Method of depositing metal nitride layer on substrate by cyclic deposition process

Abstract

A method of depositing a metal nitride layer using a low temperature cyclic deposition process including a cyclic compound is disclosed. The cyclic deposition process includes repeatedly performing a deposition cycle including introducing a metal precursor into the reaction chamber, introducing a nitrogen reactant into the reaction chamber, and introducing a reducing agent including a cyclic compound into the reaction chamber. A metal nitride layer and a semiconductor structure including the metal nitride layer are also disclosed.

Description

Technical Field

[0001] This disclosure generally relates to the fields of semiconductor processing methods, related structures, and the manufacture of devices and integrated circuits. More specifically, this disclosure generally relates to methods for depositing metal nitride layers on a substrate, metal nitride-containing layers, and structures including metal nitride layers. Background Technology

[0002] Semiconductor device fabrication processes typically employ advanced deposition methods to form metal-containing layers with specific properties. Metal nitrides in Group 4 (titanium, zirconium, hafnium), Group 5 (vanadium, niobium, tantalum), and Group 6 (chromium, molybdenum, and tungsten) metals have potential applications across a range of semiconductor applications. In particular, these materials have been proposed for back-end process (BEOL) barrier and liner applications, where low resistivity is critical. Furthermore, many applications require low-temperature deposition of these materials due to integrated thermal budget constraints.

[0003] Any discussion set forth in this section (including discussions of problems and solutions) is included in this disclosure merely for the purpose of providing background to this disclosure and should not be construed as an admission that any or all of the discussions were known at the time the invention was made or otherwise constituted prior art. Summary of the Invention

[0004] This summary presents a simplified description of the selected concepts, which will be described in further detail below. This summary is not intended to require the identification of key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0005] Various embodiments provided include a method for depositing a metal nitride layer on a substrate disposed in a reaction chamber via a cyclic deposition process comprising one or more repeated deposition cycles, each deposition cycle comprising: (a) first introducing a metal precursor into the reaction chamber; (b) introducing a nitrogen reactant into the reaction chamber; and (c) introducing a reducing agent comprising a cyclic compound into the reaction chamber; wherein step (c) is performed after step (b), or step (c) is performed simultaneously with step (b).

[0006] In some embodiments, the cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes: (a) first contacting the substrate with a metal precursor; after step (a), (b) contacting the substrate with a nitrogen reactant; and after step (b), (c) contacting the substrate with a cyclic compound.

[0007] In some embodiments, the cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes: (a) first contacting the substrate with a metal precursor; and after step (a), (b) and (c) contacting the substrate simultaneously with a nitrogen reactant and a cyclic compound.

[0008] In some embodiments, the cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes a deposition supercycle, each deposition supercycle including: performing one or more first subcycles including: contacting the substrate with a metal precursor; and contacting the substrate with a nitrogen reactant; and performing one or more second subcycles including: contacting the substrate with a cyclic compound.

[0009] In some embodiments, the cyclic compound includes a cyclic diene compound.

[0010] In some embodiments, the cyclodiene compound is selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene.

[0011] In some embodiments, the cyclic compound includes a polycyclic hydrocarbon compound.

[0012] In some embodiments, the polycyclic hydrocarbon compound is selected from 1,2,3,4-tetrahydronaphthalene and 9,10-dihydroanthracene.

[0013] In some embodiments, the metal precursor is selected from titanium precursors, molybdenum precursors, hafnium precursors, and niobium precursors.

[0014] In some embodiments, the cyclic deposition process is carried out at a deposition temperature between 350°C and 500°C.

[0015] The various embodiments provided include a method for thermally depositing a metal nitride layer on a substrate, the method comprising: heating the substrate to a deposition temperature between 350°C and 500°C; and repeating a deposition cycle of an atomic layer deposition process, each deposition cycle comprising: (a) first contacting the substrate with a transition metal precursor; after contacting the substrate with the transition metal precursor, (b) contacting the substrate with a nitrogen reactant; and after contacting the substrate with the nitrogen reactant, (c) contacting the substrate with a reducing agent comprising a cyclodiene compound selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene.

[0016] In some embodiments, the transition metal precursor is selected from titanium halide precursors and molybdenum halide precursors.

[0017] In some embodiments, the molybdenum halide precursor includes a molybdenum halide precursor.

[0018] The various embodiments provided include a method of forming a semiconductor structure, the method comprising: placing a substrate in a reaction chamber, the substrate comprising a metal oxide layer; heating the substrate to a deposition temperature between 350°C and 500°C; and depositing a metal nitride layer on the metal oxide layer by a deposition cycle of repeatedly performing an atomic layer deposition process, each deposition cycle comprising: (a) first contacting the substrate with a metal precursor; after contacting the substrate with the metal precursor, (b) contacting the substrate with a nitrogen reactant; and after contacting the substrate with the nitrogen reactant, (c) contacting the substrate with a reducing agent comprising a cyclodiene compound selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene.

[0019] In some embodiments, the method further includes depositing the metal nitride intermediate layer directly onto the metal oxide layer before depositing the metal nitride layer directly onto the metal nitride intermediate layer.

[0020] In some embodiments, the metal nitride intermediate layer is deposited via a second atomic layer deposition process, which includes sequentially and alternately contacting the substrate with the metal precursor and the nitrogen reactant.

[0021] In some embodiments, the metal nitride layer is a conductive layer, and the metal nitride intermediate layer is an insulating layer.

[0022] In some embodiments, the metal nitride layer has a first stoichiometry, and the metal nitride intermediate layer has a second stoichiometry, wherein the first stoichiometry and the second stoichiometry are different.

[0023] In some embodiments, the metal nitride layer includes a first hafnium nitride layer, and the metal nitride intermediate layer includes a second hafnium nitride layer.

[0024] In some embodiments, the first hafnium nitride layer has an HfN stoichiometry, and the second hafnium nitride layer has an Hf3N4 stoichiometry.

[0025] For the purpose of summarizing the advantages of the present invention and its implementation relative to prior art, certain objects and advantages of the present invention have been described above. It should be understood, of course, that not all of these objects or advantages may be achieved according to any particular embodiment of the present invention. Therefore, for example, those skilled in the art will recognize that the present invention may be implemented or performed in a manner that achieves or optimizes one or more advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0026] All these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, and the invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0027] To facilitate the identification of any particular element or action in the discussion, one or more of the most significant digits in the reference numerals refer to the figure number in which the element was first introduced.

[0028] A more complete understanding of embodiments of this disclosure can be derived by referring to the detailed description and claims when considered in conjunction with the following illustrative drawings.

[0029] Figure 1 A method for depositing a metal nitride layer according to one or more embodiments of the present disclosure is shown.

[0030] Figure 2 A deposition supercycle for depositing metal nitride layers according to one or more embodiments of the present disclosure is illustrated.

[0031] Figure 3 A first sub-cycle is shown in the deposition of a metal nitride layer according to one or more embodiments of the present disclosure.

[0032] Figure 4 A second sub-cycle is shown in the deposition of a metal nitride layer according to one or more embodiments of the present disclosure.

[0033] Figure 5 A substrate on which a metal nitride layer is deposited is shown according to one or more embodiments of the present disclosure.

[0034] Figure 6 The diagram illustrates a structure including a substrate and a metal nitride layer deposited according to one or more embodiments of the present disclosure.

[0035] Figure 7 A method for forming a structure including a metal nitride intermediate layer and a metal nitride layer according to one or more embodiments of the present disclosure is shown.

[0036] Figure 8 A structure including a substrate and a metal oxide layer according to one or more embodiments of the present disclosure is shown.

[0037] Figure 9 A structure comprising a substrate, a metal oxide layer, and a metal nitride intermediate layer according to one or more embodiments of the present disclosure is shown.

[0038] Figure 10 A structure comprising a substrate, a metal oxide layer, a metal nitride intermediate layer, and a metal nitride layer according to one or more embodiments of the present disclosure is shown.

[0039] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the embodiments illustrated in this disclosure. Detailed Implementation

[0040] The following description of exemplary embodiments of the methods and compositions is merely illustrative and intended for purposes of explanation only. The following description is not intended to limit the scope of this disclosure or the claims. Furthermore, the description of multiple embodiments having indicated features or steps is not intended to exclude other embodiments having additional features or steps, or other embodiments including different combinations of said features or steps.

[0041] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films can be formed using methods according to embodiments of the invention. A substrate may comprise a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or III-V semiconductor materials), and may comprise one or more layers overlying or underlying the bulk material. A substrate may include various topologies, such as gaps, including recesses, lines, trenches, or spaces between protrusions (e.g., fins) formed within or on at least a portion of the layers of the substrate. For example, a substrate may comprise a bulk semiconductor material and an insulating or dielectric material layer covering at least a portion of the bulk semiconductor material. Furthermore, the term "substrate" can refer to any one or more underlying materials that can be used or on which devices, circuits, or films can be formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous. A "substrate" can be any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. The substrate can be made of materials such as silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. The continuous substrate can extend beyond the boundary of the processing chamber where the deposition process occurs, and the continuous substrate can move through the processing chamber such that the process continues until the end of the substrate is reached. The continuous substrate can be supplied from a continuous substrate feed system, allowing the continuous substrate to be manufactured and output in any suitable form. Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, meshes, flexible materials, bundles of continuous filaments or fibers (i.e., ceramic fibers or polymer fibers). The continuous substrate may also include a carrier or sheet on which a non-continuous substrate is mounted.

[0042] As used herein, the term "layer" can refer to any continuous or discontinuous structure and material. For example, a layer can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers, partially or entirely atomic layers, or atomic and / or molecular clusters. A layer can include a material or a layer with pinholes, which can be at least partially continuous.

[0043] As used herein, the terms "precursor" and "reactant" can refer to a molecule (compound or molecule containing a single element) that participates in a chemical reaction to produce another compound. A precursor typically contains a portion that is at least partially bound to the compound or element produced by the chemical reaction in question. The resulting compound or element can then be deposited on a substrate. A reactant can be an element or compound that is not significantly bound to the resulting compound or element. In some cases, the term reactant may be used interchangeably with the term precursor.

[0044] As used herein, the term “cyclic deposition process” or “cyclic deposition process” can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclic CVD components.

[0045] As used herein, the term "atomic layer deposition" can refer to a vapor phase deposition process in which deposition cycles, typically multiple consecutive deposition cycles, are performed in a processing chamber. The term atomic layer deposition, as used herein, is also intended to include processes specified by related terms such as chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed using alternating pulses of precursor / reactive gases and purge gases (e.g., inert carrier gases).

[0046] Typically, for an ALD process, during each deposition cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other materials) and forms a monolayer or submonolayer of material that does not readily react with additional precursors (i.e., a self-limiting reaction). Subsequently, in some cases, a reactant (e.g., another precursor or reactive gas) may be introduced into the processing chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant may be able to further react with the precursor. During one or more deposition cycles, such as during each step of each cycle, a purging step may be used to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction byproducts from the reaction chamber.

[0047] In this disclosure, any two numbers of a variable may constitute a working range of the variable, and any range indicated may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and include equivalents, and in some embodiments may refer to an average, median, representative value, multi-value, etc. Furthermore, in this disclosure, the terms “comprising,” “consisting of,” and “having” may, in some embodiments, independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of.” The meaning of any definition in this disclosure does not necessarily exclude the common and conventional meaning in some embodiments. In some cases, percentages indicated herein may be relative or absolute percentages.

[0048] Numerous example materials are given throughout the embodiments of this disclosure. It should be noted that the chemical formulas given for each example material should not be interpreted as limiting, and the non-limiting example materials given should not be limited by the given example stoichiometry.

[0049] In this specification, it will be understood that the terms "on" or "above" can be used to describe relative positional relationships. Another element, film, or layer may be directly on the mentioned layer, or another layer (intermediate layer) or element may be inserted therebetween, or a layer may be disposed on the mentioned layer but not completely cover the surface of the mentioned layer. Therefore, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it should be understood that the terms "below," "under," or "beneath" will be interpreted as relative concepts.

[0050] Various embodiments of this disclosure relate to methods for depositing metal nitride layers on a substrate, layers including metal nitrides, and structures including metal nitride layers. Various metal nitride layers can be used in the manufacture of semiconductor devices and integrated circuits. For example, metal nitride layers can be used as work function metals, gate stack liners, cover materials, etc.

[0051] Metal precursors used for depositing metal nitride layers often have oxidation states higher than the stoichiometry of the desired metal nitride layer. Therefore, reduction of the metal element (i.e., the metal center) of the metal precursor can be employed during the deposition process. Typically, nitrogen reactants can be used as the nitrogen source / reducing agent during metal nitride deposition. However, nitrogen reactants alone may be insufficiently reactive at the desired deposition temperature. Therefore, at lower deposition temperatures (e.g., below 500°C), the reduction of the metal component supplied by the metal precursor may be incomplete. Incomplete reduction of the metal component in the metal nitride layer can adversely affect the properties of the deposited metal nitride layer. For example, incomplete reduction may result in a metal nitride layer with high resistivity and a higher concentration of undesirable impurities. This adverse effect can be problematic for certain applications / integration schemes employing low thermal budgets.

[0052] According to various embodiments of this disclosure, additional co-reactants are employed during the cyclic deposition process for depositing metal nitride layers. These additional co-reactants can catalyze the reduction of metal centers, which in turn can improve the properties of the metal nitride layers deposited by the methods disclosed herein. Various examples include methods for depositing metal nitride layers at reduced deposition temperatures, thereby reducing the thermal budget of the deposition process used in the fabrication of devices and integrated circuits including such layers. Furthermore, various examples include methods for depositing metal nitride layers at reduced deposition temperatures without significantly adversely affecting the resistivity and / or impurity concentration of the deposited metal nitride layer.

[0053] Now turn to the attached diagram. Figure 1 An exemplary method 100 for depositing a metal nitride layer is shown. In short, method 100 may include placing a substrate in a reaction chamber and heating the substrate to a deposition temperature (step 102), and then depositing a metal nitride layer on the substrate by employing a cyclic deposition process 104.

[0054] According to an example of the invention, a substrate on which a metal nitride layer is deposited may include one or more partially fabricated device structures, such as logic elements and / or memory elements. In some embodiments, the substrate may include a dielectric material, such as a high-k dielectric layer disposed on the surface of the substrate, as further described below. The high-k dielectric layer may include a material with a dielectric constant greater than that of silicon dioxide, such as, for example, hafnium oxide, hafnium zirconium oxide, etc.

[0055] According to examples of this disclosure, the reaction chamber in which the substrate is placed for deposition can be or includes a reaction chamber configured for performing a cyclic deposition process of a semiconductor deposition apparatus (such as an atomic layer deposition apparatus). The reaction chamber can be a standalone reaction chamber or part of a cluster tool. The reaction chamber can be part of a batch processing tool. In some embodiments, a flow-type reaction chamber can be utilized. In some embodiments, a spray-head type reaction chamber can be utilized. In some embodiments, a spatially partitioned reaction chamber can be utilized. In some embodiments, a single-wafer reaction chamber capable of high-volume manufacturing can be utilized. In other embodiments, a batch reaction chamber comprising multiple substrates can be utilized. For embodiments in which a batch reaction chamber is used, the number of substrates can range from 10 to 200, or 50 to 150, or even 100 to 130. In various embodiments, the substrates are placed in a reaction chamber configured as a thermal reactor—i.e., without plasma excitation equipment. Alternatively, the reaction chamber can include direct and / or remote plasma equipment.

[0056] According to examples of this disclosure, a substrate disposed in a reaction chamber can be heated to a desired deposition temperature (i.e., the temperature of the substrate during the deposition of a metal nitride layer). In various embodiments, the deposition temperature can be below 600°C, below 450°C, below 400°C, below 350°C, below 300°C, below 250°C, or below 200°C. In various embodiments, the deposition temperature can be above room temperature, between 700°C and 300°C, between 325°C and 500°C, between 350°C and 500°C, or between 350°C and 450°C.

[0057] According to examples of this disclosure, in addition to controlling the deposition temperature, the pressure in the reaction chamber can also be adjusted to enable the deposition of a metal nitride layer with desired layer properties. In such examples, the pressure in the reaction chamber can be less than 760 Torr, between 0.1 Torr and 10 Torr, between 0.5 Torr and 5 Torr, or between 1 Torr and 4 Torr.

[0058] Based on the examples in this disclosure, adopting Figure 1 The method 100 shown deposits a metal nitride layer on a substrate by performing one or more deposition cycles of a cyclic deposition process 104. In such an example, each deposition cycle of the cyclic deposition process 104 may include the following steps: introducing a metal precursor into a reaction chamber (step 106) (also referred to herein as step a), introducing a nitrogen reactant into a reaction chamber (step 108) (also referred to herein as step b), and introducing a reducing agent comprising a cyclic compound into a reaction chamber (step 110) (also referred to herein as step c).

[0059] In some embodiments, steps 106, 108, and 110 can be started and / or terminated in any order. In some embodiments, steps 106, 108, and 110 can be performed simultaneously, or there can be at least some time overlap between the steps of the cyclic deposition process 104. In some embodiments, the cyclic deposition process 104 may include repeating each of steps 106, 108, and 110 once or more (e.g., 1-10 times or 1-5 times) before proceeding to subsequent steps. Furthermore, the cyclic deposition process 104 may include one or more additional steps (…). Figure 1 (Not shown in the diagram). For example, one or more additional steps may be performed during each deposition cycle of the cyclic deposition process 104, or alternatively, one or more additional steps may be performed during selected cycles of the cyclic deposition process 104. A purging step (to remove excess precursors / reactants and any reaction byproducts from the reaction chamber) may be performed after one or more of steps 106, 108, and 110 have been performed and / or before and / or upon completion of each deposition cycle (as shown in the cyclic loop 112).

[0060] In some embodiments, the steps (i.e., steps a, b, and c) of each or one deposition cycle of the cyclic deposition process 104 may be performed in a specific order. It should be noted that the order described below may additionally include a purge cycle at the completion of each process step.

[0061] In some embodiments, each or one of the deposition cycles may include the following sequential steps: first, introducing a metal precursor into the reaction chamber (step 106), then introducing a nitrogen reactant into the reaction chamber (step 108), and finally introducing a reducing agent containing a cyclic compound into the reaction chamber (step 110). This deposition cycle sequence may be represented by the notation a(b|c), where parentheses indicate that steps b and c are performed after step a, and "|" represents the logical operation "OR", indicating that either step b or step c may follow step a.

[0062] In some embodiments, each or one of the deposition cycles may include the following sequential steps: first, introducing a metal precursor into the reaction chamber (step 106), then introducing a nitrogen reactant into the reaction chamber (step 108), followed by introducing a reducing agent containing a cyclic compound into the reaction chamber (step 110). This deposition cycle sequence may be denoted by the name abc. In such embodiments, the reducing agent containing the cyclic compound is introduced into the reaction chamber after the nitrogen reactant is introduced (step 108). In other words, step 110 may be performed after step 108. In some examples, the nitrogen reactant introduced into the reaction chamber forms a nitrided surface on the substrate. In such examples, the nitrided surface is formed and subsequently contacted with the cyclic compound, for example, by introducing the cyclic compound into the reaction chamber after the nitrogen reactant. In such examples, the cyclic compound may interact (e.g., react) with the previously formed nitrided surface on the substrate.

[0063] In some embodiments, each or one of the deposition cycles may include the following sequential steps: first, introducing a metal precursor into the reaction chamber (step 106), followed by the simultaneous introduction of a nitrogen reactant (step 108) and a reducing agent comprising a cyclic compound (step 110). In other words, steps 108 and 110 may be performed simultaneously after the metal precursor is first introduced in step 106. Such a deposition cycle sequence may be represented by the notation A(b∧c), where parentheses indicate that steps b and c are performed after step A has been performed, and “∧” represents the logical AND operation, indicating that steps b and c are performed simultaneously. As used herein, the term “simultaneously” may refer to the co-flow of the reducing agent and nitrogen reactant into the reaction chamber, wherein there is at least a time overlap between the introduction of the reducing agent and nitrogen reactant into the reaction chamber. Additionally, as used herein, the term “simultaneously” does not require that steps 108 and 110 be started and terminated simultaneously.

[0064] In some embodiments, the cyclic deposition process 104 includes an atomic layer deposition process, and each deposition cycle includes steps 106, 108, and 110 performed in the following order: first, contacting the substrate with a metal precursor (step 106); after step 106, contacting the substrate with a nitrogen reactant (step 108); and after step 108, contacting the substrate with a cyclic compound (step 110).

[0065] In some embodiments, the cyclic deposition process 104 includes an atomic layer deposition process, and each deposition cycle includes steps 106, 108, and 110 performed in the following order: first, contacting the substrate with a metal precursor (step 106), and after step 106, contacting the substrate simultaneously with a nitrogen reactant (step 108) and a reducing agent containing a cyclic compound (step 110).

[0066] In some embodiments, the metal nitride layer is deposited via a cyclic deposition process including atomic layer deposition, and each deposition cycle includes a deposition supercycle. In such embodiments, each deposition supercycle may include two or more sub-cycles, each of which may be performed once or more to deposit a metal nitride layer on the substrate.

[0067] Figure 2 A cyclic deposition process 204 is illustrated, which includes a deposition supercycle 206 for depositing a metal nitride layer on a substrate. In such an example, each deposition supercycle 206 may be repeated once or multiple times, as shown in supercycle loop 208, and may include a first sub-cycle 210 and a second sub-cycle 212.

[0068] In various embodiments, each first sub-loop 210 (e.g.) Figure 3 The process (as shown) may include contacting the substrate with a metal precursor (sub-step 306) and contacting the substrate with a nitrogen reactant (sub-step 308). The first sub-cycle 210 may be repeated once or multiple times as needed within each deposition supercycle 206, as shown in the first sub-cycle loop 312. In some embodiments, each first sub-cycle 210 may include first contacting the substrate with a metal precursor (sub-step 306), followed by contacting the substrate with a nitrogen reactant (sub-step 308).

[0069] In various embodiments, each second sub-loop 212 (e.g.) Figure 4 (As shown) may include contacting the substrate with a reducing agent containing a cyclic compound (sub-step 410). The second sub-cycle 212 may be repeated once or multiple times as needed within each deposition supercycle 206.

[0070] According to examples of this disclosure, the reaction chamber may be purged concurrently with the execution of each sub-cycle 210 and 212, for example, after each pulse of the precursor / reactant and / or upon completion of sub-cycles 210 and 212, and / or after completion of deposition supercycle 206. In some embodiments, sub-cycles 210 and 212 may be repeated as shown in supercycle loop 208. For example, deposition supercycle 206 may be performed 1 or more times, 2 or more times, 3 or more times, 5 or more times, 10 or more times, 25 or more times, or between 1 and 25 times.

[0071] According to examples of this disclosure, the first sub-loop 210 and the second sub-loop 212 can be started and / or terminated in any order or in a specific order. In some embodiments, the deposition superloop 206 may include executing the first sub-loop 210 one or more times before executing the second sub-loop 212 one or more times.

[0072] In various embodiments, each deposition supercycle 206 may include multiple repetitions of a first subcycle 210 and a second subcycle 212 before proceeding to subsequent subcycles of deposition supercycle 206. In some embodiments, each deposition supercycle 206 may also include one or more additional steps and / or subcycles that may be performed during each deposition supercycle 206 or during a selected deposition supercycle 206 of 204.

[0073] In some embodiments, the properties of the metal nitride layer deposited using the cyclic deposition process 204 can be adjusted by controlling the ratio (i.e., the subcycle ratio) of the number of times the first subcycle 210 is executed relative to the number of times the second subcycle 212 is executed within each supercycle loop 208. In some examples, the subcycle ratio is selected to obtain the desired composition of the deposited metal nitride layer. For example, the subcycle ratio can be selected to deposit a metal-rich metal nitride layer or a nitrogen-rich metal nitride layer.

[0074] The cyclic deposition processes of this disclosure (e.g., 104 and 204) include introducing a metal precursor into the reaction chamber, for example during step 106 of cyclic deposition process 104 and during sub-step 306 of cyclic deposition process 204. In various embodiments, the metal precursor may comprise a transition metal precursor.

[0075] In various embodiments, the metal precursor includes a metal element having a first oxidation state (i.e., a metal center), and the metal nitride layer deposited by a cyclic deposition process (e.g., 104 and 204) includes a metal element having a second oxidation state, wherein the first oxidation state and the second oxidation state are different from each other.

[0076] In some embodiments, the metal precursor comprises a metal selected from transition metals. In such embodiments, the metal precursor may comprise a transition metal selected from Group 4 of the periodic table, including, for example, titanium, zirconium, and hafnium. In some embodiments, the metal precursor may comprise a transition metal selected from Group 5 of the periodic table, including, for example, vanadium, niobium, and tantalum. In some embodiments, the metal precursor may comprise a transition metal selected from Group 6 of the periodic table, including, for example, chromium, molybdenum, and tungsten.

[0077] In some embodiments, the metal precursor comprises a metal halide precursor. In some embodiments, the metal precursor comprises a metal halide oxide precursor. In some embodiments, the metal precursor comprises an organometallic precursor. In some embodiments, the metal precursor comprises a halide-free metal precursor.

[0078] In some embodiments, the metal precursor is selected from one or more of titanium precursors, molybdenum precursors, hafnium precursors, and niobium precursors. In some embodiments, the metal precursor is selected from one or more of titanium halide precursors, molybdenum halide precursors, hafnium halide precursors, and niobium halide precursors. In some embodiments, the metal precursor is selected from one or more of organometallic titanium precursors, organometallic molybdenum precursors, organometallic hafnium halide precursors, and organometallic niobium halide precursors.

[0079] In some embodiments, the metal precursor includes a molybdenum precursor comprising molybdenum metal. In some embodiments, the molybdenum precursor includes molybdenum halides, including but not limited to MoCl5 and MoCl6. In some examples, the molybdenum precursor includes molybdenum halide, comprising (but not limited to) MoOCl3, MoOCl4, and MoO2Cl2. In some examples, the molybdenum precursor includes organometallic molybdenum precursors, comprising (but not limited to) Mo(CO)6, Mo(tBuN)2(NMe2)2, Mo(NBu)2(StBu)2, (Me2N)4Mo, and (iPrCp)2MoH2.

[0080] In some embodiments, the metal precursor includes a titanium precursor comprising titanium metal. In some embodiments, the titanium precursor includes titanium halides, including but not limited to TiCl4, TiF4, and TiI4. In some embodiments, the titanium precursor includes titanium organometallic precursors, including but not limited to Ti(NEt2)4, Ti(NEtMe)4, Ti(NMe2)4, and TiCp2(… i PrN)2C(NH i Pr)), Ti(Cp)CH3, Ti(CpMe)(O i Pr)3, Ti(CpMe5)(OMe)3, Ti(NEt2)4, Ti(NMe2)3(CpMe) and Ti(NMe2)3(CpN).

[0081] In some embodiments, the metal precursor includes a hafnium precursor comprising hafnium metal. In some examples, the hafnium precursor includes hafnium halides, including but not limited to HfCl4, HfI4, and HfBr4. In some examples, the hafnium precursor includes organometallic hafnium precursors, including but not limited to Hf(NEtMe)4, Hf(NMe2)4, Hf(NEt2)4, HfCp(NMe2)3, and (MeCp)2Hf(CH)3(OCH3).

[0082] In some embodiments, the metal precursor includes a niobium precursor comprising niobium metal. In some examples, the niobium precursor includes niobium halides, including but not limited to NbCl5 and NbF5. In some examples, the niobium precursor includes organometallic niobium precursors, including but not limited to Nb(N...t Bu)(NEt2)3、Nb(N t Bu)(NEt2)2(Cp), Nb(N t Bu)(NEtMe)3, Nb(OEt)5 and Nb(OEt)5.

[0083] The cyclic deposition processes of this disclosure (e.g., 104 and 204) include introducing a nitrogen reactant into a reaction chamber, for example during step 108 of cyclic deposition process 104 and during sub-step 308 of cyclic deposition process 204. In various embodiments, the nitrogen reactant comprises a nitriding agent.

[0084] In some embodiments, the nitrogen reactant is selected from ammonia (NH3), hydrazine (N2H4), other nitrogen and hydrogen-containing gases (e.g., mixtures of nitrogen and hydrogen). In some examples, the nitrogen reactant may include nitrogen and hydrogen or consist thereof. In some examples, the nitrogen reactant does not include diatomic nitrogen. In some examples, the nitrogen reactant includes a substituted hydrazine compound. In such examples, the substituted hydrazine compound may include a mixture selected from C4H9N2H3, CH3NHNH2, C2H8N2, and C4H 12 Alkyl-hydrazine of N2. In some examples, the substituted hydrazine compound may include one or more of 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-methyl-N-phenylhydrazine, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-methyl-1-(m-tolyl)hydrazine, and 1-ethyl-1-(p-tolyl)hydrazine. In some embodiments, the nitrogen reactant comprises one or more of ammonia, hydrazine, or amine. In some embodiments, the nitrogen reactant comprises or is substantially composed of ammonia (NH3).

[0085] The cyclic deposition processes of this disclosure (e.g., 104 and 204) include introducing a reducing agent comprising a cyclic compound into a reaction chamber, for example during step 110 of cyclic deposition method 104 and during sub-step 410 of cyclic deposition method 204. In various embodiments, the cyclic compound (or cyclic compound) comprises a cyclic hydrocarbon.

[0086] In various embodiments, the cyclic compound comprises carbon, hydrogen, and at least two unsaturated carbon-carbon bonds. In some embodiments, the cyclic compound comprises a cyclic hydrocarbon having at least two unsaturated carbon-carbon bonds. In some embodiments, the cyclic compound comprises a 6-membered ring comprising carbon, hydrogen, and at least two double bonds between the carbon atoms. In some embodiments, the cyclic compound comprises a 6-membered ring comprising carbon, hydrogen, and one or more additional elements, such as nitrogen.

[0087] According to examples of this disclosure, cyclic compounds may include cyclic diene compounds. In some embodiments, cyclic compounds include cyclohexadiene compounds. In some embodiments, cyclic compounds include cyclohexadiene compounds selected from 1,4-cyclohexadiene and 1,3-cyclohexadiene.

[0088] In some embodiments, the cyclic compound comprises a cyclic diene compound containing one or more substituents. For example, the substituents may be selected from alkyl, amino, dimethylamino, and alkoxy groups. In some embodiments, the cyclic compound comprises a cyclic diene compound containing one or more alkyl substituents. In some embodiments, the cyclic compound comprises a cyclic diene. In some examples, the cyclic compound comprises 1-methyl-1,4-cyclohexadiene.

[0089] In various embodiments, the cyclic compound includes one or more of 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene. In some embodiments, the cyclic compound is 1,4-cyclohexadiene. In some embodiments, the cyclic compound is 1,3-cyclohexadiene. In some embodiments, the cyclic compound is 1-methyl-1,4-cyclohexadiene.

[0090] According to examples of this disclosure, cyclic compounds may include polycyclic hydrocarbon compounds. In some embodiments, the polycyclic hydrocarbon compound includes benzene compounds. In some embodiments, the polycyclic hydrocarbon compound includes tetrahydronaphthalene. In some embodiments, the polycyclic hydrocarbon compound includes anthracene. In some embodiments, the polycyclic hydrocarbon compound is selected from 1,2,3,4-tetrahydronaphthalene and 9,10-dihydroanthracene.

[0091] In various embodiments, the cyclic compound is free of silicon (Si). In various embodiments, the cyclic compound is free of alkylsilyl substituents.

[0092] Various embodiments include methods for forming structures comprising one or more metal nitride layers. In such embodiments, the metal nitride layers are deposited by methods previously described above, such as through cyclic deposition processes 104 and 204.

[0093] Based on the examples in this disclosure, Figure 5 The substrate 502, as described in the detailed description above, is shown, and Figure 6 A structure 600 including a substrate 502 is shown, wherein a metal nitride layer 602 is disposed on the surface of the substrate and deposited by the method described above.

[0094] In some embodiments, the metal nitride layer 602 comprises a transition metal nitride layer. In some examples, the metal nitride layer 602 comprises or is substantially composed of a molybdenum nitride layer. In some examples, the metal nitride layer 602 comprises or is substantially composed of a titanium nitride layer. In some examples, the metal nitride layer 602 comprises or is substantially composed of a hafnium nitride layer. In some examples, the metal nitride layer 602 comprises or is substantially composed of a niobium nitride layer.

[0095] In some embodiments, the metal nitride layer 602 has an average layer thickness of less than 10 nanometers (nm), less than 8 nm, less than 6 nm, less than 5 nm, less than 4 nm, less than 3 nm, less than 2 nm, less than 1 nm, or between 1 nm and 10 nm. In some embodiments, the metal nitride layer 602 has an average thickness non-uniformity (NU%) of less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, less than 1%, or between 1% and 10%.

[0096] In some embodiments, the metal nitride layer 602 has a resistivity (μΩ·cm) of less than 3000 μΩ·cm, less than 2000 μΩ·cm, less than 1000 μΩ·cm, less than 750 μΩ·cm, or less than 500 μΩ·cm. In some embodiments, the metal nitride layer 602 has an average layer thickness of less than 10 nanometers (nm), less than 8 nm, less than 6 nm, less than 5 nm, less than 4 nm, less than 3 nm, less than 2 nm, less than 1 nm, or between 1 nm and 10 nm, and a resistivity of less than 1000 μΩ·cm, less than 750 μΩ·cm, less than 500 μΩ·cm, or between 500 μΩ·cm and 1000 μΩ·cm.

[0097] According to examples of this disclosure, substrate 502 may further include a surface metal oxide layer (not shown) having an initial average layer thickness. In some embodiments, metal nitride layer 602 may be directly deposited on the surface metal oxide layer using the described cyclic deposition methods (e.g., cyclic deposition processes 104 and 204). In some embodiments, directly depositing metal nitride layer 602 on the surface metal oxide layer does not remove or significantly remove the thickness of the surface metal oxide layer.

[0098] Various embodiments include methods of forming a structure comprising a metal nitride layer and a metal nitride intermediate layer. In such embodiments, the introduction of a cyclic compound into the reaction chamber can be controlled to tailor the stoichiometry of the metal nitride layer deposited on the substrate to a desired stoichiometry. For example, in some embodiments, it may be advantageous to first deposit a first metal nitride layer (referred herein to as a metal nitride intermediate layer) comprising a first stoichiometry on the substrate, followed by depositing a second metal nitride layer comprising a second stoichiometry, different from the first stoichiometry, on the metal nitride intermediate layer. In some examples, the initial metal nitride intermediate layer may comprise a first stoichiometry that is less susceptible to oxidation than a subsequent metal nitride layer comprising a second stoichiometry deposited or directly deposited on the metal nitride intermediate layer. In such examples, the metal nitride intermediate layer may form an interface layer (or capping layer) between the underlying material and the metal nitride layer disposed on the metal nitride intermediate layer. As a non-limiting example, the underlying material may include a metal oxide layer, and the metal nitride intermediate layer may form an interface layer between the metal oxide layer and subsequent metal nitride layers formed on the metal nitride intermediate layer.

[0099] Based on the examples in this disclosure, Figure 7 A method 700 for forming a structure is shown. In short, method 700 includes placing a substrate in a reaction chamber, the substrate comprising a metal oxide layer (step 702), heating the substrate to a deposition temperature (step 704), depositing a metal nitride intermediate layer on the metal oxide layer by a cyclic deposition process (step 706), and depositing a metal nitride layer on the metal nitride intermediate layer by a cyclic deposition process (step 708).

[0100] According to examples of this disclosure, the substrate may include one or more of those previously described above. For example, Figure 8 This diagram shows a substrate 802 (as shown in the previous reference). Figure 5 The substrate 800 is similar to or the same as the substrate described in the original text (substrate 502). Furthermore, the structure 800 includes a metal oxide layer 804 formed on the substrate 802. Figure 8 As shown, a metal oxide layer 804 is disposed on a substrate 802. In some embodiments, the metal oxide layer 804 includes a dielectric layer. In some embodiments, the metal oxide layer 804 includes a high dielectric constant (high k) layer.

[0101] In some embodiments, the metal oxide layer 804 may include a hafnium-containing metal oxide layer. In some examples, the hafnium-containing metal oxide layer may include a hafnium high-k layer. In some examples, the hafnium-containing metal oxide layer may include a ternary hafnium high-k layer. In some examples, the metal oxide layer may include hafnium oxide (HfO2), doped HfO2, hafnium zirconium oxide (HfZrO), doped HfZrO, etc.

[0102] In some embodiments, the metal oxide layer 804 may include a high-k metal oxide layer, such as titanium oxide, zirconium oxide, aluminum oxide, barium strontium titanate, erbium oxide, hafnium silicate, lanthanum oxide, niobium oxide, lead zirconium titanate, strontium titanate, tantalum oxide, titanium oxide, zirconium oxide, or other high-k or ultra-high-k metal oxides (e.g., having a k value greater than about 40).

[0103] According to an example of this disclosure, method 700 includes placing a substrate in a reaction chamber (step 702) and heating the substrate to a deposition temperature (step 704). In such an example, the reaction chamber may include any one or more of those previously described above. Furthermore, in such an example, the substrate may be heated to a temperature as previously referenced. Figure 1 The deposition temperature described in method 100. As a non-limiting example, the substrate may be placed in a reaction chamber configured for a cyclic deposition process (e.g., configured for an ALD process or a similar ALD process), and the substrate may be heated to a deposition temperature between 350°C and 500°C.

[0104] According to an example of this disclosure, method 700 includes depositing a metal nitride intermediate layer on a metal oxide layer by repeatedly performing a cyclic deposition process (step 706). In such an example, the metal nitride intermediate layer may be deposited before the metal nitride layer is deposited or deposited directly on the metal nitride intermediate layer. In some embodiments, method 700 includes depositing the metal nitride intermediate layer directly on the metal oxide layer before depositing the metal nitride layer directly on the metal nitride intermediate layer.

[0105] According to examples of this disclosure, a metal nitride intermediate layer can be deposited via an atomic layer deposition process (referred to herein as a second atomic layer deposition process). In such embodiments, the second atomic layer deposition process for depositing the metal nitride intermediate layer may include sequentially and alternately contacting a substrate with a metal precursor and a nitrogen reactant. In some embodiments, the second atomic layer deposition process may be combined with the above-referenced... Figure 3 The first sub-cycle 210 is identical, similar, or substantially similar. In such embodiments, the metal precursor and nitrogen reactant may include any one or more of the metal precursor and nitrogen reactant described above with reference to cycle deposition processes 104 and 204. In some embodiments, the second atomic layer deposition method may exclude the introduction of a reducing agent comprising a cyclic compound.

[0106] Figure 9 Structure 900 is shown, which includes the previous structure 800 after a metal nitride intermediate layer is deposited through a second atomic layer deposition process. Figure 8 ).like Figure 9As shown, structure 900 includes a substrate 802, a metal oxide layer 804, and an additional metal nitride intermediate layer 902 deposited or directly deposited on the metal oxide layer 804. In such an example, the metal nitride intermediate layer 902 may form an interface layer between the metal oxide layer 804 and subsequent metal nitride layers deposited or directly deposited on the metal nitride intermediate layer 902, as described below.

[0107] According to an example of this disclosure, method 700 includes depositing a metal nitride layer over a metal oxide layer, particularly or directly on a metal nitride intermediate layer disposed on the metal oxide layer (step 708). In such an example, the metal nitride layer can be deposited by a cyclic deposition process including an atomic layer deposition process (referred to herein as a first atomic layer deposition process). In such an example, the first atomic layer deposition process for depositing the metal nitride layer on or directly on the metal nitride intermediate layer can include previously referenced... Figure 1 , Figure 2 and Figure 3 One or more of the described cyclic deposition processes, such as cyclic deposition processes 104 and 204. In some examples, the first atomic layer deposition process may include a deposition cycle in which the first atomic layer deposition process is repeated, wherein each deposition cycle includes: first contacting the substrate with a metal precursor, then contacting the substrate with a nitrogen reactant after contacting the substrate with the metal precursor, and then contacting the substrate with a reducing agent after contacting the substrate with the nitrogen reactant, the reducing agent comprising a cyclodiene compound selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene.

[0108] Figure 10 Structure 1000 is shown, which includes a previous structure 900 following the deposition of a metal nitride layer by a first atomic layer deposition process. Figure 9 ).like Figure 10 As shown, structure 1000 includes a substrate 802, a metal oxide layer 804, a metal nitride intermediate layer 902 deposited or directly deposited on the metal oxide layer 804, and a metal nitride layer 1002 further deposited or directly deposited on the metal nitride intermediate layer 902. In such an example, the metal nitride intermediate layer 902 may form an interface layer between the metal oxide layer 804 and the metal nitride layer 1002, such that the metal nitride intermediate layer 902 is disposed or directly disposed between the metal oxide layer 804 and the metal nitride layer 1002.

[0109] According to examples of this disclosure, both the metal nitride intermediate layer 902 and the metal nitride layer 1002 may comprise metal nitride materials, including metals selected from transition metals, including but not limited to titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten.

[0110] In some embodiments, both the metal nitride intermediate layer 902 and the metal nitride layer 1002 may comprise titanium nitride or be substantially composed therefrom. In some embodiments, both the metal nitride intermediate layer 902 and the metal nitride layer 1002 may comprise molybdenum nitride or be substantially composed therefrom. In some embodiments, both the metal nitride intermediate layer 902 and the metal nitride layer 1002 may comprise hafnium nitride or be substantially composed therefrom. In some embodiments, both the metal nitride intermediate layer 902 and the metal nitride layer 1002 may comprise niobium nitride or be substantially composed therefrom.

[0111] According to examples of this disclosure, the metal nitride layer 1002 may include a material having a first conductivity, and the metal nitride intermediate layer 902 may include a material having a second conductivity, wherein the first conductivity is different from the first conductivity. In one example, the metal nitride layer 1002 may include a conductive layer, and the metal nitride intermediate layer 902 may include an insulating layer. In another example, the metal nitride layer 1002 may include a conductive layer, and the metal nitride intermediate layer 902 may include a semiconductor layer. In another example, the metal nitride layer 1002 may include an insulating layer, and the metal nitride intermediate layer 902 may include a conductive layer. In yet another example, the metal nitride layer 1002 may include a semiconductor layer, and the metal nitride intermediate layer 902 may include a conductive layer. In various examples of this disclosure, the metal nitride layer 1002 may include a conductive layer, and the metal nitride intermediate layer 902 may include an insulating layer.

[0112] In some embodiments, the metal nitride intermediate layer 902 may include insulating hafnium nitride, and the metal nitride layer 1002 may include conductive hafnium nitride. In some embodiments, the metal nitride intermediate layer 902 may include insulating molybdenum nitride, and the metal nitride layer 1002 may include conductive molybdenum nitride. In some embodiments, the metal nitride intermediate layer 902 may include insulating niobium nitride, and the metal nitride layer 1002 may include conductive niobium nitride. In some embodiments, the metal nitride intermediate layer 902 may include insulating niobium nitride, and the metal nitride layer 1002 may include conductive niobium nitride.

[0113] According to examples of this disclosure, metal nitride layer 1002 may include a metal nitride comprising or substantially thereof a first stoichiometry, and metal nitride intermediate layer 902 may include a metal nitride comprising or substantially thereof a second stoichiometry, wherein the first stoichiometry differs from the second stoichiometry. As a non-limiting example, metal nitride layer 1002 may include or substantially consist of a first hafnium nitride layer having a first stoichiometry, and metal nitride intermediate layer 902 may include or substantially consist of a second hafnium nitride layer having a second stoichiometry, wherein the first stoichiometry differs from the second stoichiometry. In such a non-limiting example, the first hafnium nitride layer (i.e., metal nitride layer 1002) may include or substantially consist of HfN, and the second hafnium nitride layer (i.e., metal nitride intermediate layer 902) may include or substantially consist of Hf3N4. As a further non-limiting example, the metal nitride layer 1002 may include or be substantially composed of a first molybdenum nitride layer having a first stoichiometry, and the metal nitride intermediate layer 902 may include or be substantially composed of a second molybdenum nitride layer having a second stoichiometry, wherein the first stoichiometry differs from the second stoichiometry. As a further non-limiting example, the metal nitride layer 1002 may include or be substantially composed of a first titanium nitride layer having a first stoichiometry, and the metal nitride intermediate layer 902 may include or be substantially composed of a second titanium nitride layer having a second stoichiometry, wherein the first stoichiometry differs from the second stoichiometry.

[0114] In some embodiments, an additional conductive layer may be deposited on or directly on the metal nitride layer 1002. As a non-limiting example, a titanium nitride layer may be deposited on or directly on the metal nitride layer 1002 via an atomic layer deposition process.

[0115] For the purpose of summarizing the advantages of the present invention and its implementation relative to prior art, certain objects and advantages of the present invention have been described above. It should be understood, of course, that not all of these objects or advantages may be achieved according to any particular embodiment of the present invention. Therefore, for example, those skilled in the art will recognize that the present invention may be implemented or performed in a manner that achieves or optimizes one or more advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0116] All these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings, and the invention is not limited to any particular embodiment disclosed.

Claims

1. A method for depositing a metal nitride layer on a substrate disposed in a reaction chamber via a cyclic deposition process, the cyclic deposition process comprising one or more repeated deposition cycles, each deposition cycle comprising: (a) First, the metal precursor is introduced into the reaction chamber; (b) Introduce the nitrogen reactants into the reaction chamber; as well as (c) Introduce a reducing agent containing cyclic compounds into the reaction chamber; Step (c) is performed after step (b), or step (c) is performed simultaneously with step (b).

2. The method according to claim 1, wherein, The cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes: (a) First, bring the substrate into contact with the metal precursor; After step (a), (b) the substrate is brought into contact with the nitrogen reactant; and After step (b), (c) the substrate is brought into contact with the cyclic compound.

3. The method according to claim 1, wherein, The cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes: (a) First, bring the substrate into contact with the metal precursor; and After step (a), (b) and (c) the substrate is simultaneously brought into contact with the nitrogen reactant and the cyclic compound.

4. The method according to claim 1, wherein, The cyclic deposition process is an atomic layer deposition process, and each deposition cycle includes a deposition supercycle, each deposition supercycle including: Execute one or more first sub-loops, including: Contact the substrate with the metal precursor; and Contact the substrate with the nitrogen reactant; and Execute one or more second sub-loops, including: The substrate is brought into contact with the cyclic compound.

5. The method according to any one of claims 1 to 4, wherein, The cyclic compounds include cyclodiene compounds.

6. The method according to claim 5, wherein, The cyclodiene compound is selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene, and 1-methyl-1,4-cyclohexadiene.

7. The method according to any one of claims 1 to 4, wherein, The cyclic compounds include polycyclic hydrocarbons.

8. The method according to claim 7, wherein, The polycyclic hydrocarbon compound is selected from 1,2,3,4-tetrahydronaphthalene and 9,10-dihydroanthracene.

9. The method according to any one of claims 1 to 4, wherein, The metal precursor is selected from titanium precursor, molybdenum precursor, hafnium precursor and niobium precursor.

10. The method according to claim 1, wherein, The cyclic deposition process is carried out at a deposition temperature between 350°C and 500°C.

11. A method for thermally depositing a metal nitride layer on a substrate, the method comprising: The substrate is heated to a deposition temperature between 350°C and 500°C; and A deposition cycle that repeatedly performs the atomic layer deposition process, each deposition cycle including: (a) First, bring the substrate into contact with the transition metal precursor; After contacting the substrate with the transition metal precursor, (b) contact the substrate with the nitrogen reactant; and After contacting the substrate with the nitrogen reactant, (c) the substrate is contacted with a reducing agent comprising a cyclodiene compound selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene and 1-methyl-1,4-cyclohexadiene.

12. The method according to claim 11, wherein, The transition metal precursor is selected from titanium halide precursors and molybdenum halide precursors.

13. The method according to claim 12, wherein, The molybdenum halide precursor includes molybdenum halide precursor.

14. A method for forming a semiconductor structure, the method comprising: A substrate is placed in the reaction chamber, and the substrate includes a metal oxide layer; The substrate is heated to a deposition temperature between 350°C and 500°C; and A metal nitride layer is deposited on a metal oxide layer by repeatedly performing a deposition cycle of an atomic layer deposition process. Each deposition cycle includes: (a) First, bring the substrate into contact with the metal precursor; After contacting the substrate with the metal precursor, (b) contact the substrate with the nitrogen reactant; and After contacting the substrate with the nitrogen reactant, (c) the substrate is contacted with a reducing agent comprising a cyclodiene compound selected from 1,4-cyclohexadiene, 1,3-cyclohexadiene and 1-methyl-1,4-cyclohexadiene.

15. The method of claim 14, further comprising depositing the metal nitride intermediate layer directly onto the metal oxide layer before depositing the metal nitride layer directly onto the metal nitride intermediate layer.

16. The method according to claim 15, wherein, The metal nitride intermediate layer is deposited via a second atomic layer deposition process, which involves sequentially and alternately contacting the substrate with the metal precursor and the nitrogen reactant.

17. The method according to claim 16, wherein, The metal nitride layer is a conductive layer, and the metal nitride intermediate layer is an insulating layer.

18. The method according to claim 16, wherein, The metal nitride layer has a first stoichiometry, and the metal nitride intermediate layer has a second stoichiometry, wherein the first stoichiometry and the second stoichiometry are different from each other.

19. The method of claim 17, wherein, The metal nitride layer includes a first hafnium nitride layer, and the metal nitride intermediate layer includes a second hafnium nitride layer.

20. The method according to claim 19, wherein, The first hafnium nitride layer has an HfN stoichiometry, and the second hafnium nitride layer has an Hf3N4 stoichiometry.

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