, oxygen, hydrogen, and one or more halogen atoms selected from Cl, I, and Br. In some embodiments, the co-reactant is selected from the group consisting of halosilanes, alkyl halides, and acyl halides. In some embodiments, the co-reactant is pulsed into the reaction chamber at least partially simultaneously with the Lewis acid reactant. In some embodiments, the co-reactant and the Lewis acid reactant are pulsed into the reaction chamber simultaneously.

[0089] In some embodiments, the co-reactant includes a halogen selected from chlorine, bromine, and iodine. In some embodiments, the co-reactant includes an alkyl halide. In some embodiments, the co-reactant includes an alkyl chloride. In some embodiments, the co-reactant includes an alkyl bromide. In some embodiments, the co-reactant includes an alkyl iodide. In some embodiments, the co-reactant includes an aryl halide. In some embodiments, the co-reactant includes an aryl chloride. In some embodiments, the co-reactant includes an aryl bromide. In some embodiments, the co-reactant includes an aryl iodide.

[0090] In some embodiments, the co-reactant includes a halogenated organic compound (organohalide). In some embodiments, the co-reactant is selected from the group consisting of alkyl halides and acyl halides. In some embodiments, the halogen of the organohalide (e.g., alkyl halide or acyl halide) is selected from the group consisting of fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0091] In some embodiments, the co-reactant comprises a hydrocarbon containing one F, Cl, Br, or I atom. In some embodiments, the co-reactant comprises a hydrocarbon containing at least one halogen atom, each halogen independently selected from F, Cl, Br, and I. In some embodiments, the halogen in the co-reactant is chlorine. In some embodiments, the halogen in the co-reactant is bromine. In some embodiments, the halogen in the co-reactant is iodine. In some embodiments, the alkyl halide comprises iodoethane, is substantially composed of iodoethane, or is composed of iodoethane. In some embodiments, the alkyl halide comprises chloroethane, is substantially composed of chloroethane, or is composed of chloroethane. In some embodiments, the co-reactant comprises a hydrocarbon containing two or more chlorine, bromine, or iodine atoms. In embodiments in which the co-reactant comprises at least two halogen atoms, the halogen atoms may be bonded to the same or different carbon atoms. In some embodiments, the co-reactant comprises a hydrocarbon in which two or more chlorine, bromine, or iodine atoms are bonded to a single carbon atom. In some embodiments, the co-reactant comprises a hydrocarbon in which two or more chlorine, bromine, or iodine atoms are bonded to different carbon atoms, for example, two different carbon atoms. In some embodiments, at least two halogen atoms in the co-reactant are bonded to adjacent carbon atoms of the hydrocarbon. In some embodiments, the carbon atoms are not adjacent, i.e., the carbon atoms bonded to the halogen atoms are not directly bonded to each other.

[0092] In some embodiments, the co-reactant comprises a 1,2-dihaloalkane, a 1,2-dihaloalkene, a 1,2-dihaloalkyne, or a 1,2-dihaloaromatic hydrocarbon. In some embodiments, the halogen atoms of the co-reactant are the same halogen. In some embodiments, the two halogen atoms of the co-reactant are chlorine. In some embodiments, the two halogen atoms of the co-reactant are iodine. In some embodiments, the two halogen atoms of the co-reactant are bromine. In some embodiments, the co-reactant comprises 1,2-diiodoethane. In some embodiments, the co-reactant is substantially composed of 1,2-diiodoethane or is composed of 1,2-diiodoethane. In some embodiments, the co-reactant comprises 1,2-dichloroethane. In some embodiments, the co-reactant is substantially composed of 1,2-dichloroethane or is composed of 1,2-dichloroethane.

[0093] In some embodiments, the co-reactants have the general formula X a R b C—CX a R' b , where X is a halogen selected from F, Cl, Br and I, R and R' are independently H or alkyl, and a and b are independently 1 or 2, such that for each carbon atom, a + b = 3.

[0094] In some embodiments, the co-reactant is selected from alkyl chlorides. In some embodiments, the co-reactant is an alkyl chloride and is selected from the group consisting of 1,2-dichloroethane, chloromethane, 2-chloro-2-methylpropane, chloroform, 2-methyl-2-chlorobutane, and tert-butyl chloride.

[0095] In some embodiments, the co-reactant comprises an alkyl halide, including 1,2-diiodoethane or iodobutane. In some embodiments, the co-reactant comprises 1,2-diiodoethane. In some embodiments, the co-reactant comprises iodobutane. In some embodiments, the co-reactant is 1,2-diiodoethane. In some embodiments, the co-reactant is iodobutane. In some embodiments, the co-reactant comprises iodomethane, is substantially composed of iodomethane, or is composed of iodomethane. In some embodiments, the co-reactant comprises tert-butyl iodide, is substantially composed of tert-butyl iodide, or is composed of tert-butyl iodide. In some embodiments, the co-reactant comprises 2-iodo-2-methylbutane, is substantially composed of 2-iodo-2-methylbutane, or is composed of 2-iodo-2-methylbutane.

[0096] In some embodiments, the co-reactant comprises an acyl halide. In some embodiments, the halogen in the co-reactant is selected from chlorine, bromine, iodine, and fluorine (F). In some embodiments, the co-reactant comprises an acyl chloride. In some embodiments, the co-reactant comprises an acyl bromide. In some embodiments, the co-reactant comprises an acyl iodide. In some embodiments, the co-reactant comprises an acyl fluoride. In some embodiments, the acyl halide is selected from the group consisting of: acetyl chloride (CH3COCl), propionyl chloride (or propanoyl chloride, CH3CH2COCl), butyryl chloride / butanoyl chloride, CH3CH2CH2COCl, benzoyl chloride (C6H5COCl) and formyl chloride / methanoyl chloride, HCOCl, acetyl bromide / ethanoyl bromide, CH3COBr, acetyl fluoride / ethanoyl fluoride, CH3COF, acetyl bromide, valerate bromide, 2-methylpropionyl bromide, acetyl iodide, propionyl bromide, 2,2-dimethylpropionyl bromide, neovalerate chloride, neovalerate bromide, neovalerate fluoride and neovalerate iodide.

[0097] In some embodiments, the co-reactant comprises a halosilane. In some embodiments, the co-reactant is a halosilane. In some embodiments, the halosilane is an iodosilane. In some embodiments, the halosilane is a chlorosilane. In some embodiments, the halosilane is a bromosilane. In some embodiments, the halosilane is a fluorosilane.

[0098] In some embodiments, halosilanes have the general formula SiH a X b , wherein X is a halogen selected from F, Cl, Br and I, and wherein a is 0, 1, 2 or 3, and b is 1, 2, 3 or 4, such that a + b = 4. In some embodiments, the halosilane is selected from SiHCl3, SiH2Cl2, SiHI3, SiH2I2, SiHBr3, SiH2Br2, SiHF3 and SiH2F2.

[0099] In some embodiments, the co-reactants have the general formula X a R b Si—SiX a R' b , where X is a halogen selected from F, Cl, Br and I, R and R' are independently H or alkyl, a is independently 1, 2 or 3, and b is 0, 1 or 2, so for each silicon atom, a + b = 3. In some embodiments, the halosilane is selected from SiHCl2-SiHCl2, SiH2Cl-SiH2Cl, SiHCl2-SiH2Cl, SiCl3-SiH2Cl, SiCl3-SiHCl2, SiHI2-SiHI2, SiH2I-SiH2I, SiHI2-SiH2I, SiI3-SiH2I, SiI3-SiHI2, SiHBr2-SiHBr2, SiH2Br-SiH2Br, SiHBr2-SiH2Br, SiBr3-SiH2Br, SiBr3-SiHBr2, SiHF2-SiHF2, SiH2F-SiH2F, SiHF2-SiH2F, SiF3-SiH2F, SiF3-SiHF2, and SiCl3-SiCl3.

[0100] In some embodiments, the halosilane is a halopropylsilane. In some embodiments, the halosilane is selected from Si3Cl8 and Si3Br8.

[0101] Metallic materials

[0102] The metallic materials deposited according to this disclosure include metals from Group 4, Group 5, or Group 6 of the periodic table. In some embodiments, the metal in the metallic material is a Group 4 metal. In some embodiments, the metal in the metallic material is a Group 5 metal. In some embodiments, the metal in the metallic material is a Group 6 metal. In some embodiments, the metallic material contains only one metallic element. In some embodiments, the metallic material includes at least one metal. In some embodiments, the metallic material includes at least two metals. In some embodiments, the metallic material includes at least three metals. In some embodiments, the metallic material includes no more than two metals. In some embodiments, the metallic material includes no more than three metals. Impurities or contaminants are not considered components of the material herein. For example, in embodiments where the metallic material includes only one metal, it should be understood that deposition is performed using only one metallic element.

[0103] In some embodiments, the metal in the metallic material is selected from the group consisting of titanium, zirconium, and hafnium. In some embodiments, the metal in the metallic material is selected from the group consisting of vanadium, niobium, and tantalum. In some embodiments, the metal in the metallic material is selected from the group consisting of chromium, molybdenum, and tungsten. In some embodiments, the metal in the metallic material is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.

[0104] Metal carbides

[0105] In some embodiments, materials comprising Group 4 to 6 transition metals include metal carbides. Therefore, in some embodiments, the deposited material is a metal carbide, wherein the metal is a Group 4, Group 5, or Group 6 metal. Metal carbide herein refers to a material containing at least one metal and carbon. Metal carbides according to this disclosure can exhibit at least some degree of crystalline structure. In some embodiments, the metal carbide is substantially fully arranged in a crystalline structure. In some embodiments, the metal carbide is at least partially amorphous. In some embodiments, the metal carbide is substantially amorphous. In some embodiments, the metal carbide is deposited by providing a metal precursor and a Lewis acid reactant into a reaction chamber. In some embodiments, the metal precursor and Lewis acid reactant are provided alternately and sequentially into the reaction chamber. In such embodiments, deposition can be performed in an ALD manner. Specifically, in some embodiments where the metal material comprises a metal carbide, the deposition process does not include providing a co-reactant into the reaction chamber. Therefore, the deposition process can be an AB-type cyclic deposition process, wherein the two precursors are alternated. This can be distinguished from embodiments where a co-reactant is also provided into the reaction chamber, the latter being classified as an ABC-type process.

[0106] The dosage of the Lewis acid reactant is important for obtaining the desired composition and properties of the deposited material. The Lewis acid reactant can be supplied to the reaction chamber in short pulses to avoid undesirable reactions. The pulse length of the Lewis acid reactant can be shorter than the pulse length of the metal precursor. For example, the pulse length of the Lewis acid reactant can be less than half the length of the metal precursor pulse. The pulse length of the Lewis acid reactant can be less than 10%, or less than 5%, or less than 3%, or less than 1% of the length of the metal precursor pulse. Alternatively or additionally, the gas flow rate of the Lewis acid reactant can be reduced compared to the gas flow rate of the metal precursor and / or optionally the gas flow rate of the co-reactants.

[0107] In some embodiments, the metal-containing material comprises essentially only metal and carbon, and trace amounts of impurities. In some embodiments, the metal-containing material comprises essentially only metal carbides. In some embodiments, the metal-containing material comprises at least 10 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 20 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 30 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 50 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 60 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 75 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 80 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 90 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 95 atomic percent of metal carbides. In some embodiments, the metal-containing material comprises at least 98 atomic percent of metal carbides.

[0108] In some embodiments, the metal-containing material comprises titanium carbide, and the metal precursor is a titanium precursor. In some embodiments, the metal-containing material comprises zirconium carbide, and the metal precursor is a zirconium precursor. In some embodiments, the metal-containing material comprises hafnium carbide, and the metal precursor is a hafnium precursor. In some embodiments, the metal-containing material comprises vanadium carbide, and the metal precursor is a vanadium precursor. In some embodiments, the metal-containing material comprises niobium carbide, and the metal precursor is a niobium precursor. In some embodiments, the metal-containing material comprises tantalum carbide, and the metal precursor is a tantalum precursor. In some embodiments, the metal-containing material comprises chromium carbide, and the metal precursor is a chromium precursor. In some embodiments, the metal-containing material comprises molybdenum carbide, and the metal precursor is a molybdenum precursor. In some embodiments, the metal-containing material comprises tungsten carbide, and the metal precursor is a tungsten precursor.

[0109] elemental metals

[0110] In some embodiments, materials comprising Group 4 to Group 6 transition metals include elemental metals from any of Groups 4 to 6 of the periodic table.

[0111] In some embodiments, the metal-containing material is elemental titanium, and the metal precursor is a titanium precursor. In some embodiments, the metal-containing material is elemental zirconium, and the metal precursor is a zirconium precursor. In some embodiments, the metal-containing material is elemental hafnium, and the metal precursor is a hafnium precursor. In some embodiments, the metal-containing material is elemental vanadium, and the metal precursor is a vanadium precursor. In some embodiments, the metal-containing material is elemental niobium, and the metal precursor is a niobium precursor. In some embodiments, the metal-containing material is elemental tantalum, and the metal precursor is a tantalum precursor. In some embodiments, the metal-containing material is elemental chromium, and the metal precursor is a chromium precursor. In some embodiments, the metal-containing material is elemental molybdenum, and the metal precursor is a molybdenum precursor. In some embodiments, the metal-containing material is elemental tungsten, and the metal precursor is a tungsten precursor.

[0112] Without limiting this disclosure to any particular theory, the Lewis acid reactant provided to the reaction chamber can react with a metal precursor and / or co-reactant or its derivatives chemisorbed on the substrate surface to form a metal-containing material on the substrate. Specifically, the Lewis acid reactant can be provided to the reaction chamber at least partially simultaneously with the co-reactant, such that it can catalyze the reaction between the co-reactant and the metal precursor. The Lewis acid reactant can be provided to the reaction chamber before the co-reactant is provided. The Lewis acid reactant can be provided to the reaction chamber in short pulses. For example, the pulse length of the Lewis acid reactant can be less than half the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 20% of the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 10% of the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 5% of the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 2% of the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 1% of the pulse length of the co-reactant. The pulse length of the Lewis acid reactant can be less than 0.5% of the pulse length of the co-reactant.

[0113] In some embodiments, the duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the length for which the metal precursor is provided to the reaction chamber. It should be understood that, during the deposition process, the total duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the duration for which the metal precursor is provided to the reaction chamber. In some embodiments, the duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the length for which the co-reactant is provided to the reaction chamber. It should be understood that, during the deposition process, the total duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the duration for which the co-reactant is provided to the reaction chamber. Similarly, in some embodiments, the duration for which the Lewis acid reactant is provided to the reaction chamber is less than 5% or less than 10% or less than 20% of the length for which the metal precursor is provided to the reaction chamber. In some embodiments, the duration for which the Lewis acid reactant is provided to the reaction chamber is less than 5% or less than 10% or less than 20% of the length for which the co-reactant is provided to the reaction chamber.

[0114] In some embodiments, the substrate is thermally annealed for about 1 to about 15 minutes. In some embodiments, the substrate is thermally annealed at a temperature of about 200°C to about 600°C.

[0115] Attached Figure

[0116] This disclosure is further explained by the following exemplary embodiments depicted in the accompanying drawings. The illustrations presented herein are not intended to be actual views of any particular material, structure, or component, but are merely schematic representations illustrating embodiments of this disclosure. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. The structures, devices, and components depicted in the drawings may include additional elements and details, which may be omitted for clarity.

[0117] For the sake of brevity, the conventional manufacturing, connection, fabrication, and other functional aspects of the methods and components described herein may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0118] Figure 1This is a block diagram illustrating an exemplary embodiment of method 100 according to the present disclosure. First, at block 102, a substrate is provided in a reaction chamber. For example, the surface of the substrate may be a dielectric surface, or a metallic or metallic surface. In some embodiments, the substrate surface is a high-k surface, such as a hafnium oxide or zirconium oxide surface. In some embodiments, the substrate surface is a silicon-containing dielectric surface, such as a low-k surface, such as a silicon oxide, silicon carbide, or silicon carbonitride surface. In some embodiments, the substrate surface is a metallic surface, such as a copper surface, a molybdenum surface, a tantalum surface, or a tungsten surface. In some embodiments, the substrate surface is a metallic surface, such as a titanium nitride surface. In some embodiments, the substrate surface is an amorphous carbon surface. In some embodiments, the substrate surface is a metal oxide surface or a metal nitride surface (e.g., a metallic surface). In some embodiments, the substrate comprises a pre-cleaned silicon or silicon-germanium substrate. In some embodiments, the substrate has a pre-cleaned silicon or silicon-germanium substrate. The substrate may be heated at block 102 before the metal precursor, Lewis acid reactant, and / or co-reactant are provided into the reaction chamber.

[0119] At frame 104, a metal precursor is provided in the gas phase into the reaction chamber. In an exemplary embodiment, the metal precursor is a molybdenum precursor or a niobium precursor as disclosed herein. For example, the molybdenum precursor may include bis(ethylphenyl)molybdenum or bis(1,3,5-trimethylphenyl)niobium, substantially composed of or composed of the latter. The metal precursor is chemisorbed onto the substrate surface. The metal precursor may be provided into the reaction chamber (i.e., pulsed) for about 1 to 30 seconds, such as about 1.5 seconds, about 10 seconds, about 15 seconds, about 20 seconds, or about 25 seconds. The reaction chamber may be purged after the metal precursor pulse. Purge is not performed in the following steps. Figure 1 The purging can be indicated in the middle, but it can optionally be included in box 104. The duration of the purging can be from about 0.5 seconds to about 15 seconds, for example, about 1 second, about 3 seconds, about 5 seconds or about 8 seconds.

[0120] At frame 106, a Lewis acid reactant is provided in the gas phase into the reaction chamber. Without limiting this disclosure to any particular theory, the Lewis acid reactant pulse may be shorter than the metal precursor pulse. The Lewis acid reacts with a chemisorbed metal precursor or its derivative to form a material comprising Group IV to Group VI metals (i.e., a metal-containing material) on a substrate surface. In an exemplary embodiment, the metal precursor is bis(ethylphenyl)molybdenum, the Lewis acid reactant is TiCl4, and molybdenum carbide is deposited on the substrate surface. In another exemplary embodiment, the metal precursor is bis(1,3,5-trimethylphenyl)niobium, the Lewis acid reactant is AlCl3, and niobium carbide is deposited on the substrate. The reaction chamber may be purged after the Lewis acid reactant pulse. Purge is not performed in... Figure 1 It is indicated in the text, but it can optionally be included in box 106.

[0121] A shorter pulse time than that of a Lewis acid reactant can be used. In an exemplary embodiment, a pulse time of 0.01 seconds to about 1.0 second can be used for a Lewis acid reactant. For example, a pulse time of 0.02 seconds, or 0.04 seconds, or 0.08 seconds, or 0.1 seconds can be used. The selected pulse time can vary depending on the deposition equipment used and other conditions. For example, a flow rate of about 80 to about 1,200 sccm can be used for a Lewis acid reactant, such as about 100 to about 700 sccm, or about 100 sccm, about 200 sccm, about 500 sccm, or about 600 sccm.

[0122] The deposition process according to this disclosure is a cyclic deposition process. Therefore, frames 104 and 106 form a deposition cycle. At cycle 108, the deposition cycle is restarted. The deposition cycle can be repeated multiple times as needed to deposit a metallic material of the desired thickness on the substrate. For example, the deposition cycle can be performed 2 to about 600 times, or 2 to about 500 times, or about 5 to about 200 times, or about 10 to 400 times. For example, the deposition cycle can be performed about 100 times, about 150 times, about 200 times, about 300 times, or about 350 times.

[0123] It is worth noting that, in Figure 1 In the embodiments described, no co-reactants were provided. The resulting metal-containing material was... Figure 1 In an exemplary embodiment, the material is a metal carbide. For example, the metal content of the material may be from about 40 at-% to about 55 at-%, such as about 46 at-%, about 48 at-%, or about 50 at-%. The carbon content of the material may be from about 40 at-% to about 60 at-%, such as from about 40 at-% to about 45 at-%, such as about 42 at-%, or about 44 at-%. The deposited metal-containing material may contain impurities, such as oxygen, or components of Lewis acid reactants (e.g., aluminum, titanium, and chlorine in the current example). The level of such impurities may be, for example, less than about 3.5 at-% for oxygen, less than about 1.1 at-% for halogens, and less than about 2 at-% for aluminum and titanium.

[0124] The resistivity of metallic materials depends on the thickness of the deposited layer. However, in some examples, resistivity below 270 μOhm cm can be obtained where the material (i.e., film) thickness is about 37 nm, or below 260 μOhm cm where the film thickness is about 22 nm. Even very thin films can be deposited, and in some preliminary examples, metallic material films including molybdenum carbide have a resistivity of about 340 μOhm cm at a film thickness of about 3 nm, and about 635 μOhm cm at a film thickness of about 2.4 nm. Furthermore, when materials containing elemental metals are deposited on metal surfaces using the methods according to this disclosure, surface roughness can be reduced compared to prior art processes. For example, when molybdenum is deposited on a copper surface, the roughness of the deposited material can be reduced by about 74%, and on a cobalt surface, the roughness of the deposited material can be reduced by about 61%.

[0125] Process temperatures, such as those of the reaction chamber or substrate support, can range from about 200°C to about 450°C, or from about 300°C to about 400°C, or from about 300°C to about 3750°C. For example, process temperatures can be about 250°C, about 300°C, about 350°C, or about 375°C, such as about 300°C or about 350°C. Without limiting this disclosure to any particular theory, the selected temperature can be related to the deposition rate and the controllability of the deposition process. The temperature range (i.e., the ALD window) for depositing metallic materials in ALD schemes is wide for current processes. In some embodiments, the ALD window is from about 250°C to about 400°C. ALD-type processes allow conformal deposition of materials, i.e., deposition rates are substantially the same on both the vertical and horizontal portions of the structure. The inventors of this disclosure have demonstrated near 100% conformality on structures with a critical dimension of 20 nm and a depth of 100 nm. Therefore, the metallic materials described herein can be deposited in a conformal manner, thus confirming that the deposition can be described as ALD.

[0126] Although not described in detail in this disclosure, the process may include additional steps such as heat treatment (e.g., annealing), intermediate etching back, or post-deposition etching. Although not described in detail... Figure 1 and Figure 2 As shown, however, the boxes for the deposition process can overlap. For example, boxes 104 and 106 can be performed at least partially simultaneously. In some embodiments, boxes 104 and 106 are performed at least partially simultaneously.

[0127] Figure 2 This is a block diagram of another exemplary embodiment of the method according to the present disclosure, illustrating the deposition of a elemental metal. Figure 1 Compared to the previous embodiment, Figure 2 Examples include providing co-reactants into the reaction chamber as part of the deposition process. Figure 2 In the embodiments described herein, the metallic material deposited on the substrate comprises elemental metals. Depositing elemental metals on the substrate should be understood as depositing metals from any of Groups 4 to 6 of the periodic table, which are essentially in elemental form. If the metal's oxidation state is zero, the metal is deposited in elemental form. For example, in the deposition method of this disclosure, at least about 65 at-%, or at least about 80 at-%, or at least about 90% of the metal is deposited in elemental form.

[0128] exist Figure 2 In the embodiments, process 200 and Figure 1 Those begin similarly. Boxes 202, 204, and 206 correspond to... Figure 1 Boxes 102, 104, and 106. Figure 2 Implementation examples and Figure 1 The difference in the embodiments is that the co-reactants, as described in this disclosure, are provided to the reaction chamber in the gas phase. As mentioned above, including co-reactants significantly alters the composition of the metal-containing material. Instead of metal carbides, the deposited material primarily comprises elemental metals.

[0129] exist Figure 2 In the middle, at box 206, that is, before the co-reactant is provided into the reaction chamber at box 208, the Lewis acid reactant is provided into the reaction chamber. Although boxes 206 and 208 are in Figure 2 The process is described as separate stages, but they do not need to be discrete. In contrast, Figure 2 This can be understood as describing the initiation of the Lewis acid reactant before or simultaneously with the introduction of the co-reactant into the reaction chamber. The pulse length of the Lewis acid reactant can be much shorter than the pulse lengths of the metal precursor and co-reactant. The lengths of all precursor and reactant pulses depend on the equipment and process parameters used in the specific process.

[0130] The co-reactant provided to reaction chamber 208 is a co-reactant as disclosed herein. In some examples, the co-reactant is 1,2-diiodoethane or iodobutane.

[0131] according to Figure 2 The deposition process is cyclic, and as described above, the deposition cycle (in this case, including boxes 204, 206, and 208) is repeated a predetermined number of times as shown in cycle 210 to deposit the required amount of metallic material. In some preliminary examples, the deposition cycle is performed approximately 400 times.

[0132] Figure 2Optional cycle 212 (indicated by the dashed arrow) is also included. The Lewis acid reactant and co-reactant are provided (e.g., pulsed) and can be repeated a predetermined number of times before the metal precursor is reintroduced into the reaction chamber in the next deposition cycle. Thus, cycle 212 defines a sub-cycle of the deposition cycle (defined by cycle 210), which can be referred to as the main cycle.

[0133] Figure 3 Depicting something similar to Figure 2 The embodiments described have respectively corresponding to Figure 2 The deposition process 300 of frames 202 and 204 and frames 302 and 304. However, due to Figure 3 The option to provide (e.g., pulse) the co-reactant into the reaction chamber before or simultaneously with the Lewis acid reactant is highlighted; therefore, box 306 corresponds to box 208, and box 308 corresponds to box 206. A cycle 312 is included for use as... Figure 2 The optional sub-loop modification of the process is specified in loop 310, which indicates the overall loop characteristics of the process.

[0134] according to Figure 2 and 3 The deposited elemental metal may contain impurities. The elemental metal material deposited according to this disclosure contains low-carbon impurities, for example, less than about 5 atomic percent, or less than about 2.5 atomic percent. Therefore, the metallic material (e.g., a metal film) possesses properties particularly suitable for certain applications in the manufacture of semiconductor devices. For example, when deposited on a silicon substrate material, a metal-containing material including elemental metals can be used as a contact material. Sharp metal-silicon interfaces, especially those with low oxygen content, can be advantageous for such applications using the methods and materials according to this disclosure. In some preliminary tests of the process, a contact resistivity of less than 6 × 10⁻⁶ was observed on the silicon. -9 Ohm cm 2 When deposited on a metal surface (e.g., a copper surface), a decrease in roughness was observed and no metal (e.g., molybdenum) mixed with the underlying metal (e.g., copper).

[0135] In some examples, elemental molybdenum is deposited using bis(ethylphenyl)molybdenum as a metal precursor, iodobutane as a co-reactant, and TiCl4 as a Lewis acid reactant. After each precursor and reactant is supplied to the reaction chamber, the reaction chamber is purged.

[0136] Figure 4 This is a schematic diagram of an embodiment of a semiconductor processing assembly according to the present disclosure. In one aspect, a semiconductor processing assembly configured and arranged to perform the methods according to the present disclosure is disclosed.

[0137] Therefore, a semiconductor processing assembly 400 for depositing a metallic material (particularly a single metal or a metal carbide) on a substrate is disclosed. The semiconductor processing assembly 400 includes: one or more reaction chambers 420 configured and arranged to hold a substrate; and a precursor injector system 401 configured and arranged to provide a metal precursor comprising a metal-organic compound in the gas phase into the reaction chambers 420. The semiconductor processing assembly 400 also includes a metal precursor source container 402 and a Lewis acid reactant source container 403. The precursor injector system 401 is configured and arranged to provide the metal precursor and the Lewis acid reactant in the gas phase into the reaction chambers 420. The metal precursor and the Lewis acid reactant can be provided alternately and sequentially into the reaction chambers to form a metallic material, particularly a metal carbide, on the substrate.

[0138] The semiconductor processing assembly 400 also includes an optional co-reactant source container 404 configured and arranged to contain the co-reactant according to the present disclosure. The semiconductor processing assembly 400 is configured and arranged to provide the co-reactant to a reaction chamber 420 via a precursor implanter system 401 for forming a metallic material, particularly a material containing an elemental metal, on a substrate.

[0139] Processing assembly 400 may include an optional additional source container (not shown) configured and arranged to contain additional reactants used in the processing of the substrate. For example, the additional source container may be configured and arranged to contain additional metal precursors or etchants.

[0140] Processing assembly 400 is configured and arranged to perform the methods described herein. In the example shown, semiconductor processing assembly 400 includes one or more reaction chambers 420, a precursor injector system 401, source containers 402, 403, optional and additional source containers (e.g., co-reactant source container 404), an exhaust source 422, and a controller 430. Processing assembly 400 may include one or more additional gas sources (not shown), such as inert gas sources, carrier gas sources, and / or purge gas sources. Reaction chamber 420 may include any suitable reaction chamber, such as the ALD or CVD reaction chambers described herein.

[0141] Metal precursor source container 402 may include a container and a metal precursor as described herein—alone or mixed with one or more carrier (e.g., inert) gases. Reactant source container 403 may include a container and a reactant as described herein—alone or mixed with one or more carrier (e.g., inert) gases. Thus, although three source containers 402-404 are shown, the processing assembly 400 may include any suitable number of source containers. Source containers 402-404 may be coupled to reaction chamber 420 via lines 412-414, each of which may include a flow controller, valve, heater, etc. In some embodiments, each of source containers 402-404 may be independently heated or maintained at ambient temperature. In some embodiments, the source container is heated such that the precursor or reactant reaches a suitable evaporation temperature.

[0142] The exhaust source 422 may include one or more vacuum pumps.

[0143] Controller 430 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in processing assembly 400. The controller is programmed to perform methods as disclosed herein. Such circuitry and components operate to introduce precursors, reactants, and other gases from appropriate sources. Controller 430 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 420, the pressure within the reaction chamber 420, and various other operations to provide appropriate operation of processing assembly 400. Controller 430 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursors, reactants, and other gases from reaction chamber 420. Controller 430 may include modules, such as software or hardware components, to perform certain tasks.

[0144] Other configurations of the processing assembly 400 are possible, including different numbers and types of precursor and source containers. For example, the reaction chamber 420 may include more than one, such as two or four deposition stations. Such a multi-station configuration may be advantageous if, for example, suppression, passivation, deposition, and / or etching are to be performed in the same reaction chamber. Furthermore, it should be understood that numerous arrangements of valves, piping, precursor sources, and reactant sources exist that can be used to achieve the goal of supplying gas to the reaction chamber 420 in a coordinated manner. Additionally, for the sake of simplicity, many components have been omitted from the schematic diagram of the processing assembly 400, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0145] During operation of the processing component 400, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to a reaction chamber 420. Once the substrate(s) are transferred to the reaction chamber 420 (i.e., provided in the reaction chamber 420), one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) from a gas source are introduced into the reaction chamber 420.

[0146] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in other orders, or in some cases omitted.

[0147] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various methods and components disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for depositing a material comprising group IV to group VI transition metals on a substrate via a cyclic deposition process, the method comprising: A substrate is provided in the reactor chamber; A metal precursor, including an organometallic compound, is provided in the gas phase into the reaction chamber; as well as Lewis acid reactants are provided in the gas phase into the reaction chamber to react with the metal precursor; and the material comprising the transition metal of any group from group 4 to group 6 is formed on the substrate.

2. The method of claim 1, further comprising providing the co-reactant in the gas phase into the reaction chamber.

3. The method according to claim 1 or 2, wherein, The organometallic compounds include metals selected from the group consisting of vanadium, niobium, tantalum, chromium, molybdenum and tungsten.

4. The method according to any one of the preceding claims, wherein, The metal precursors include zero-valent organometallic compounds.

5. The method according to any one of the preceding claims, wherein, The metal precursor includes a diaromatic complex.

6. The method according to any one of the preceding claims, wherein, The Lewis acid reactants include inorganic halides.

7. The method according to claim 6, wherein, The Lewis acid reactants are selected from the group consisting of metal halides and non-metal halides.

8. The method according to any one of claims 6 or 7, wherein, The inorganic halide is a chloride.

9. The method according to any one of claims 6 to 8, wherein, The inorganic halide is a metal halide selected from the group consisting of aluminum chloride, molybdenum chloride, ferric chloride, and titanium tetrachloride.

10. The method according to any one of claims 1 to 5, wherein, The Lewis acid reactants include Group 13 elements and one or more ligands selected from halides, alkoxides, alkyl groups, dialkylamides, and combinations thereof.

11. The method according to claim 1, wherein, The materials, including transition metals from Group IV to Group VI, include metal carbides.

12. The method according to any one of claims 2 to 10, wherein, The co-reactants are selected from the group consisting of free silanes, alkyl halides and acyl halides.

13. The method according to claim 12, wherein, The co-reactants include alkyl halides, which include 1,2-diiodoethane or iodobutane.

14. The method according to claim 12, wherein, The co-reactants are selected from alkyl chlorides.

15. The method according to claim 14, wherein, The co-reactant is an alkyl chloride and is selected from the group consisting of 1,2-dichloroethane, chloromethane, 2-chloro-2-methylpropane, chloroform, 2-methyl-2-chloro-butane, and tert-butyl chloride.

16. The method according to any one of claims 12 to 15, wherein, The material comprising the transition metals of Groups 4 to 6 includes elemental metals from any of Groups 4 to 6 of the periodic table.

17. The method according to any one of claims 2 to 16, wherein, The metal precursor, the Lewis acid reactant, and the co-reactant are supplied in a pulsed manner, and the reaction chamber is purged after a series of pulses of the Lewis acid reactant and the co-reactant.

18. The method according to any one of claims 2 to 17, wherein, The Lewis acid reactant and the co-reactant are provided in any order.

19. The method according to any one of the preceding claims, wherein, The duration for which the Lewis acid reactant is provided to the reaction chamber is less than 2% of the duration for which the metal precursor is provided to the reaction chamber.

20. The method according to any one of the preceding claims, wherein, The process temperature is between approximately 150-400°C.

21. The method according to any one of the preceding claims, wherein, The substrate includes a pre-cleaned silicon or silicon-germanium substrate.

22. A semiconductor processing assembly configured and arranged to perform the method according to any one of claims 1 to 21.

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