Method for forming a rhenium-containing film on a substrate by a periodic deposition process and related semiconductor device structures

Abstract

To provide a method for depositing a rhenium containing film on a base material by periodic deposition.SOLUTION: A method for depositing a rhenium containing film on a base material by periodic deposition comprises: contacting the base material to a first gas phase reaction material including a rhenium precursor; and contacting the base material to a second gas phase reaction material. A semiconductor device structure includes the rhenium containing film deposited by the method.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates in general to a method for forming a rhenium-containing film on a substrate by a periodic deposition process, and in particular to a method for forming a rhenium-containing film by a periodic deposition process utilizing a rhenium precursor. [Background technology]

[0002] Rhenium-containing films can be utilized in a wide range of technical applications. For example, elemental rhenium films can be used as catalysts in high-temperature superalloys, superconducting applications, adhesive layers, liners, diffusion barriers, seed layers, seed layers for improving the growth of other materials, and microelectronic applications. Furthermore, rhenium oxide can exhibit low electrical resistivity and can therefore be used as electrodes in semiconductor device structures, such as dynamic random-access memory (DRAM) devices. Moreover, rhenium sulfides, such as rhenium disulfide (ReS2), have been shown to exhibit behavior similar to that of 2D materials, even in 3D bulk form. Therefore, rhenium sulfides can find applications in tribology, other low-friction applications, solar cell applications, and in quantum computing and ultrafast data processing. Thus, methods for forming rhenium-containing films and related semiconductor device structures containing rhenium-containing films are highly desirable. [Overview of the project]

[0003] This summary of the invention is provided to introduce the selection of concepts in a simplified manner. These concepts are described in more detail in the "Modes for Carrying Out the Invention" of the exemplary embodiments of this disclosure below. This summary of the invention is not intended to identify any major or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0004] In some embodiments, a method is provided for forming a rhenium-containing film on a substrate by a periodic deposition process. The method may include contacting the substrate with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and contacting the substrate with a second gas-phase reactant.

[0005] For the purpose of summarizing the invention and its advantages achieved beyond the prior art, certain objectives and advantages of the invention are described above herein. Naturally, it should be understood that not all of these objectives or advantages are necessarily achieved by any particular embodiment of the invention. Therefore, those skilled in the art will recognize that the invention may be embodied or practiced in a manner that achieves or optimizes one or a group of advantages, for example, as taught or suggested herein, without necessarily achieving other objectives or advantages as may be taught or suggested herein.

[0006] All of these embodiments are intended to be within the scope of the invention disclosed herein. To those skilled in the art, these and other embodiments will be readily apparent from the embodiments for carrying out the invention described below with reference to the accompanying drawings, and the invention is not limited to all specific embodiments disclosed. [Brief explanation of the drawing]

[0007] While this specification specifically points out embodiments of the present invention and concludes in the explicitly claimed claims, the advantages of the embodiments of this disclosure can be more readily determined from the descriptions of certain embodiments of this disclosure when read in conjunction with the accompanying drawings.

[0008] [Figure 1] Figure 1 shows a non-limiting, exemplary process flow illustrating a method for forming a rhenium oxide film on a substrate by a periodic deposition process according to embodiments of the present disclosure.

[0009] [Figure 2] Figure 2 shows a non - limiting exemplary process flow illustrating an additional method for forming a rhenium oxide film on a substrate by a periodic deposition process according to an embodiment of the present disclosure.

[0010] [Figure 3] Figure 3 shows a non - limiting exemplary process flow illustrating a further method for forming a rhenium oxide film on a substrate by a periodic deposition process according to an embodiment of the present disclosure.

[0011] <​​​​​​​​​​​​​​​​​​​​​​​​​​

[0016] [Figure 9] Figure 9 shows a schematic cross-sectional view of a semiconductor device structure including a rhenium-containing film formed by an embodiment of the present disclosure.

[0017] [Figure 10] Figure 10 shows an exemplary reaction system configured to carry out a periodic deposition method according to an embodiment of the present disclosure. [Modes for carrying out the invention]

[0018] While several embodiments and examples are disclosed below, it will be understood by those skilled in the art that the present invention extends beyond the embodiments and / or uses of the invention specifically disclosed, as well as their obvious modifications and equivalents. Therefore, the scope of the disclosed invention is not intended to be limited by the specific embodiments described below.

[0019] The figures shown herein are not intended to be actual diagrams of any particular material, structure, or device, but are merely idealized representations used to illustrate embodiments of the present disclosure.

[0020] As used herein, the term "rhenium oxyhalide precursor" refers to the general formula Re a O b X c It may also refer to a molecule having the formula, where Re is rhenium, O is oxygen, X is a halogen atom such as fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), and a, b, and c are integers of 1 or more.

[0021] As used herein, the term “periodic chemical vapor deposition” may refer to any process in which a substrate is successively exposed to two or more volatile precursors, the precursors reacting and / or decomposing on the substrate to produce a desired deposit.

[0022] As used herein, the term “substrate” may refer to any base material or combination of materials on which a device, circuit, or film can be used or formed.

[0023] As used herein, the term “atomic layer deposition” (ALD) refers to a deposition process in which a series of deposition cycles, including multiple consecutive deposition cycles, are carried out in a reaction chamber. Typically, during each cycle, a precursor is chemisorbed onto the deposition surface (e.g., the surface of a substrate or a previously deposited underlayment, e.g., a material deposited using a previous ALD cycle) to form a monolayer or sub-monolayer that does not readily react with additional precursors (i.e., a self-controlled reaction). Subsequently, if necessary, reactants (e.g., another precursor or reaction gas) can be introduced into the process chamber for use in converting the chemisorbed precursor into the desired material on the deposition surface. Typically, these reactants can further react with the precursor. Furthermore, a purging step can be utilized during each cycle to remove excess precursor from the process chamber after the conversion of the chemisorbed precursor, as well as / or excess reactants and / or reaction byproducts from the process chamber. Furthermore, as used herein, the term “atomic layer deposition” also means processes represented by related terms, such as “chemical vapor deposition atomic layer deposition,” “atomic layer epitaxy” (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, and chemical beam epitaxy when carried out with alternating pulses of precursor composition, reactive gas, and purge gas (e.g., inert carrier).

[0024] As used herein, the terms “film” and “thin film” are intended to mean any continuous or discontinuous structure and material formed by the methods disclosed herein. Examples of “film” and “thin film” include 2D materials, nanorods, nanolaminates, nanotubes, or nanoparticles, or partial or complete molecular layers, or partial or complete atomic layers, or clusters of atoms and / or molecules. “Film” and “thin film” may include materials or layers having pinholes, but are still at least partially continuous.

[0025] It should be noted that while many exemplary materials are given through embodiments of this disclosure, the chemical formulas given for each exemplary material should not be interpreted as restrictive, and the non-restrictive exemplary materials given should not be limited by any exemplary stoichiometry.

[0026] This disclosure includes methods for forming and utilizing rhenium-containing films and related semiconductor device structures. For example, rhenium-containing films such as elemental rhenium films, rhenium oxide films, rhenium sulfide films, and rhenium boride films can be used in a wide variety of technical applications.

[0027] As a non-limiting example, certain rhenium oxide films, such as rhenium trioxide (ReO3), can exhibit very low electrical resistivity and can therefore be used in a number of semiconductor device applications, including, but not limited to, device interconnects, barrier layers, Schottky devices, metal-insulating semiconductor (MIS) devices, metal-insulating-metal devices (MIM) devices, and as part of gate electrodes.

[0028] Rhenium oxides can also be used for doping semiconductor devices. For example, rhenium oxides can be used to adjust the conductivity of semiconductor materials and to control the adhesion of specific materials. In a further example, rhenium oxides can be used to form interesting mixed compounds, for example, in solid-solid reactions.

[0029] For example, the attractive physical properties of rhenium oxides such as rhenium dioxide, rhenium trioxide, or dirhenium heptoxide can open up several novel applications. In some embodiments, rhenium oxides can be used for bottom-up filling or filling of trench structures, pits, or gap structures in composite 3D structures. Bottom-up and / or gap filling with rhenium oxide can be achieved in many ways, including, but are not limited to, depositing rhenium oxide at a low deposition temperature, then annealing the deposited rhenium oxide film at a higher temperature to lift the rhenium oxide film into the lower region of the 3D structure. The annealing temperature of the rhenium oxide film may be above 50°C, above 100°C, above 200°C, above 300°C, or above 350°C. The annealing of the rhenium oxide film may be carried out in an oxidizing or reducing environment to maintain a specific composition of the rhenium oxide film. For example, annealing of a rhenium oxide film may be carried out in an environment containing at least one of nitric oxide (NO), nitrogen dioxide (NO2), sulfur oxides (e.g., SO2 or SO3), oxygen, or water.

[0030] As a further non-limiting example, rhenium oxide such as Re2O7 may be used as a raw material in chemical vapor deposition (CVD) processes, and to deposit Re2O7 for thin film applications and / or gap filling applications, Re2O7 may begin to sublimate at temperatures above approximately 100°C, above approximately 150°C, or above approximately 180°C.

[0031] In some embodiments of this disclosure, the deposition temperature can be carefully controlled so that a first composition of rhenium oxide film can be deposited on top of a second composition of rhenium oxide film, and the first and second compositions are different from each other. For example, at deposition temperatures of about 220°C to 350°C, a rhenium oxide film that does not contain composition Re2O7 can be deposited.

[0032] In some embodiments, rhenium oxide films can be deposited on template structures, such as corrugated surfaces and / or patterned surfaces, for example, to form quantum dots, nanodots, nanowires, or nanopatterns containing rhenium oxide material. In such embodiments, the initial or final material may be rhenium oxide, elemental rhenium metal, rhenium boride, or rhenium sulfide. Depending on the desired rhenium-containing material, various processing steps such as oxidation, reduction, or sulfidation of the initial rhenium-containing film may be utilized. As described above, an annealing step may also be used to allow the rhenium-containing material to accumulate at the lower vertices of a corrugation or in the lower regions of a 3D structure.

[0033] In some embodiments, the deposited rhenium-containing films or alloys thereof may contain boron, sulfur, carbon, nitrogen, phosphorus, or any combination thereof. In some embodiments, the rhenium-containing films may be classified as one of the possible phases of rhenium carbide, rhenium boride, rhenium nitride, or rhenium phosphide, or may contain two or more elements. For example, the rhenium-containing films may contain boron and carbon, nitrogen and boron, or any possible combination of boron, carbon, nitrogen, and phosphorus. In some embodiments of the present disclosure, the rhenium-containing films may contain rhenium-boron carbide (ReBC), rhenium diboride (ReB2), dirhenium triboride (Re2B3), or rhenium boride (ReB, Re3B7, Re3B, and Re2B).

[0034] In some embodiments of this disclosure, the rhenium-containing film may contain boron, carbon, nitrogen, sulfur, phosphorus, or any possible combination thereof. Non-limiting applications of such mixed alloys of rhenium, boron, carbon, nitrogen, or phosphorus may be utilized as adhesion-enhancing layers, seed layers, diffusion barriers, hard coatings, high modulus superhard layers, or liners.

[0035] In some embodiments, the rhenium-containing film may comprise at least one of ReBC, ReB, ReC, Re3P4, Re2P, ReP4, Re3N, Re2N, ReN, ReN2, ReN4, Re2C, ReC, Re4C, and ReB2. In some embodiments, the rhenium-containing film may be used as a superconducting layer, a hard mask in patterning applications, an etch-stop layer in patterning applications, a reaction chamber and components of a reaction chamber, a coating for an etching reactor, a protective coating against etching chemicals, and ReP4 as a semiconductor layer.

[0036] In some cases, it is desirable to form voids, and low-boiling-point rhenium oxide films can be used in such applications. For example, by annealing the rhenium oxide film at a temperature above approximately 400°C, the rhenium oxide film may be completely sublimated from the gap features filled with voids, or the deposited rhenium oxide film may be sublimated. In some embodiments, the sublimation of the rhenium oxide film may leave voids, or alternatively, the rhenium oxide film may be used as a sacrificial layer and / or a patterning layer for patterning applications.

[0037] In some embodiments, the rhenium-containing film may be used in back-end (BEOL) applications such as metal contacts, which may be deposited on a lower liner layer, adhesive layer, seed layer, or diffusion barrier layer, and in some applications, the metal contacts may be capped with a metal alloy. For example, in some applications, the metal interconnect may be elemental rhenium and may be deposited on a lower rhenium alloy such as rhenium carbide, rhenium boride, rhenium nitride, or rhenium phosphide. In some embodiments, the metal precursor used to deposit the metal contact is the same as that used for depositing the liner layer, adhesive layer, seed layer, or diffusion barrier layer, and only the selection of a second reactant and / or process conditions (e.g., deposition temperature) may differ. This approach may be advantageous in processing because only one metal precursor is used, and this approach can be applied to other processes that utilize different metals, such as cobalt as a metal contact or interconnect and cobalt phosphide as an adhesive layer or liner layer. A similar approach can be used for ruthenium-based processes and their associated carbides.

[0038] In addition, rhenium oxide films, such as rhenium(VII)(Re2O7), may exhibit dielectric properties and can therefore be used in DRAM devices and as capacitor structures. ReO2 can find applications in spintronic devices and memory devices such as resistive random-access memory (RAM). In some embodiments, rhenium oxide can be used in catalytic science. In some embodiments, deposited rhenium-containing films can facilitate selective deposition or etching. For example, ReO x The catalytic effect can support several ALD precursors for reaction or decomposition on its surface.

[0039] Furthermore, rhenium oxide films, such as rhenium trioxide (ReO3), exhibit a low melting point, which can be advantageous by capping the rhenium oxide film with a capping layer, such as titanium nitride (TiN), and then thermally annealing the rhenium oxide film to form a single-crystal rhenium oxide film, or by increasing the particle size of the crystal containing the rhenium oxide film, thereby reducing the electrical resistivity of the rhenium oxide film.

[0040] Accordingly, embodiments of the present disclosure may include a method for forming a rhenium-containing film on a substrate by a periodic deposition process. In some embodiments, the method may include contacting the substrate with a first gas-phase reactant comprising a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and contacting the substrate with a second gas-phase reactant.

[0041] The methods for forming rhenium-containing films disclosed herein may include, for example, periodic deposition processes such as atomic layer deposition (ALD) or periodic chemical vapor deposition (CCVD).

[0042] A non-limiting exemplary embodiment of a periodic deposition process includes atomic layer deposition (ALD), which is based on a typical self-controlled reaction that deposits approximately one atomic (or molecular) monolayer of material per deposition cycle using sequential and alternating pulses of reactants. The deposition conditions and precursors are typically selected to provide a self-saturating reaction such that an adsorbed layer of one reactant leaves a surface end that is unreactive with the gas-phase reactant of the same reactant. The substrate is then brought into contact with a different reactant that reacts with the previous end, enabling continuous deposition. Thus, each cycle of the alternating pulse typically leaves a monolayer of approximately one or less of the desired material. However, as described above, it will be recognized that more than one monolayer of material can be deposited in one or more ALD cycles, for example, if several gas-phase reactions occur despite the nature of the alternating process.

[0043] For example, in an ALD-type process used for forming a rhenium-containing film such as an elemental rhenium film, a rhenium oxide film, a rhenium sulfide film, or a rhenium boride film, one deposition cycle can include exposing a substrate to a first gaseous reactant, removing all unreacted first reactant and reaction by-products from the reaction chamber, and exposing the substrate to a second gaseous reactant, followed by a second removal step. In some embodiments of the present disclosure, the first gaseous reactant can include a rhenium precursor, and the second gaseous reactant can include at least one of an oxygen-containing precursor, a sulfur-containing precursor, a boron-containing precursor, and a hydrogen-containing precursor.

[0044] In some embodiments of the present disclosure, the boron-containing precursor has the general formula B n H n+x borane, where n and x are integers greater than or equal to 1. In some embodiments, the boron-containing precursor may contain an alkyl borate of the general formula R 1 R 2 R 3 O3B, where R is any alkyl or aryl group. In some embodiments, the boron-containing precursor can include at least one of borane (BH3), diborane (B2H6), decaborane (B 10 H 14 ), tetraborane (B4H 10 ), trimethyl borate, or triethyl borate.

[0045] The precursor can be separated by an inert gas, such as argon (Ar) or nitrogen (N2), to prevent gas-phase reactions between the reactants and enable self-saturated surface reactions. However, in some embodiments, the substrate can be moved to bring the first gas-phase reactant and the second gas-phase reactant into contact separately. Since the reaction is self-saturated, strict temperature control of the substrate and precise dosage control of the precursor may not be necessary. However, the substrate temperature should be such that the incident gas species do not condense into a single layer and do not decompose on the surface. Before contacting the substrate with the next reactive chemical, any excess chemicals and reaction byproducts are removed from the substrate surface, for example, by purging the reaction space or by moving the substrate. Undesirable gas molecules can be effectively removed from the reaction space using an inert purge gas. A vacuum pump can be used to facilitate purging.

[0046] Reactors that can be used to deposit rhenium-containing films can be used for the periodic deposition processes described herein. Such reactors include ALD reactors and CVD reactors configured to supply precursors. According to some embodiments, showerhead reactors may be used. According to some embodiments, cross-flow, batch, mini-batch, or space ALD reactors may be used.

[0047] In some embodiments of this disclosure, a batch reactor may be used. In some embodiments, a vertical batch reactor may be used. In other embodiments, the batch reactor comprises a minibatch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 or fewer wafers. In some embodiments in which a batch reactor is used, the non-uniformity between wafers is less than 5% (1 sigma), or less than 3%, or less than 2%, or less than 1%, or even less than 0.5%.

[0048] The exemplary periodic deposition processes described herein may optionally be carried out in reactors or reaction chambers connected to a cluster tool. In a cluster tool, since each reaction chamber is dedicated to one type of process, the temperature of the reaction chambers within each module can be kept constant, resulting in improved throughput compared to reactors that heat the substrate to process temperature before each operation. Furthermore, a cluster tool makes it possible to reduce the time required to evacuate the reaction chambers between substrates to a desired process pressure level. In some embodiments of this disclosure, the exemplary periodic deposition process for forming rhenium-containing films disclosed herein may be carried out in a cluster tool comprising multiple reaction chambers, each of which may be used to expose the substrate to an individual precursor gas, or the substrate may be transported between different reaction chambers to expose it to multiple precursor gases, with the transport of the substrate carried out in a controlled environment to prevent oxidation / contamination of the substrate. In some embodiments of this disclosure, the periodic deposition process for forming rhenium-containing films may be carried out in a cluster tool comprising multiple reaction chambers, each of which may be configured to heat the substrate to different temperatures.

[0049] Standalone reactors may be equipped with load locks. In that case, it is not necessary to cool the reaction chamber between each operation.

[0050] In some embodiments, the deposition process used in forming the rhenium-containing film may include multiple deposition cycles, such as an ALD cycle or a periodic CVD cycle.

[0051] In some embodiments, the periodic deposition process can be a hybrid ALD / CVD or a periodic CVD process. For example, in some embodiments, the growth rate of the ALD process may be lower compared to the CVD process. One approach to increase the growth rate is to operate at a substrate temperature higher than that typically used in the ALD process, which consequently becomes part of the chemical deposition process, but further utilizes the sequential introduction of precursors; such a process may be called periodic CVD. In some embodiments, the periodic CVD process may involve the introduction of two or more precursors into the reaction chamber, and the overlapping periods between the two or more precursors in the reaction chamber result in both the ALD component of the deposition and the CVD component of the deposition. For example, the periodic CVD process may include a continuous flow of a first precursor and periodic pulse injection of a second precursor into the reaction chamber.

[0052] According to some embodiments of the present disclosure, an ALD process is used to deposit a rhenium-containing film onto a substrate, such as an integrated circuit workpiece. In some embodiments of the present disclosure, each ALD cycle may comprise two or more separate deposition steps or stages. In the first stage of the deposition cycle ("rhenium stage"), the surface of the substrate to be deposited may be brought into contact with a first gas-phase reactant comprising a rhenium precursor that is chemiadsorbed onto the surface of the substrate, forming a monolayer of about one or less layers of reactant species on the surface of the substrate. In the second stage of deposition, the surface of the substrate to be deposited may be brought into contact with a second gas-phase reactant comprising at least one of an oxygen-containing precursor, a sulfur-containing precursor, a boron-containing precursor, or a hydrogen-containing precursor. Additional steps may include an oxidation step, a reduction step, and / or a pre-washing step.

[0053] In some embodiments of this disclosure, specific oxides of rhenium may be selectively deposited on the surface of another composition of rhenium oxide. Such selective oxidation can be controlled by specifically selecting the oxidation environment. In some embodiments, a particular oxidation environment may be periodically suitable for a periodic deposition process.

[0054] In some embodiments of the present disclosure, a reduction step may be applied to a periodic deposition process. In such embodiments, a reduction step may be required to maintain a specific oxidation state of rhenium in the rhenium-containing film, which may contain, but is not limited to, rhenium, oxygen, carbon, hydrogen, nitrogen, halogen compounds, phosphorus, sulfur, or boron.

[0055] Exemplary periodic deposition process for rhenium oxide film formation In some embodiments of this disclosure, the periodic deposition process is, for example, rhenium(IV) oxide (ReO2), rhenium trioxide (ReO3), rhenium(VII) oxide (Re2O7), or the general formula Re a O b Rhenium oxide having the formula ReO x It may contain a suboxide having the following properties, where x is less than 2.

[0056] In some embodiments, the periodic deposition process may include forming a rhenium oxide film by a surface reaction between a first gas-phase reactant and a second gas-phase reactant. In some embodiments, the periodic deposition process may include forming an intermediate rhenium oxide film, followed by contacting the intermediate rhenium oxide film with a reducing agent precursor to form a rhenium oxide film of a desired composition. In some embodiments, the periodic deposition process may include forming an intermediate rhenium oxide film, followed by contacting the intermediate rhenium oxide film with a further oxygen-containing precursor to form a rhenium oxide film of a desired composition.

[0057] An exemplary rhenium oxide film formation process can be understood by referring to Figure 1, which shows an exemplary periodic deposition process 100 for the formation of a rhenium oxide film.

[0058] More specifically, Figure 1 shows an exemplary rhenium oxide formation process 100, which includes a periodic deposition phase 105. The exemplary rhenium oxide formation process 100 may be initiated by a process block 110, which includes supplying a substrate into a reaction chamber and heating the substrate to a desired deposition temperature.

[0059] In some embodiments of the present disclosure, the substrate may include a planar substrate or a patterned substrate including high aspect ratio features, e.g., trench structures and / or fin structures. The substrate may include, but is not limited to, one or more materials including silicon (Si), germanium (Ge), germanium tin (GeSn), silicon germanium (SiGe), silicon germanium tin (SiGeSn), silicon carbide (SiC), or III-V semiconductor materials, e.g., gallium arsenide (GaAs), gallium phosphide (GaP), or gallium nitride (GaN). In some embodiments of the present disclosure, the substrate may comprise a designed substrate, and the surface semiconductor layer is disposed on a bulk support by interposed embedded oxide (BOX) placed between them. In some embodiments, a liner may be used, which may include, for example, a metal, a metal nitride, a metal boride, a metal carbide, a metal phosphide, or a metal sulfide. In some embodiments, the liner may contain at least one of titanium nitride, tantalum nitride, tantalum carbide, tungsten carbide, molybdenum, niobium boride, or niobium carbide.

[0060] A patterned substrate may include a substrate that can contain semiconductor device structures formed within or on the surface of the substrate. For example, a patterned substrate may include partially manufactured semiconductor device structures, such as transistors and / or memory elements. In some embodiments, the substrate may include one or more secondary surfaces, which may include single-crystal surfaces and / or polycrystalline surfaces and / or non-single-crystal surfaces such as amorphous surfaces. Single-crystal surfaces may include, for example, one or more of silicon (Si), silicon germanium (SiGe), germanium tin (gESn), or germanium (Ge). Polycrystalline or amorphous surfaces may include dielectric materials, such as oxides, oxynitrides, or nitrides, such as silicon oxide and silicon nitride.

[0061] The reaction chamber used for deposition may be an atomic layer deposition reaction chamber, a chemical vapor deposition reaction chamber, or any of the reaction chambers described herein. In some embodiments of the present disclosure, the substrate may be heated to a desired deposition temperature for the subsequent periodic deposition phase 105. For example, the substrate may be heated to a substrate temperature of less than about 750°C, or less than about 650°C, or less than about 550°C, or less than about 450°C, or less than about 350°C, or less than about 250°C, or less than about 150°C. In some embodiments of the present disclosure, the substrate temperature during the periodic deposition phase may be between 300°C and 750°C, or between 400°C and 600°C, or between 400°C and 450°C. In some embodiments, the substrate temperature during the periodic deposition phase may be between 80°C and 150°C, or between 150°C and 200°C, or even between 200°C and 350°C.

[0062] In heating the substrate to a desired deposition temperature, the exemplary rhenium oxide deposition process 100 may be continued by a process block 120 through a periodic deposition phase 105, which includes contacting the substrate with a first gas-phase reactant, in particular, in some embodiments, namely, contacting the substrate with a first gas-phase reactant containing a rhenium gas-phase reactant, which is a rhenium precursor.

[0063] In some embodiments of this disclosure, the rhenium precursor may include a rhenium halide precursor. In some embodiments, the rhenium halide precursor may have any of the oxidation states of 4, 5, 6, or 7. In some embodiments, the rhenium halide precursor may include at least one of rhenium chloride, rhenium fluoride, rhenium bromide, or rhenium iodide. In some embodiments, the first gas-phase reactant may include rhenium chloride, such as rhenium hexachloride (ReCl6) or rhenium pentachloride (ReCl5). In some embodiments, the first gas-phase reactant may include rhenium bromide, such as rhenium pentabromide (ReBr5). In some embodiments, the first gas-phase reactant may include rhenium fluoride, such as rhenium pentafluoride (ReF5), rhenium heptafluoride (ReF7), or rhenium hexafluoride (ReF6).

[0064] In some embodiments of this disclosure, the rhenium precursor may include a rhenium oxyhalide precursor, and the term “rhenium oxyhalide precursor” is defined as having the general formula Re a O b X c It may also refer to a molecule having the formula, where Re is rhenium, O is oxygen, X is a halogen atom such as fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), and a, b, and c are integers of 1 or more.

[0065] In some embodiments, the rhenium oxyhalide may encompass various oxidation states. For example, the oxidation state of rhenium in the rhenium oxyhalide may be 2, 3, 4, 5, 6, or even 7. In some embodiments, the rhenium oxyhalide may contain one, two, or three neutral ligands. For example, the neutral ligands may be alkyl or arylamines, alkyl or arylphosphines, or cyclic amines such as pyridine. In some embodiments, the rhenium oxyhalide may include oxotrichlorobis(triphenylphosphine)rhenium(V)ReOCl3[PPh3]2, oxotrichlorobis(trimethylphosphine)rhenium(V)ReOCl3[(CH3)3P]2, or oxotrichlorobis(dimethylamino)rhenium(V)ReOCl3[(Me2NH)]2. In some embodiments, the rhenium precursor may include, but are not limited to, rhenium oxyfluoride (ReOF), rhenium trioxyfluoride (ReO3F), rhenium oxytetrafluoride (ReOF4), rhenium oxypentafluoride (ReOF5), or rhenium dioxyfluoride (ReO2F2). In some embodiments, the rhenium precursor may include, but are not limited to, rhenium oxychloride (ReOCl), rhenium trioxychloride (ReO3Cl), or rhenium dioxydichloride (ReO2Cl3).

[0066] In some embodiments, the rhenium precursor may include alkylrhenium oxides, such as alkylrhenium trioxide (RReO3, where R is an alkyl group). In some embodiments, the alkylrhenium oxide precursor may include methylrhenium trioxide (CH3ReO3).

[0067] In some embodiments, the rhenium precursor may include a cyclopentadienyl rhenium precursor. In some embodiments, the cyclopentadienyl rhenium precursor may be cyclopentadienylrhenium hydride, pentacarbonylhydride rhenium ReH[CO]5, cyclopentadienylrhenium carbonyl, or zirenium decarbonyl Re2[CO] 10 It may contain at least one of the following. In some embodiments, the cyclopentadienylrhenium hydride precursor may include ReHCp2. In some embodiments, the cyclopentadienylrhenium carbonyl may have any of the oxidation states of 1, 2, 3, 4, 5, or 6. For example, the cyclopentadienylrhenium carbonyl may include ReCp[CO]3, aminocyclopentadienylrhenium carbonyl Re(C5H4NH2)(CO)3, or Re[C5Me5][CO]3.

[0068] In some embodiments, the rhenium precursor is in oxidation state 1, 2, 3, 4, 5, or 6, and the general formula is ReX a [CO] b The present invention comprises a rhenium carbonyl halide precursor having the formula, where X may be fluorine, bromine, chlorine, or iodine, and "a" and "b" may be 1 or more. In some embodiments, the rhenium carbonyl halide precursor may include chloropentacarbonylrhenium(I)ReCl[CO]5 or bromopentacarbonylrhenium(I)ReBr[CO]5.

[0069] In some embodiments of the present disclosure, the metal precursor may be selected to deposit metals and metal alloys by the selection of a second reactant and / or by changing the processing conditions. In some embodiments, the second reactant may be a hydrogen or nitrogen-containing precursor such as hydrogen gas, ammonia, alkylamines, ammonia-hydrogen mixtures, nitrogen-hydrogen plasma, or hydrogen plasma; or a boron-containing precursor such as borane, alkyl borate; or a carbon-containing precursor such as alkyl halides, organic halogen compounds, saturated or unsaturated and aliphatic or non-aliphatic alkanes; or a phosphorus-containing precursor such as phosphine (PH3) or alkylphosphine.

[0070] In some embodiments, the organic mixed halide is of the general formula C a X b Y d The formula consists of, where C is carbon, X is a halide such as chlorine, bromine, iodine, or fluorine, and a, b, and d are integers greater than 1.

[0071] In some embodiments of this disclosure, contacting a substrate with a first gas-phase reactant containing a rhenium precursor may include contacting the substrate with the rhenium precursor for about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5.0 seconds. Furthermore, during contact between the substrate and the rhenium precursor, the flow rate of the rhenium precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the substrate and the rhenium precursor, the flow rate of the rhenium precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0072] The exemplary rhenium oxide formation process 100 shown in Figure 1 may be continued by purging the reaction chamber. For example, excess first gas-phase reactants and reaction by-products (if any) can be removed from the substrate surface by, for example, pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purge cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. For example, excess first gas-phase reactants, such as excess rhenium precursors and possible reaction by-products, may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0073] When the reaction chamber is purged in a purge cycle, the exemplary rhenium oxide formation process 100 may continue with a second stage of periodic deposition phase 105 by process block 130, which includes contacting the substrate with a second gas-phase reactant, and in particular contacting the substrate with a second gas-phase reactant containing an oxygen-containing precursor ("oxygen precursor").

[0074] In some embodiments, the oxygen-containing precursor may include at least one of oxygen, ozone (O3), oxygen plasma, hydrogen peroxide (H2O2), water (H2O), or formic acid. In some embodiments, the rhenium precursor may include rhenium oxydifluoride (ReOF2) or rhenium dioxydichloride (ReOCl2), and the second gas-phase reactant may include water (H2O), ozone (O3), or hydrogen peroxide (H2O2). In some embodiments, the rhenium precursor may include rhenium oxytetrafluoride (ReOF4) or rhenium oxytetrachloride (ReOCl4), and the second gas-phase reactant may include water (H2O), ozone (O3), or hydrogen peroxide (H2O2).

[0075] In some embodiments of this disclosure, the oxygen-containing precursor may include at least one of water (H2O), ozone (O3), hydrogen peroxide (H2O2), oxygen molecules (O2), oxygen atoms (O), sulfur trioxide (SO3), or an oxygen-based plasma, the oxygen-based plasma comprising oxygen atoms (O), oxygen ions, oxygen radicals, and excited oxygen species, and can be generated by excitation of an oxygen-containing gas (e.g., by the application of RF power). Note that the term “gas-phase reactant” includes the excited plasma and the excited species comprising the plasma.

[0076] In some embodiments of this disclosure, contacting the substrate with an oxygen-containing precursor may include contacting the oxygen precursor with the substrate for a period of time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, during contact between the substrate and the oxygen precursor, the flow rate of the oxygen precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the substrate and the oxygen precursor, the flow rate of the oxygen precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0077] Once the substrate is brought into contact with the oxygen precursor, the exemplary rhenium oxide formation process 100 can proceed by purging the reaction chamber. For example, excess oxygen precursor and reaction byproducts (if any) can be removed from the surface of the substrate by, for example, exhausting with an inert gas flow. In some embodiments of the present disclosure, the purging process may include purging the substrate surface for about 0.1 seconds to about 10 seconds, or about 0.5 seconds to about 3 seconds, or even about 1 second to 2 seconds.

[0078] Once the purging of the second gas-phase reactant, i.e., the oxygen precursor (and reaction byproducts) from the reaction chamber is complete, the periodic deposition phase 105 of the exemplary rhenium oxide formation process 100 continues at the determination gate 140, which depends on the thickness of the deposited rhenium oxide film. For example, if the rhenium oxide film is deposited to an insufficient thickness for the desired device application, the periodic deposition phase 105 may be repeated by returning to process block 120 and continuing further deposition cycles, one unit deposition cycle may include contacting the substrate with the rhenium precursor (process block 120), purging the reaction chamber, contacting the substrate with the oxygen-containing precursor (process block 130), and also purging the reaction chamber. The unit deposition cycle of the periodic deposition phase 105 may be repeated once or more times until a rhenium oxide film of the desired thickness is deposited on the substrate. Once the rhenium oxide film is deposited to the desired thickness, the exemplary process 100 is terminated via the process block 150, and the substrate on which the rhenium oxide film is deposited can be subjected to further processing for the formation of a device structure.

[0079] In some embodiments of this disclosure, the order in which the substrate is contacted with a first gas-phase reactant (e.g., a rhenium precursor) and a second gas-phase reactant (e.g., an oxygen precursor) can be such that the substrate is first contacted with the second gas-phase reactant, and then with the first gas-phase reactant. Furthermore, in some embodiments, the periodic deposition phase 105 of exemplary process 100 may include contacting the substrate with the first gas-phase reactant one or more times before contacting the substrate with the second gas-phase reactant one or more times. Furthermore, in some embodiments, the periodic deposition phase 105 of exemplary process 100 may include contacting the substrate with the second gas-phase reactant one or more times before contacting the substrate with the first gas-phase reactant one or more times.

[0080] As a non-limiting example, the reaction chamber may be equipped with an ALD reactor, and the substrate may be heated to a temperature of approximately 200°C (process block 110). The substrate may then be subjected to one or more deposition cycles of periodic deposition phase 105, which may include contacting the substrate with ReOF2 or ReOF4, and then contacting the substrate with water vapor or ozone to form a rhenium trioxide (ReO3) film.

[0081] As a further non-limiting example, the reaction chamber may be equipped with an ALD reactor, and the substrate may be heated to a temperature of approximately 180°C (process block 110). The substrate may then be subjected to one or more deposition cycles of periodic deposition phase 105, which may include contacting the substrate with ReOF5 and then contacting the substrate with water vapor to form a rhenium(VII)(Re2O7) oxide film.

[0082] In some embodiments, the substrate may then be subjected to one or more deposition cycles of periodic deposition phase 105, which may include contacting the substrate with ReOCl or ReOF, and then contacting the substrate with oxygen, ozone, hydrogen peroxide, or water vapor to form a rhenium(IV)(ReO2) oxide film.

[0083] Further exemplary rhenium oxide formation processes can be understood by referring to Figure 2, which shows a periodic deposition process for the formation of a rhenium oxide film.

[0084] More specifically, the periodic deposition process 200 can be initiated by process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 200.

[0085] In heating the substrate to a desired deposition temperature, the periodic deposition process 200 may be continued by a periodic deposition phase 105 in a suitable reaction chamber, which includes periodically depositing a rhenium oxide film to a desired thickness. The periodic deposition phase 105 for depositing the rhenium oxide film has already been described in detail with reference to Figure 1 (exemplary process 100) and is therefore described in a shortened form with respect to the periodic deposition process 200. More specifically, the periodic deposition phase 105 may comprise one or more periodic deposition cycles, each of which includes contacting the substrate with a rhenium precursor, purging excess rhenium precursor and any reaction byproducts from the reaction chamber, contacting the substrate with an oxygen-containing precursor, and purging excess oxygen precursor and any reaction byproducts from the reaction chamber.

[0086] As a non-limiting example, periodic deposition phase 105 may include depositing a rhenium oxide film, such as rhenium(VII)(Re2O7), by contacting the substrate with a rhenium oxyfluoride such as ReOF5, and by contacting the substrate with water vapor (H2O).

[0087] In some embodiments, an intermittent reduction step, i.e., contacting the deposited rhenium oxide film with a reducing agent precursor, may be applied after depositing a rhenium oxide film of a specific thickness. For example, the reduction step may be applied to the rhenium oxide film after depositing a rhenium oxide film with a thickness of approximately 0.5 angstroms, or after depositing a film of less than 1 nanometer, or less than 3 nanometers, or 5 nanometers or less, or even after depositing a film of more than 5 nanometers.

[0088] As a further non-limiting example, periodic deposition phase 105 may include depositing a rhenium oxide film, such as rhenium trioxide (ReO3), by contacting the substrate with a rhenium oxyfluoride such as ReOF4, and by contacting the substrate with water vapor (H2O).

[0089] In embodiments of the present disclosure, the periodic deposition phase 105 may be used to deposit a rhenium oxide film to a thickness of less than 1 angstrom, less than 2 angstroms, less than 5 angstroms, less than 10 angstroms, or even less than 100 angstroms. In embodiments of the present disclosure, the periodic deposition phase 105 may be used to deposit a rhenium oxide film to a thickness that can subsequently be completely reduced by contacting the rhenium oxide film with a reducing agent precursor ("reduction step"), and in some alternative embodiments, the periodic deposition phase 105 may be used to deposit a rhenium oxide film to a thickness that can subsequently be partially reduced by contacting the rhenium oxide film with a reducing agent precursor.

[0090] In forming a rhenium oxide film to a desired thickness, exemplary process 200 can be carried out by process block 220, which includes contacting a substrate and, in particular, contacting the rhenium oxide film with a reducing agent precursor. In some embodiments, the reducing agent precursor may include diones such as 2,5-hexanedione, cyclohexene-1,4-dione, or cyclohexanedione. In some embodiments, the reducing agent precursor may include hydrogen halides such as glyoxylic acid (OCHCO2H), formic acid (HCOOH), HCl, HF, HI, HBr, or acids or carboxylic acids such as oxalic acid (COOH)2. In some embodiments, the reducing agent precursor may include ethylene oxide (C2H4O) or ethylene carbonate. In some embodiments, the reducing agent precursor may include anhydrides such as acetic anhydride (CH3CO)2O), phthalic anhydride, or maleic anhydride (C2H2(CO)2O), but is not limited to these. In some embodiments, the reducing agent precursor may include carbon monoxide (CO), nitric oxide (NO), sulfur monoxide (SO), sulfur dioxide (SO2), hydrogen (H2), hydrazine (N2H4), foaming gas (H2+N2), ammonia (NH3), or an ammonia-hydrogen (NH3-H2) mixture.

[0091] In some embodiments of this disclosure, contacting the substrate with the reducing agent precursor may include contacting the substrate with the reducing agent precursor for about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 10 seconds, or about 0.1 seconds to about 5.0 seconds. Furthermore, during contact between the substrate and the reducing agent precursor, the flow rate of the reducing agent precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Furthermore, during contact between the reducing agent precursor and the substrate, the flow rate of the reducing agent precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0092] As a non-limiting example, the periodic deposition phase 105 of the exemplary process 200 may involve depositing a rhenium(VII)(Re2O7) oxide film to a thickness of less than approximately 100 angstroms, after which the rhenium(VII)(Re2O7) oxide film may be contacted with a reducing agent precursor, such as carbon monoxide (CO), for a period of longer than 1 second at a substrate temperature below 250°C, or for a period of longer than 100 seconds at a substrate temperature below 350°C, but is not limited to this. For example, the reducing agent precursor may include carbon monoxide (CO), nitric oxide (NO), or sulfur monoxide (SO) vapor, and the reducing agent precursor may come into contact with the rhenium(VII)(Re2O7) oxide film, thereby reducing the film to form a rhenium trioxide (ReO3) film.

[0093] As a further non-limiting example, the periodic deposition phase 105 of exemplary process 200 deposits rhenium trioxide (ReO3) to a thickness of less than approximately 1000 angstroms, or less than 500 angstroms, or less than 100 angstroms, or less than 1 angstrom, and subsequently the rhenium trioxide (ReO3) film is exposed to, for example, but not limited to, carbon monoxide (CO), nitric oxide (NO), glyoxylic acid (OCHCO2H). ), 2,5-hexanedione, cyclohexene-1,4-dione, cyclohexanedione, sulfur dioxide (SO2), formic acid (HCOOH), acetic anhydride (CH3CO)2O, oxalic acid (COOH)2, or maleic anhydride (C2H2(CO)2O) may be contacted for less than 5 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature above 60°C, or above 120°C, or above 180°C, or even above 250°C. For example, the reducing agent precursor may include nitric oxide (NO) vapor that can reduce the rhenium(IV)(ReO3) film by contact with it, thereby forming a rhenium(IV)(ReO2) film.

[0094] In some embodiments, the entire rhenium oxide film deposited by periodic deposition phase 105 can be reduced by contacting the rhenium oxide film with a reducing agent precursor, while in some alternative embodiments of the present disclosure, only a portion of the rhenium oxide film deposited by periodic deposition phase 105 can be reduced by contacting the rhenium oxide film with a reducing agent precursor.

[0095] Once the substrate is brought into contact with the reducing agent precursor, the exemplary rhenium oxide formation process 200 can be advanced by purging the reaction chamber. For example, excess reducing agent precursor and reaction by-products can be removed from the substrate surface by, for example, pumping them in while flowing an inert gas. In some embodiments of the present disclosure, the purging process may include purging the substrate surface for about 0.1 seconds to about 10 seconds, or about 0.5 seconds to about 3 seconds, or even about 1 second to 2 seconds.

[0096] Once the purging of excess reducing agent precursor (and any reaction by-products) from the reaction chamber is complete, the exemplary rhenium oxide formation process 200 continues at a determination gate 240, the determination gate 240 depending on the thickness of the formed rhenium oxide film. For example, if the rhenium oxide film is formed to an insufficient thickness for the desired apparatus application, the periodic deposition phase 205 of the exemplary process 200 may be repeated by returning to the periodic deposition phase 105 and continuing through one or more periodic deposition cycles 205, where a unit deposition cycle of periodic deposition cycle 205 may include periodically depositing a rhenium oxide film to a desired thickness (periodic deposition phase 105), purging the reaction chamber, contacting the substrate with the reducing agent precursor (process block 220), and purging the reaction chamber again. A unit deposition cycle of periodic deposition phase 205 may be repeated one or more times until a rhenium oxide film of a desired thickness and having a desired composition is formed on the substrate. Once the rhenium oxide film is formed to the desired thickness and composition, the exemplary process 200 ends via the process block 250, and the substrate on which the rhenium oxide film is formed can be subjected to further processing for the formation of a device structure.

[0097] Further exemplary rhenium oxide formation processes can be understood by referring to Figure 3, which shows a periodic deposition process 300 for the formation of a rhenium oxide film.

[0098] More specifically, the periodic deposition process 300 can be initiated by a process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 300.

[0099] Once the substrate is heated to a desired deposition temperature in a suitable reaction chamber, the periodic deposition process 300 can be continued using either periodic deposition phase 105 (process 100, Figure 1) or periodic deposition phase 205 (process 200, Figure 2). Since both periodic deposition phase 105 and periodic deposition phase 205 have already been described in detail, the periodic deposition process 300 will be described in a shortened form.

[0100] More specifically, in some embodiments, the periodic deposition phase 105 may be used to deposit rhenium oxide to a desired thickness and composition, and may comprise one or more periodic deposition cycles of the periodic deposition phase 105, each unit deposition cycle comprising contacting the substrate with a rhenium precursor, purging excess rhenium precursor and any reaction byproducts from the reaction chamber, contacting the substrate with an oxygen-containing precursor, and purging excess oxygen precursor and any reaction byproducts from the reaction chamber. In some alternative embodiments, the periodic deposition phase 205 may be used to deposit rhenium oxide to a desired thickness and composition, and may comprise unit cycles of the periodic deposition phase 205, each unit cycle may comprise periodic deposition of a rhenium oxide film to a desired thickness, purging excess precursor and any reaction byproducts from the reaction chamber, contacting the substrate with a reducing agent precursor, and purging excess reducing agent precursor and any reaction byproducts from the reaction chamber.

[0101] As a non-limiting example, periodic deposition phase 105 can be utilized by depositing a rhenium oxide film, such as rhenium trioxide (ReO3), by contacting the substrate with a rhenium oxyfluoride such as ReOF4, and by contacting the substrate with water vapor (H2O).

[0102] As a further non-limiting example, periodic deposition phase 205 can be used to form a rhenium oxide film of a desired thickness, such as rhenium trioxide (ReO3), by contacting rhenium trioxide (ReO3) with a reducing agent precursor to form a rhenium(IV)(ReO2) film of the desired thickness.

[0103] In embodiments of the present disclosure, periodic deposition phases 105 and 205 may be used to deposit a rhenium oxide film to a thickness of less than 1000 angstroms, less than 500 angstroms, less than 100 angstroms, or even less than 10 angstroms. In embodiments of the present disclosure, periodic deposition phases 105 and 205 may be used to deposit a rhenium oxide film to a thickness that can be completely oxidized by subsequently contacting the rhenium oxide film with an additional oxygen-containing precursor, and in some alternative embodiments, periodic deposition phases 105 and 205 may be used to form rhenium oxide to a thickness that can be partially oxidized by subsequently contacting the rhenium oxide film with an additional oxygen-containing precursor.

[0104] Once the rhenium oxide film is formed to the desired thickness and composition, the exemplary process 300 can be carried out by process block 320, which includes contacting the substrate and, in particular, contacting the rhenium oxide film with an additional oxygen-containing precursor.

[0105] In some embodiments of this disclosure, the additional oxygen-containing precursor may include at least one of water (H2O), ozone (O3), formic acid (CH2O2), hydrogen peroxide (H2O2), oxygen molecules (O2), oxygen atoms (O), sulfur trioxide (SO3), or an oxygen-based plasma, the oxygen-based plasma comprising oxygen atoms (O), oxygen ions, oxygen radicals, and excited oxygen species, and can be generated by excitation of an oxygen-containing gas (e.g., by the application of RF power). Note that the term “gas-phase reactant” includes the excited plasma and the excited species comprising the plasma.

[0106] In some embodiments of this disclosure, contacting the substrate with an additional oxygen-containing precursor may include contacting the substrate with the additional oxygen precursor for a period of time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, while the additional oxygen precursor is in contact with the substrate, the flow rate of the additional oxygen precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Furthermore, while the additional oxygen precursor is in contact with the substrate, the flow rate of the additional oxygen precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0107] As a non-limiting example, the periodic deposition phase 105 of exemplary process 300 may be used to deposit a rhenium trioxide (ReO3) film to a thickness of less than approximately 1000 angstroms, less than 500 angstroms, less than 100 angstroms, or even less than 1 angstrom, and the rhenium trioxide (ReO3) film may then be brought into contact with an additional oxygen precursor, such as oxygen, water, oxygen-containing plasma, ozone, acetic acid, or hydrogen peroxide, for a time of less than 10 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature of less than 400°C, less than 300°C, less than 200°C, or even less than 100°C. For example, the additional oxygen-containing precursor may include ozone (O3), which, upon contact with the rhenium trioxide (ReO3), can oxidize the film to form a rhenium(VII)(Re2O7) oxide film.

[0108] As a further non-limiting example, the periodic deposition phase 105 of the exemplary process 300 may be used to deposit a rhenium(IV)(ReO2) oxide film to a thickness of less than approximately 1000 angstroms, less than 500 angstroms, less than 100 angstroms, or even less than 10 angstroms, and the rhenium(IV)(ReO2) oxide film may then be brought into contact with an additional oxygen precursor, such as oxygen, water, oxygen-containing plasma, ozone, acetic acid, or hydrogen peroxide, for a period of less than 10 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature of less than 400°C, less than 300°C, less than 200°C, or even less than 100°C. For example, the additional oxygen-containing precursor may include hydrogen peroxide (H2O2), which, upon contact with the rhenium(IV)(ReO2) oxide film, can oxidize the film to form a rhenium(VII)(Re2O7) oxide film.

[0109] As a further non-limiting example, the periodic deposition phase 205 of the exemplary process 300 may be used to form a rhenium(IV)(ReO2) oxide film to a thickness of less than approximately 1000 angstroms, less than 500 angstroms, less than 100 angstroms, or less than 10 angstroms, and the rhenium(IV)(ReO2) oxide film may then be brought into contact with an additional oxygen precursor, such as oxygen, water, oxygen-containing plasma, ozone, acetic acid, or hydrogen peroxide, for a period of less than 10 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature of less than 400°C, less than 300°C, less than 200°C, or even less than 100°C. For example, the additional oxygen-containing precursor may include an oxygen-based plasma that, upon contact with the rhenium(IV)(ReO2) oxide film, oxidizes the film to form a rhenium(VII)(Re2O7) oxide film.

[0110] Accordingly, in some embodiments of the present disclosure, the rhenium oxide film comprises at least one of a rhenium(IV)(ReO2) oxide film or a rhenium trioxide(ReO3) film, and the method of the present disclosure further comprises forming a rhenium(VII)(Re2O7) oxide film by contacting the rhenium oxide film with an additional oxygen-containing precursor.

[0111] Once the substrate is brought into contact with an additional oxygen precursor, the exemplary rhenium oxide formation process 300 can be advanced by purging the reaction chamber. For example, excess additional oxygen precursor and reaction byproducts (if any) can be removed from the surface of the substrate by, for example, exhausting with an inert gas flow. In some embodiments of the present disclosure, the purging process may include purging the substrate surface for about 1 second to about 100 seconds, or about 0.1 seconds to about 10 seconds, or about 0.5 seconds to about 3 seconds, or even about 1 second to 2 seconds.

[0112] Once the purging of excess additional oxygen precursors (and any reaction byproducts) from the reaction chamber is complete, the exemplary rhenium oxide formation process 300 continues at a determination gate 340, the determination gate 340 depending on the thickness of the formed rhenium oxide film. For example, if the rhenium oxide film is formed to an insufficient thickness for the desired apparatus application, the periodic deposition phase 305 may be repeated by returning to periodic deposition phase 105 or 205 and continuing through the periodic deposition phase 305, where a unit deposition cycle of periodic deposition cycle 305 may include forming a rhenium oxide film of the desired thickness and composition (periodic phase 105 or 205), purging the reaction chamber, contacting the substrate with additional oxygen-containing precursors (process block 320), and purging the reaction chamber again. A unit deposition cycle of periodic deposition phase 305 may be repeated one or more times until a rhenium oxide film of the desired thickness and having the desired composition is formed on the substrate. Once the rhenium oxide film is formed to the desired thickness and composition, the exemplary process 300 ends via the process block 350, and the substrate on which the rhenium oxide film is formed can be subjected to further processing for the formation of a device structure.

[0113] In some embodiments of this disclosure, the rhenium oxide film formed by the exemplary processes disclosed herein may include a dielectric material. For example, the rhenium(VII)(Re2O7) or rhenium(IV)(ReO2) film formed by the methods disclosed herein may include a dielectric material.

[0114] In some embodiments of this disclosure, the rhenium oxide film formed by the exemplary processes disclosed herein may include a conductive rhenium oxide film. In some embodiments, the conductive phase of the rhenium oxide film may include a rhenium(IV)(ReO2) or rhenium trioxide(ReO3) film. In some embodiments, the conductive rhenium oxide film may have the general formula ReO xIt may also contain a suboxide having the formula, where x is less than 2. In some embodiments, the conductive phase of the rhenium oxide film formed by embodiments of the present disclosure may have an immediate electrical resistivity of less than 1000 μΩ-cm, or less than 700 μΩ-cm, or less than 500 μΩ-cm, or less than 250 μΩ-cm, or less than 100 μΩ-cm, or less than 50 μΩ-cm, or less than 25 μΩ-cm, or 10 μΩ-cm, or even less than 5 μΩ-cm. In some embodiments, the conductive phase of the rhenium oxide film formed by embodiments of the present disclosure may have an immediate electrical resistivity between 5 μΩ-cm and 1000 μΩ-cm.

[0115] In some embodiments of this disclosure, the rhenium oxide film formed according to the embodiments of this disclosure can be subjected to one or more further processes to further improve the electrical resistivity of the rhenium oxide film.

[0116] More specifically, Figures 4A–4C show schematic cross-sectional views of semiconductor structures formed using exemplary processes for forming low-resistance conductive rhenium oxide films. In some embodiments, the methods of the present disclosure may include providing a substrate such as the substrate 400 shown in Figure 4A. The substrate 400 may include non-planar or planar (as shown) and may further include one or more materials, as already disclosed with reference to process block 110 in Figure 1.

[0117] The substrate 400 can be placed in a suitable reaction chamber, such as an atomic layer deposition (ALD) reaction chamber, and heated to a desired deposition temperature. Once the substrate is heated to the desired deposition temperature, a rhenium oxide film 402 (Figure 4B) can be deposited on the substrate 400 using one of the exemplary processes 100 (Figure 1), 200 (Figure 2), or 300 (Figure 3). In some embodiments, the rhenium oxide film 402 includes a conductive rhenium oxide film. In some embodiments, the conductive rhenium oxide film 402 may include at least one of rhenium(IV) oxide (ReO2) or rhenium trioxide (ReO3). In some embodiments, the conductive rhenium oxide film has the general formula ReO x It may also contain a suboxide having the formula, where x is less than 2. In some embodiments, the conductive rhenium oxide film may be formed to a thickness of less than 1000 angstroms, or less than 500 angstroms, or less than 250 angstroms, or less than 100 angstroms, or less than 50 angstroms, or even less than 20 angstroms, and may have an electrical resistivity of less than 1000 μΩ-cm, or less than 500 μΩ-cm, or less than 100 μΩ-cm, or less than 50 μΩ-cm, or even less than 20 μΩ-cm.

[0118] In some embodiments of this disclosure, a method for forming a low-electrically-resistive conductive rhenium oxide film may further include forming a capping layer on the surface of the rhenium oxide film. For example, the capping layer 404 can be deposited directly on the surface exposed above the rhenium oxide film 402, thereby forming a semiconductor structure 406, as shown in Figure 4C. In some embodiments, the capping layer 404 may include a conductive layer such as titanium nitride (TiN), tantalum nitride (TaN), tantalum (Ta), tungsten carbide (WC), molybdenum (Mo), or niobium boride (NbB). While not bound by any particular theory or mechanism, it is believed that adding a capping layer on the surface of a rhenium oxide film can prevent, or substantially prevent, the sublimation of the rhenium oxide film.

[0119] Once the capping layer 404 is deposited on the surface of the rhenium oxide film 402, the method of the present disclosure may further include thermal annealing of the rhenium oxide film 402. For example, a semiconductor structure 406 containing the rhenium oxide film 402 may be thermal annealed at a temperature above 50°C, or above 100°C, or above 200°C, or above 300°C, or even above 400°C, or in a temperature range of 50°C to 400°C. In some embodiments, thermal annealing of the rhenium oxide film 402 may further include increasing the grain size of the crystal containing the rhenium oxide film 402. In some embodiments, thermal annealing of the rhenium oxide film 402 may further include forming a substantially single-crystal rhenium oxide film. In some embodiments, thermal annealing of the rhenium oxide film 402 may further include reducing the density of grain boundaries within the rhenium oxide film. In some embodiments, thermal annealing of the rhenium oxide film 402 may further include reducing the electrical resistivity of the rhenium oxide film. For example, a rhenium oxide film after thermal annealing may have an electrical resistivity of less than 1000 μΩ-cm, less than 100 μΩ-cm, or less than 10 μΩ-cm.

[0120] Exemplary periodic deposition process for rhenium sulfide film formation In some embodiments of this disclosure, the periodic deposition process is based on the general formula ReS a Also Re x S y It may be used to form rhenium sulfide, where a, x, and y are 7 or less, for example, rhenium disulfide (ReS2) or dillenium heptasulfide (Re2S7). In some embodiments, the periodic deposition process may include forming a rhenium sulfide film by a surface reaction between a first gas-phase reactant and a second gas-phase reactant. In some embodiments, the periodic deposition process may include forming an intermediate rhenium oxide film, followed by contacting the intermediate rhenium oxide film with a sulfur-containing precursor.

[0121] An exemplary rhenium sulfide formation process can be understood by referring to Figure 5, which shows an exemplary periodic deposition process for the formation of a rhenium sulfide film.

[0122] More specifically, the periodic deposition process 500 can be initiated by a process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 500.

[0123] Once the substrate is heated to a desired deposition temperature in a suitable reaction chamber, the periodic deposition process 500 can be continued by a periodic deposition phase 505 process, which can be initiated via a process block 120. The process block 120 has already been described in detail with reference to Figure 1 (periodic deposition process 100) and is therefore represented in a shortened form with respect to the periodic deposition process 500.

[0124] More specifically, process block 120 may include contacting a substrate with a rhenium precursor. In some embodiments, the rhenium precursor may include rhenium halides such as rhenium chloride, rhenium boride, rhenium fluoride, or rhenium iodide. In certain embodiments, the rhenium precursor may include rhenium oxyhalides such as rhenium oxyhalide or rhenium oxyfluoride. In some embodiments, the rhenium oxyhalide is ReOF 4、 The rhenium precursor may include at least one of ReOF5, ReO2F2, or ReO2Cl3. In some embodiments, the rhenium precursor may include an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor.

[0125] The exemplary rhenium sulfide formation process 500 in Figure 5 may be continued by purging the reaction chamber. For example, excess rhenium precursor and reaction byproducts (if any) can be removed from the substrate surface by, for example, pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purge cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess rhenium precursor and possible reaction byproducts may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0126] A periodic deposition phase 505 of an exemplary rhenium sulfide formation process 500 may be continued by block 530, which includes contacting the substrate with a sulfur-containing precursor ("sulfur precursor"). In some embodiments, the sulfur-containing precursor includes at least one of hydrogen sulfide (H2S), sulfur dioxide (SO2), carbon disulfide (CS2), dimethyl sulfide (C2H6S), methanethiol (CH3SH), or dialkyl disulfide.

[0127] In some embodiments of this disclosure, contacting the substrate with a sulfur-containing precursor may include contacting the substrate with the sulfur precursor for a time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, during contact between the substrate and the sulfur precursor, the flow rate of the sulfur precursor may be less than 2000 sccm, less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the substrate and the sulfur precursor, the flow rate of the sulfur precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0128] The exemplary rhenium sulfide formation process 500 in Figure 5 may be continued by purging the reaction chamber. For example, excess sulfur precursors and reaction byproducts (if any) can be removed from the substrate surface by, for example, pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purge cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess sulfur precursors and possible reaction byproducts may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0129] Once the purging of excess sulfur precursor (and any reaction byproducts) from the reaction chamber is complete, the exemplary rhenium sulfide formation process 500 continues at the determination gate 540, which depends on the thickness of the deposited rhenium sulfide film. For example, if the rhenium sulfide film is deposited to an insufficient thickness for a desired device application, the periodic deposition phase 505 may be repeated by returning to process block 120 and continuing the periodic deposition phase 505. A unit deposition cycle of the periodic deposition phase 505 may include contacting the substrate with a rhenium oxyhalide precursor (process block 120), purging the reaction chamber, contacting the substrate with a sulfur-containing precursor (process block 530), and also purging the reaction chamber. A unit deposition cycle of the periodic deposition phase 505 may be repeated one or more times until a rhenium sulfide film of a desired thickness and having a desired composition is formed on the substrate. Once the rhenium sulfide film is deposited to the desired thickness and composition, the exemplary process 500 ends via the process block 550, and the substrate on which the rhenium sulfide film is formed can be subjected to further processing for the formation of a device structure.

[0130] Naturally, in some embodiments of this disclosure, the order in which the substrate is brought into contact with a first gas-phase reactant (e.g., a rhenium precursor) and a second gas-phase reactant (e.g., a sulfur precursor) can be such that the substrate is first brought into contact with the second gas-phase reactant, followed by contact with the first gas-phase reactant. Furthermore, in some embodiments, the periodic deposition phase 505 of the exemplary process 500 may include bringing the substrate into contact with the first gas-phase reactant one or more times before bringing the substrate into contact with the second gas-phase reactant one or more times. Furthermore, in some embodiments, the periodic deposition phase 505 of the exemplary process 500 may include bringing the substrate into contact with the second gas-phase reactant one or more times before bringing the substrate into contact with the first gas-phase reactant one or more times.

[0131] As a non-limiting example, the reaction chamber may be equipped with an ALD reactor, and the substrate may be heated to a temperature of approximately 100°C to approximately 400°C (process block 110). The substrate may then be subjected to one or more deposition cycles of periodic deposition phase 505, which may include contacting the substrate with ReO2F2 and then contacting the substrate with hydrogen sulfide (H2S) to form a rhenium disulfide (ReS2) film.

[0132] Further exemplary rhenium sulfide formation processes can be understood by referring to Figure 6, which shows a periodic deposition process 600 for forming a rhenium sulfide film.

[0133] More specifically, the periodic deposition process 600 can be initiated by a process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 600.

[0134] Once the substrate is heated to a desired deposition temperature in a suitable reaction chamber, the periodic deposition process 600 can be continued by forming a rhenium oxide film of a desired thickness and composition using either periodic deposition phase 105 (process 100, Figure 1), periodic deposition phase 205 (process 200, Figure 2), or periodic deposition phase 305 (Figure 3, process 300). Periodic deposition phases 105, 205, and 305 have already been described in detail, and therefore, the details of periodic deposition phases 105, 205, and 305 will not be repeated with respect to the periodic deposition process 600.

[0135] In some embodiments of the present disclosure, periodic deposition phases 105, 205, or 305 may be used to form rhenium oxide films, such as rhenium(IV)(ReO2) oxide films, rhenium trioxide(ReO3), or rhenium(VII)(Re2O7) oxide films. In some embodiments, the rhenium oxide films may be formed to a thickness of less than 1000 angstroms, or less than 500 angstroms, or less than 250 angstroms, or less than 100 angstroms, or even less than 10 angstroms.

[0136] In some embodiments of the present disclosure, rhenium oxide may be formed to a thickness such that it can be completely converted into a rhenium sulfide film when subsequently contacted with a sulfur precursor, whereas in some alternative embodiments, rhenium oxide may be formed to a thickness such that it can be partially converted into a rhenium sulfide film when subsequently contacted with a sulfur precursor.

[0137] In some embodiments of the present disclosure, the periodic deposition phase 605 may be continued by a process block 620 which includes contacting the substrate with a sulfur-containing precursor ("sulfur precursor"). In some embodiments, the sulfur-containing precursor may include at least one of hydrogen sulfide (H2S), sulfur dioxide (SO2), carbon disulfide (CS2), dimethyl sulfide (C2H6S), methanethiol (CH3SH), or dialkyl disulfide.

[0138] In some embodiments of this disclosure, contacting a substrate, and in particular a rhenium oxide film, with a sulfur-containing precursor may include contacting the sulfur precursor with the substrate for a time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, during contact between the substrate and the sulfur precursor, the flow rate of the sulfur precursor may be less than 2000 sccm, or less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the sulfur precursor with the substrate, the flow rate of the sulfur precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0139] The exemplary rhenium sulfide formation process 600 in Figure 6 may be continued by purging the reaction chamber. For example, excess sulfur precursors and reaction byproducts (if any) can be removed from the substrate surface by, for example, pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purge cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess sulfur precursors and possible reaction byproducts may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0140] Once the purging of excess additional sulfur precursor (and any reaction byproducts) from the reaction chamber is complete, the exemplary rhenium sulfide formation process 600 continues at a determination gate 640, the determination gate 640 depending on the thickness of the formed rhenium sulfide film. For example, if the rhenium sulfide film is formed to an insufficient thickness for the desired apparatus application, the periodic deposition phase 605 may be repeated by returning to periodic phases 105, 205, or 305 and continuing through the periodic deposition phase 605 to form a rhenium oxide film of the desired thickness and composition, and a unit deposition cycle of periodic deposition cycle 605 may include forming a rhenium oxide film of the desired thickness and composition (periodic phases 105, 205, or 305), purging the reaction chamber, contacting the substrate with the sulfur precursor (process block 640), and purging the reaction chamber again. A unit deposition cycle of periodic deposition phase 605 may be repeated one or more times until a rhenium sulfide film of the desired thickness and having the desired composition is formed on the substrate. Once the rhenium sulfide film is formed to the desired thickness and composition, the exemplary process 600 ends via process block 650, and the substrate on which the rhenium sulfide film is formed can be subjected to further processing for the formation of a device structure.

[0141] As a non-limiting example, periodic deposition phase 105 is utilized in periodic deposition process 600 to deposit a rhenium trioxide film (ReO3) to a thickness of less than approximately 300 angstroms, and the rhenium trioxide (ReO3) film may then be contacted with a sulfur precursor such as hydrogen sulfide (H2S), sulfur monoxide (SO), sulfur dioxide (SO2), carbon disulfide (CS2), dimethyl sulfide (C2H6S), or methanethiol (CH3SH) for a period of time of less than 10 minutes, less than 5 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature in the range of 100°C to 400°C or 150°C to 300°C. For example, the sulfur-containing precursor contacts the rhenium trioxide film (ReO3), thereby converting the rhenium oxide film to rhenium disulfide (ReS2), dillenium heptasulfide (Re2S7), or the general formula ReS aIt may contain hydrogen sulfide (H2S) that forms rhenium sulfide (where a is a non-integer less than 3.5).

[0142] Exemplary periodic deposition process for elemental rhenium film formation In some embodiments of the present disclosure, elemental rhenium films can be formed using a periodic deposition process. In some embodiments, the periodic deposition process may include forming an elemental rhenium film by a surface reaction between a first gas-phase reactant and a second gas-phase reactant. In some embodiments, the periodic deposition process may include forming an intermediate rhenium oxide film, followed by contacting the intermediate rhenium oxide film with a hydrogen-containing precursor to form an elemental rhenium film.

[0143] An exemplary elemental rhenium formation process can be understood by referring to Figure 7, which shows an exemplary periodic deposition process for the formation of an elemental rhenium film.

[0144] More specifically, the periodic deposition process 700 can be initiated by a process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 700.

[0145] Once the substrate is heated to a desired deposition temperature in a suitable reaction chamber, the periodic deposition process 700 can be continued by a periodic deposition phase 705 process, which can be initiated via a process block 120. The process block 120 has already been described in detail with reference to Figure 1 (periodic deposition process 100) and is therefore represented in a shortened form with respect to the periodic deposition process 700.

[0146] More specifically, process block 120 may include contacting a substrate with a rhenium precursor. In some embodiments, the rhenium precursor may include rhenium halides such as rhenium chloride, rhenium boride, rhenium fluoride, or rhenium iodide. In certain embodiments, the rhenium precursor may include rhenium oxyhalides such as rhenium oxyhalide or rhenium oxyfluoride. In some embodiments, the rhenium oxyhalide is ReOF 4、 The rhenium precursor may include at least one of ReOF5, ReO2F2, or ReO2Cl3. In some embodiments, the rhenium precursor may include an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor.

[0147] The exemplary elemental rhenium formation process 700 shown in Figure 7 may be continued by purging the reaction chamber. For example, excess rhenium precursor and reaction byproducts (if any) can be removed from the substrate surface by, for example, pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purge cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess rhenium precursor and possible reaction byproducts may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0148] The periodic deposition phase 705 of the exemplary elemental rhenium formation process 700 may be continued by block 730, which includes contacting the substrate with a hydrogen-containing precursor ("hydrogen precursor"). In some embodiments, the hydrogen-containing precursor comprises at least one of the following: hydrogen sulfide (H2S), hydrogen molecules (H2), hydrogen atoms (H), hydrazine (N2H4), forming gas (H2+N2), ammonia (NH3), ammonia-hydrogen (NH3-H2) mixture, or a hydrogen-based plasma, the hydrogen-based plasma comprising hydrogen atoms (H), hydrogen ions, hydrogen radicals, and excited hydrogen species, and may be generated by excitation of the hydrogen-containing gas (e.g., by applying RF power). Note that the term "gas-phase reactant" includes the excited plasma and the excited species comprising the plasma.

[0149] In some embodiments of this disclosure, contacting a substrate with a hydrogen-containing precursor may include contacting the hydrogen precursor with the substrate for a period of time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, during contact between the substrate and the hydrogen precursor, the flow rate of the hydrogen precursor may be less than 2000 sccm, less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the substrate and the hydrogen precursor, the flow rate of the hydrogen precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0150] The exemplary elemental rhenium formation process 700 shown in Figure 7 may be continued by purging the reaction chamber. For example, excess hydrogen precursors and reaction by-products (if any) can be removed from the substrate surface, for example, by pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purging cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess hydrogen precursors and possible reaction by-products may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0151] Once the purging of excess hydrogen precursor (and any reaction byproducts) from the reaction chamber is complete, the exemplary elemental rhenium formation process 700 continues at a determination gate 740, the determination gate 740 depending on the thickness of the formed elemental rhenium film. For example, if the elemental rhenium film is formed to an insufficient thickness for a desired device application, the periodic deposition phase 705 may be repeated by returning to process block 120 and continuing the periodic deposition phase 705, the unit deposition cycle of the periodic deposition phase 705 may include contacting the substrate with the rhenium precursor (process block 120), purging the reaction chamber, contacting the substrate with the hydrogen-containing precursor (process block 730), and purging the reaction chamber again. The unit deposition cycle of the periodic deposition phase 705 may be repeated one or more times until an elemental rhenium film of the desired thickness is formed on the substrate. Once the elemental rhenium film is deposited to the desired thickness, the exemplary process 700 terminates via process block 750, and the substrate on which the elemental rhenium film has been formed can be subjected to further processing for the formation of a device structure.

[0152] Naturally, in some embodiments of this disclosure, the order in which the substrate is brought into contact with a first gas-phase reactant (e.g., a rhenium precursor) and a second gas-phase reactant (e.g., a hydrogen precursor) can be such that the substrate is first brought into contact with the second gas-phase reactant, followed by contact with the first gas-phase reactant. Furthermore, in some embodiments, the periodic deposition phase 705 of the exemplary process 700 may include bringing the substrate into contact with the first gas-phase reactant one or more times before bringing the substrate into contact with the second gas-phase reactant one or more times. Furthermore, in some embodiments, the periodic deposition phase 705 of the exemplary process 700 may include bringing the substrate into contact with the second gas-phase reactant one or more times before bringing the substrate into contact with the first gas-phase reactant one or more times.

[0153] As a non-limiting example, the reaction chamber may be equipped with an ALD reactor, and the substrate may be heated to a temperature of approximately 150°C to 300°C (process block 110). The substrate may then be subjected to one or more deposition cycles of periodic deposition phase 705, which may include contacting the substrate with ReO2F2 and then contacting the substrate with a hydrogen-based plasma to form an elemental rhenium film.

[0154] Further exemplary elemental rhenium formation processes can be understood by referring to Figure 8, which shows an exemplary periodic deposition process for the formation of an elemental rhenium film.

[0155] More specifically, the periodic deposition process 800 can be initiated by process block 110, which includes supplying the substrate into the reaction chamber and heating the substrate to the deposition temperature. Process block 110 has been described in detail with reference to Figure 1 (periodic deposition process 100), and therefore the details of process block 110 will not be repeated with respect to the periodic deposition process 800.

[0156] Once the substrate is heated to a desired deposition temperature in a suitable reaction chamber, the periodic deposition process 800 can be continued by forming a rhenium oxide film of a desired thickness and composition using either periodic deposition phase 105 (process 100, Figure 1), periodic deposition phase 205 (process 200, Figure 2), or periodic deposition phase 305 (Figure 3, process 300). Periodic deposition phases 105, 205, and 305 have already been described in detail, and therefore, the details of periodic deposition phases 105, 205, and 305 will not be repeated with respect to the periodic deposition process 800.

[0157] In some embodiments of the present disclosure, periodic deposition phases 105, 205, or 305 may be used to form a rhenium oxide film, such as a rhenium(IV)(ReO2) oxide film, a rhenium trioxide(ReO3) oxide film, or a rhenium(VII)(Re2O7) oxide film. In some embodiments, the rhenium oxide film is formed to a thickness of less than 1000 angstroms, or less than 500 angstroms, or less than 100 angstroms, or less than 10 angstroms, or even less than 5 angstroms.

[0158] In some embodiments of the present disclosure, rhenium oxide may be formed to a thickness such that it can subsequently be completely converted into an elemental rhenium film by contacting a sulfur precursor, while in some alternative embodiments, rhenium oxide may be formed to a thickness such that it can subsequently be partially converted into an elemental rhenium film by contacting a hydrogen precursor.

[0159] In some embodiments of the present disclosure, the periodic deposition phase 805 may be continued by a process block 820 which includes contacting the substrate with a hydrogen-containing precursor ("hydrogen precursor"). In some embodiments, the hydrogen-containing precursor may include at least one of hydrogen sulfide (H2S), hydrazine (N2H4), forming gas (H2+N2), ammonia (NH3), ammonia-hydrogen (NH3-H2) mixture, hydrogen molecules (H2), hydrogen atoms (H), or hydrogen-based plasma, the hydrogen-based plasma which includes hydrogen atoms (H), hydrogen ions, hydrogen radicals, and excited hydrogen species, and may be generated by excitation of the hydrogen-containing gas (e.g., by applying RF power).

[0160] In some embodiments of this disclosure, contacting a substrate and, in particular, a rhenium oxide film with a hydrogen-containing precursor may include contacting the hydrogen precursor with the substrate for a time between about 0.01 seconds and about 60 seconds, between about 0.05 seconds and about 10 seconds, or between about 0.1 seconds and about 5.0 seconds. Furthermore, during contact between the substrate and the hydrogen precursor, the flow rate of the hydrogen precursor may be less than 2000 sccm, less than 500 sccm, or even less than 100 sccm. Moreover, during contact between the substrate and the hydrogen precursor, the flow rate of the hydrogen precursor may be in the range of about 1 to 2000 sccm, about 5 to 1000 sccm, or about 10 to about 500 sccm.

[0161] The exemplary elemental rhenium film formation process 800 shown in Figure 8 may be continued by purging the reaction chamber. For example, excess hydrogen precursors and reaction by-products (if any) can be removed from the substrate surface, for example, by pumping in an inert gas. In some embodiments of the present disclosure, the purging process may include a purging cycle in which the substrate surface is purged for a time of less than about 5.0 seconds, or less than about 3.0 seconds, or even less than 2.0 seconds. Excess hydrogen precursors and possible reaction by-products may be removed using a vacuum generated by a pump system in fluid communication with the reaction chamber.

[0162] Once the purging of excess hydrogen precursor (and any reaction byproducts) from the reaction chamber is complete, the exemplary elemental rhenium formation process 800 continues at a determination gate 840, the determination gate 840 depending on the thickness of the formed elemental rhenium film. For example, if the elemental rhenium film is formed to an insufficient thickness for the desired apparatus application, the periodic deposition phase 805 may be repeated by returning to periodic phases 105, 205, or 305 and continuing through the deposition cycle phase 805 to form a rhenium oxide film of the desired thickness and composition, where a unit deposition cycle of periodic deposition cycle 805 may include forming a rhenium oxide film of the desired thickness and composition (periodic phases 105, 205, or 305), purging the reaction chamber, contacting the substrate with the hydrogen precursor (process block 820), and purging the reaction chamber again. A unit deposition cycle of periodic deposition phase 805 may be repeated one or more times until an elemental rhenium film of the desired thickness is formed on the substrate. Once the elemental rhenium film is formed to the desired thickness, the exemplary process 800 ends via process block 850, and the substrate on which the elemental rhenium film is formed can be subjected to further processing for the formation of a device structure.

[0163] As a non-limiting example, periodic deposition phase 105 may be used in periodic deposition process 800 to deposit a rhenium trioxide (ReO3) film to a thickness of less than 200 angstroms, after which the rhenium trioxide (ReO3) film may be brought into contact with a hydrogen precursor such as hydrogen diatomic gas (H2), hydrogen-containing plasma, ammonia (NH3), ammonia-hydrogen mixture (NH3-H2), or foaming gas (H2-N2) for a period of less than 10 minutes, less than 5 minutes, less than 1 minute, or even less than 10 seconds, at a substrate temperature in the temperature range of 80°C to 400°C. For example, the hydrogen-containing precursor may include a hydrogen-based plasma that can come into contact with the rhenium trioxide (ReO3) film and thereby convert the oxide film to form an elemental rhenium film.

[0164] Characteristics of rhenium-containing films formed by periodic deposition processes In some embodiments of this disclosure, the growth rate of rhenium-containing films, such as elemental rhenium films, rhenium oxide films, rhenium boride films, or rhenium sulfide films, may be about 0.005 angstroms / cycle to about 5 angstroms / cycle, or about 0.01 angstroms / cycle to about 2.0 angstroms / cycle. In some embodiments, the growth rate of rhenium-containing films may be about 0.1 angstroms / cycle to about 10 angstroms / cycle. In some embodiments, the growth rate of rhenium-containing films may be greater than about 0.05 angstroms / cycle, greater than about 0.1 angstroms / cycle, greater than about 0.15 angstroms / cycle, greater than about 0.20 angstroms / cycle, greater than about 0.25 angstroms / cycle, or even greater than about 0.3 angstroms / cycle. In some embodiments, the growth rate of the rhenium-containing film is less than about 2.0 angstroms / cycle, or less than about 1.0 angstrom / cycle, or less than about 0.75 angstroms / cycle, or less than about 0.5 angstroms / cycle, or less than 0.2 angstroms / cycle. In some embodiments of the present disclosure, the rhenium-containing film can be deposited at a growth rate of less than about 2.5 angstroms / cycle, or even less than 1 angstrom / cycle.

[0165] Rhenium-containing films deposited by the methods disclosed herein may be continuous films. In some embodiments, rhenium-containing films may be continuous in thicknesses of about 100 angstroms or less, or about 60 angstroms or less, or about 50 angstroms or less, or about 40 angstroms or less, or about 30 angstroms or less, or about 20 angstroms or less, or about 10 angstroms or less, or even about 5 angstroms or less. The continuity referred to herein may be physical continuity or electrical continuity. In some embodiments of this disclosure, the thickness at which a material film may be physically continuous may not be the same as the thickness at which the film is electrically continuous, and vice versa.

[0166] In some embodiments of the present disclosure, the rhenium-containing film formed by the embodiments of the present disclosure may have a thickness of about 20 nanometers to about 100 nanometers, or about 20 nanometers to about 60 nanometers. In some embodiments, the rhenium-containing film deposited by some of the embodiments described herein may have a thickness of more than about 20 nanometers, or more than about 30 nanometers, or more than about 40 nanometers, or more than about 50 nanometers, or more than about 60 nanometers, or more than about 100 nanometers, or more than about 250 nanometers, or more than about 500 nanometers, or more than that. In some embodiments, the rhenium-containing film deposited by some of the embodiments described herein may have a thickness of less than about 50 nanometers, or less than about 30 nanometers, or less than about 20 nanometers, or less than about 15 nanometers, or less than about 10 nanometers, or less than about 5 nanometers, or less than about 3 nanometers, or even less than about 2 nanometers. In some embodiments, the rhenium-containing film may have a thickness of about 0.1 nanometers to 50 nanometers, or 1 nanometer to 30 nanometers, or 4 nanometers to 20 nanometers.

[0167] In some embodiments of the present disclosure, the rhenium-containing film may be formed on a substrate having high aspect ratio features, such as a three-dimensional, non-planar substrate. In some embodiments, the step coverage of the rhenium-containing film may be about 50% or more, or about 80% or more, or about 90% or more, or about 95% or more, or about 98% or more, or about 99% or more, or even higher, on a structure having an aspect ratio (height / width) of 2 or more, or 5 or more, or 10 or more, or 25 or more, or 50 or more, or even 100 or more.

[0168] In some embodiments of this disclosure, the rhenium-containing film may contain pure rhenium, or rhenium and hydrogen, or rhenium, hydrogen and oxygen, or rhenium, hydrogen, carbon and oxygen, or rhenium, sulfur and oxygen. In some embodiments, the rhenium-containing film may further contain impurities, including, but not limited to, halides (e.g., chlorine, fluorine, iodine, or bromine), carbon, hydrogen, and nitrogen.

[0169] Rhenium-containing films formed by embodiments of this disclosure can be used in a variety of technical applications. Non-limiting exemplary rhenium oxide films can be used as electrical interconnects, barrier layers, as part of Schottky diode devices, as part of metal-insulator-semiconductor (MIS) devices, as part of metal-insulator-metal (MIM) devices, as part of gate electrodes for semiconductor devices such as NMOS or PMOS logic devices, and as electrodes for semiconductor device structures such as DRAM devices. In addition, rhenium oxide films, such as rhenium(VII)(Re2O7), may exhibit dielectric properties and can therefore be used in DRAM devices and capacitor structures. Furthermore, rhenium sulfides, such as rhenium disulfide(ReS2), can operate in a manner similar to 2D materials and may find applications in tribology, other low-friction applications, solar cell applications, quantum computing, and ultrafast data processing.

[0170] In non-limiting exemplary embodiments, the rhenium-containing film may include a conductive rhenium oxide film and can be used in a semiconductor device structure that includes a conductive interconnect for electrically connecting one or more semiconductor device structures.

[0171] More specifically, Figure 9 illustrates a semiconductor device structure 900 that may comprise a substrate 902 which may include one or more semiconductor device structures (not shown) formed in or on the surface of the substrate. For example, the substrate 902 may include partially and / or created semiconductor device structures such as transistors and memory elements. The semiconductor device structure 900 may also include a dielectric material 904 formed on the substrate 902, the dielectric material may include a low dielectric constant material, silicon oxide, silicon nitride, silicon oxynitride, or a mixture thereof. The semiconductor device structure 900 may further comprise a barrier material 906 that prevents or substantially prevents the diffusion of a conductive interconnect material 908 into the surrounding dielectric material 904. In some embodiments of the present disclosure, the barrier material 906 may include a rhenium-containing material formed according to embodiments of the present disclosure, such as conductive rhenium oxide. The semiconductor device structure 900 may further comprise a conductive interconnect material 908 which can be used to electrically connect semiconductor device structures formed in and / or on the substrate 902. In some embodiments of the present disclosure, the conductive interconnect material 908 may also include a rhenium-containing film formed by embodiments of the present disclosure. For example, the conductive interconnect material 908 may include conductive rhenium oxide or elemental rhenium formed by the methods disclosed herein. The semiconductor device structure 900 may also include a capping layer 910, such as a conductive capping layer containing, for example, titanium nitride (TiN), tantalum nitride (TaN), or tungsten (W).

[0172] Embodiments of the present disclosure may also include a reaction system configured to form a rhenium-containing film of the present disclosure. More specifically, Figure 10 schematically illustrates a reaction system 1000 comprising a reaction chamber 1002 further comprising a mechanism for holding a substrate (not shown) under predetermined pressure, temperature, and environmental conditions and for selectively exposing the substrate to various gases. A precursor reactant source 1004 may be connected to the reaction chamber 1002 by a conduit or other suitable means 1004A, and may further be connected to a manifold, valve control system, mass flow control system, or mechanism to control a gaseous precursor originating from the precursor reactant source 1004. The precursor (not shown) and reactant (not shown) supplied by the precursor reactant source 1004 may be liquid or solid under room temperature and standard atmospheric pressure conditions. Such a precursor may be vaporized in a vacuum vessel of the reactant source, and the precursor may be maintained above its vaporization temperature in the precursor source chamber. In such embodiments, the vaporized precursor can be transported by a carrier gas (e.g., an inactive gas) and supplied to the reaction chamber 1002 through conduit 1004A. In other embodiments, the precursor can be a gas under standard conditions. In such embodiments, the precursor does not need to be vaporized and does not require a carrier gas. For example, in one embodiment, the precursor can be stored in a gas cylinder.

[0173] As described above, the reaction system 1000 may also include additional precursor reactant sources, such as a precursor reactant source 1006 which can be connected to the reaction chamber by a conduit 1006A. As described above, the reaction system may include an additional precursor reactant source 1008 which can be connected to the reaction chamber by a conduit 1008A. As described, the reaction system may also include a further additional precursor reactant source 1009 which can be connected to the reaction chamber by a conduit 1009A. In some embodiments of the present disclosure, the precursor reactant source 1004 may include a rhenium precursor, the precursor reactant source 1006 may include at least one of an oxygen-containing precursor, a sulfur-containing precursor, a boron-containing precursor, or a hydrogen-containing precursor, the precursor reactant source 1008 may include a reducing agent precursor, and the precursor reactant source 1009 may include an oxidation precursor. Accordingly, in some embodiments of the present disclosure, the exemplary periodic deposition processes 100, 200, 300, 500, 600, 700, and 800 of the present disclosure may be carried out in a single reaction chamber.

[0174] The purge gas source 1010 is also connected to the reaction chamber 1002 via conduit 1010A and selectively supplies various inert gases or noble gases to the reaction chamber 1002 to assist in the removal of precursor gases or waste gases from the reaction chamber. The various inert gases or noble gases that can be supplied may originate from solid, liquid, or stored gaseous forms.

[0175] The reaction system 1000 in Figure 10 may also include a system operation and control mechanism 1012 that provides electronic and mechanical components for selectively operating valves, manifolds, pumps, and other devices included in the reaction system 1000. Such circuits and components operate to introduce purge gas from the precursors, the respective precursor sources 1004, 1006, 1008, 1009, and the purge gas source 1010. The system operation and control mechanism 1012 also controls the timing of the gas pulse sequence, the temperature of the substrate and the reaction chamber, the pressure of the reaction chamber, and various other operations necessary for the proper operation of the reaction system 1000. The operation and control mechanism 1012 may include control software and electrical or air control valves for controlling the flow of precursors, reactants, and purge gas into and out of the reaction chamber 1002. The control system may include software or hardware components, such as modules, including FPGAs or ASICs, that perform specific tasks. The modules may be advantageously configured to reside on an addressable storage medium of the control system and may be configured to perform one or more processes.

[0176] Those skilled in the art in the relevant technical fields will understand that other forms of this reaction system are possible, comprising different numbers and types of precursor reactant sources and purge gas sources. Furthermore, such those skilled in the art will also understand that there are many arrangements of valves, conduits, precursor raw materials, and purge gas sources that can be used to achieve the objective of selectively supplying gas into the reaction chamber 1002. Furthermore, in the schematic diagram of the reaction system, many components are omitted for the sake of simplicity of explanation. Such components may include, for example, various valves, manifolds, purification devices, heaters, vessels, vents, and / or bypasses.

[0177] The exemplary embodiments of this disclosure described above are merely examples of embodiments of the invention as defined by the appended claims and their legal equivalents, and therefore do not limit the scope of the invention by these embodiments. Any equivalent embodiments are intended to fall within the scope of the invention. In fact, various modifications of this disclosure, in addition to those shown and described herein, such as useful alternative combinations of the elements described, may be apparent to those skilled in the art from this description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for forming a rhenium oxide film on a substrate by a periodic deposition process, wherein the method is The process involves contacting the substrate with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and then contacting the substrate with a second gas-phase reactant containing an oxygen-containing precursor to form an intermediate rhenium oxide film. The intermediate rhenium oxide film is made of rhenium(VII) oxide (Re ２ O ７ ) comprising, and the method comprising the rhenium(VII) oxide (Re ２ O ７ ) is brought into contact with a reducing agent precursor, thereby producing rhenium(IV) oxide (ReO ２ ), or rhenium trioxide (ReO ３ A method further comprising forming at least one of the following.

2. wherein the oxygen-containing precursor is water (H ２ O), ozone (O ３ ), hydrogen peroxide (H ２ O ２ ), oxygen molecule (O ２ ), oxygen atom (O), sulfur trioxide (SO ３ ), nitrogen oxide, formic acid (CH ２ O ２ ), or at least one of oxygen-based plasmas, the method according to claim 1.

3. The reducing agent precursor is carbon monoxide (CO), nitric oxide (NO), dione, sulfur dioxide (SO4). ２ The method according to claim 1, comprising at least one of ), oxalic acid anhydride, or an acid.

4. The method according to claim 1, wherein the rhenium oxide film comprises a conductive rhenium oxide film having an electrical resistivity of less than 700 μΩ-cm.

5. The method according to claim 1, further comprising forming a conductive capping layer on the surface of the rhenium oxide film.

6. The method according to claim 5, wherein the conductive capping layer comprises at least one of titanium nitride, rhenium boride, rhenium carbide, rhenium phosphide, rhenium nitride, tantalum nitride, tantalum, tungsten carbide, molybdenum, or niobium boride.

7. The method according to claim 5, further comprising thermal annealing the rhenium oxide film at a temperature exceeding 100°C.

8. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The substrate is brought into contact with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and This includes bringing the substrate into contact with a second gas-phase reactant, The rhenium oxyhalide comprises rhenium oxyfluoride, A method wherein the second gas-phase reactant comprises at least one of an oxygen-containing precursor, a sulfur-containing precursor, or a hydrogen-containing precursor.

9. The aforementioned rhenium oxyfluoride is rhenium oxytetrafluoride (ReOF ４ ), rhenium oxypentafluoride (ReOF ５ ), rhenium dioxydifluoride (ReO ２ F ２ ), rhenium trioxyfluoride (ReO ３ F), rhenium dioxytrifluoride (ReO ２ F ３ ), rhenium oxydifluoride (ReOF ２ ), rhenium oxytrifluoride (ReOF ３ The method according to claim 8, comprising at least one of the following: ), or rhenium oxyfluoride (ReOF).

10. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The substrate is brought into contact with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and This includes bringing the substrate into contact with a second gas-phase reactant, The rhenium oxyhalide comprises rhenium oxychloride, A method wherein the second gas-phase reactant comprises at least one of an oxygen-containing precursor, a sulfur-containing precursor, or a hydrogen-containing precursor.

11. The rhenium oxychloride is rhenium dioxytrichloride (ReO ２ Cl ３ ), rhenium oxytetrachloride (ReOCl ４ ), rhenium oxypentafluoride (ReOCl) ５ ), rhenium trioxychloride (ReO ３ Cl), rhenium dioxydichloride (ReO ２ Cl ２ ), rhenium oxydichloride (ReOCl) ２ ), rhenium oxytrichloride (ReOCl) ３ The method according to claim 10, comprising at least one of the following: ), or rhenium oxychloride (ReOCL).

12. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The substrate is brought into contact with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and This includes bringing the substrate into contact with a second gas-phase reactant, The alkylrhenium oxide precursor is methylrhenium trioxide (CH ３ ReO ３ ) including, A method wherein the second gas-phase reactant comprises at least one of an oxygen-containing precursor, a sulfur-containing precursor, or a hydrogen-containing precursor.

13. The method according to claim 1, wherein the cyclopentadienyl rhenium precursor comprises at least one of cyclopentadienylrhenium hydride or cyclopentadienylrhenium carbonyl.

14. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The substrate is brought into contact with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and This includes bringing the substrate into contact with a second gas-phase reactant, The cyclopentadienyl rhenium precursor comprises at least one of cyclopentadienylrhenium hydride or cyclopentadienylrhenium carbonyl, The rhenium carbonyl halide precursor is ReCl[CO] ５ Includes, A method wherein the second gas-phase reactant comprises at least one of an oxygen-containing precursor, a sulfur-containing precursor, or a hydrogen-containing precursor.

15. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The process involves contacting the substrate with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and then contacting the substrate with a second gas-phase reactant containing a sulfur-containing precursor to form an intermediate rhenium oxide film. The above method involves contacting the intermediate rhenium oxide film with an additional sulfur-containing precursor, thereby producing rhenium disulfide (ReS ２ A method further comprising forming a film.

16. A method for forming a rhenium-containing film on a substrate by a periodic deposition process, wherein the method is The process involves contacting the substrate with a first gas-phase reactant containing a rhenium precursor selected from the group consisting of a rhenium oxyhalide precursor, an alkylrhenium oxide precursor, a cyclopentadienyl rhenium precursor, or a rhenium carbonyl halide precursor, and then contacting the substrate with a second gas-phase reactant containing a hydrogen-containing precursor to form an intermediate rhenium oxide film. The method further comprises forming an elemental rhenium film by contacting the intermediate rhenium oxide film with a hydrogen-containing precursor.

17. The method according to claim 1, wherein the periodic deposition process includes an atomic layer deposition (ALD) process.

18. The method according to claim 1, wherein the periodic deposition process includes a periodic chemical vapor deposition (CCD) process.

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