Methods and systems for forming molybdenum-containing layers, and structures formed using these methods and systems

Abstract

This disclosure relates to a method for selectively filling gaps on a substrate with a molybdenum-containing material. In this method, the molybdenum-containing material is deposited into the gaps via a cyclic deposition process. The method includes providing a substrate into a reaction chamber, wherein the substrate includes at least one gap, and wherein the gap includes a silicon surface and a dielectric surface. The method further includes performing at least one deposition cycle. The deposition cycle includes providing a molybdenum precursor in the gas phase into the reaction chamber and providing reactants in the gas phase into the reaction chamber. The molybdenum-containing material is selectively deposited on the silicon surface of the gap to at least partially fill the gap. The invention further relates to a semiconductor processing apparatus for filling gaps using a molybdenum-containing material.

Description

Technical Field

[0001] This disclosure relates to methods and apparatus for manufacturing semiconductor devices. More specifically, the present invention relates to methods and components for depositing molybdenum-containing materials on a substrate, and to layers comprising molybdenum. Background Technology

[0002] Metal silicides can be formed in the fabrication of various semiconductor devices. Low resistivity materials for contacts, vias, and general fillers are a highly attractive area of ​​focus for logic / DRAM applications. Molybdenum and molybdenum silicide are excellent materials for such applications. Summary of the Invention

[0003] This summary is provided to present the chosen concepts in a simplified form. These concepts are further described in detail in the following description of exemplary embodiments of this disclosure. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

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

[0005] Various embodiments of this disclosure relate to methods for filling gaps, structures and devices formed using such methods, and apparatus for performing the methods and / or for forming structures and / or devices. The materials can be used in the field of integrated circuit manufacturing.

[0006] Therefore, this paper describes a method for selectively filling gaps with a molybdenum-containing material. The method includes: providing a substrate into a reaction chamber, wherein the substrate includes at least one gap, and wherein the gap includes a silicon surface and a dielectric surface; and performing at least one deposition cycle. Each deposition cycle includes providing a molybdenum precursor in the gas phase into the reaction chamber; and providing a reactant in the gas phase into the reaction chamber. In this manner, a molybdenum-containing material is selectively deposited on the silicon surface of the gap to at least partially fill the gap.

[0007] In some embodiments, the method further includes a thermal annealing step, wherein the substrate is heated to a temperature of at least 550°C.

[0008] In some embodiments, the substrate is heated to a temperature between 350°C and 550°C during the deposition cycle.

[0009] In some embodiments, the deposited molybdenum-containing material includes molybdenum silicide.

[0010] In some embodiments, the method further includes pre-cleaning the silicon-containing substrate to remove native oxides from the surface of the substrate. In some embodiments, pre-cleaning is performed by remote plasma treatment, radical treatment, hydrogen fluoride treatment, or sputtering etching. In some embodiments, radical treatment includes treating the surface with radicals obtained from NH3 gas and / or NF3 gas.

[0011] In some embodiments, the method further includes a purging step after providing the molybdenum precursor and after providing the reactants.

[0012] In some embodiments, the molybdenum precursor is provided to the reaction chamber in a pulse, and the reactants are provided to the reaction chamber continuously.

[0013] In some embodiments, the gap consists of a bottom and two sidewalls, wherein the bottom is composed of silicon and / or germanium, and the sidewalls comprise a dielectric material. In some embodiments, the dielectric material comprises silicon oxynitride. In some embodiments, the dielectric material comprises silicon oxide. In some embodiments, the dielectric material comprises silicon nitride. In some embodiments, the dielectric material comprises silicon oxycarbide. In some embodiments, the dielectric material comprises aluminum oxide.

[0014] In some embodiments, the gap may be oriented vertically or horizontally.

[0015] In some embodiments, the method further includes depositing a second material into the gaps, wherein the second material comprises metallic molybdenum. In some embodiments, the second material is deposited on top of a molybdenum-containing material.

[0016] In some embodiments, the second material is deposited by performing at least one deposition cycle, wherein the deposition cycle includes: providing a molybdenum precursor in the gas phase to the reaction chamber, providing reactants in the gas phase to the reaction chamber, wherein the pressure in the reaction chamber is higher during the deposition of the second material than during the deposition of the molybdenum-containing material.

[0017] In some embodiments, the molybdenum precursor comprises molybdenum halide. In some embodiments, molybdenum halide comprises molybdenum pentachloride.

[0018] In some embodiments, the reactants comprise hydrogen.

[0019] In another aspect of the invention, a semiconductor processing apparatus is described. The apparatus includes a reaction chamber comprising a substrate support for supporting a substrate; a heater configured and arranged to heat the substrate in the reaction chamber; a molybdenum precursor source fluidly connected to the reaction chamber via one or more precursor valves; a reactant source fluidly connected to the reaction chamber via one or more reactant valves; and a controller configured and / or programmed to cause the semiconductor processing apparatus to perform the methods described herein. Attached Figure Description

[0020] The accompanying drawings, which are included to provide a further understanding of this disclosure and form part of this specification, illustrate exemplary embodiments and, together with the description, help to explain the principles of this disclosure. In the drawings:

[0021] Figure 1A and Figure 1B An exemplary embodiment of the method according to this disclosure is shown.

[0022] Figure 2 An exemplary structure according to this disclosure is depicted.

[0023] Figure 3 The semiconductor processing apparatus according to the present disclosure is presented in an illustrative manner.

[0024] 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

[0025] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific disclosed embodiments described below.

[0026] As used herein, the term "substrate" can refer to any one or more underlying materials, including any one or more underlying materials that can be modified or on which devices, circuits, or films can be formed. A "substrate" can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. A substrate can be in any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. Substrates can be made of semiconductor materials, including, for example, silicon, silicon germanium, germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0027] As an example, the substrate in powder form can have applications for pharmaceutical manufacturing. Porous substrates can contain polymers. Examples of workpieces may include medical devices (e.g., stents and syringes), jewelry, tooling devices, components for battery manufacturing (e.g., anodes, cathodes, or separators), or components for photovoltaic cells, etc.

[0028] A continuous substrate can extend beyond the boundaries of the processing chamber, where a deposition process takes place. In some processes, the continuous substrate can move through the processing chamber, allowing the process to continue until the end of the substrate is reached. A continuous substrate can be supplied from a continuous substrate feed system to allow for the fabrication and output of the continuous substrate in any suitable form.

[0029] Non-limiting examples of continuous substrates may include sheets, nonwoven films, rollers, foils, meshes, flexible materials, bundles of continuous filaments or fibers (e.g., ceramic or polymer fibers). Continuous substrates may also include carriers or sheets on which discontinuous substrates are mounted.

[0030] The terms "precursor" and "reactant" can refer to molecules (compounds or molecules containing a single element) that participate 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. The terms precursor and reactant are used interchangeably.

[0031] In some embodiments, the precursor or reactant is provided as a mixture of two or more compounds. In the mixture, the compounds other than the precursor may be inert compounds or elements. In some embodiments, the precursor or reactant is provided in the composition. The composition may be a solution or a gas under standard conditions.

[0032] According to the present disclosure, the vapor deposition method refers to the process in which material is deposited from the vapor phase onto a substrate.

[0033] Typically, in cyclic deposition processes according to this disclosure (such as atomic layer deposition (ALD) and molecular layer deposition (MLD)), during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the substrate surface (e.g., the substrate surface may include previously deposited material or other material from a previous deposition cycle). In some embodiments, the precursor on the substrate surface is not readily reactive with another precursor (i.e., the deposition of the precursor may be partially or fully self-limiting). Subsequently, another precursor or reactant may be introduced into the reaction chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant may be able to further react with the precursor. During one or more 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. Therefore, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a molybdenum precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the reactant to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the molybdenum precursor into the reaction chamber and after providing the reactants into the reaction chamber. Without limiting this disclosure to any particular theory, ALD and MLD can be similar processes in terms of self-limiting reactions and can be slower and more controllable layer growth rates compared to CVD. Typically, ALD is used to deposit inorganic materials, while in MLD, the precursor can be a completely organic molecule.

[0034] The process may include one or more cyclic phases. In some embodiments, the process includes one or more acyclic (i.e., continuous) phases. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In such embodiments, the process includes a continuous flow of a first polymer precursor or a second polymer precursor. In some embodiments, one or more precursors are continuously provided in a reaction chamber.

[0035] In some embodiments, at least one of the molybdenum precursor and reactant is provided to the reaction chamber in a pulsed manner. In some embodiments, the molybdenum precursor is supplied in a pulsed manner and the reactant is supplied in a pulsed manner, and the reaction chamber is purged between consecutive pulses of the molybdenum precursor and the reactant. The duration for which the molybdenum precursor and / or reactant is provided to the reaction chamber (i.e., the molybdenum precursor pulse time and the reactant pulse time, respectively) can be, for example, from about 0.01 seconds (s) to about 100 seconds, for example from about 0.01 seconds to about 5 seconds, or from about 1 second to about 20 seconds, or from about 0.5 seconds to about 10 seconds, or from about 5 seconds to about 15 seconds, or from about 10 seconds to about 30 seconds, or from about 10 seconds to about 60 seconds, or from about 20 seconds to about 60 seconds. The duration of the molybdenum precursor or reactant pulse can be, for example, 0.03s, 0.1s, 0.5s, 1s, 1.5s, 2s, 2.5s, 3s, 4s, 5s, 8s, 10s, 12s, 15s, 25s, 30s, 40s, 50s, 60s, 80s, or 100s.

[0036] In some embodiments, the molybdenum precursor pulse duration may be at least 5 seconds or at least 10 seconds. In some embodiments, the molybdenum precursor pulse duration may be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds. In some embodiments, the reactant pulse duration may be at least 5 seconds, at least 10 seconds, or at least 20 seconds. In some embodiments, the reactant pulse duration may be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds.

[0037] The pulse times used for the molybdenum precursor and reactant vary independently depending on the process under discussion. The appropriate pulse time may depend on the substrate topology. For structures with higher aspect ratios, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Furthermore, the selected molybdenum precursor and reactant chemicals can influence the appropriate pulse time. For process optimization purposes, shorter pulse times may be preferred, provided that suitable layer properties are achieved. In some embodiments, the molybdenum precursor pulse time is longer than the reactant pulse time. In some embodiments, the reactant pulse time is longer than the molybdenum precursor pulse time. In some embodiments, the molybdenum precursor pulse time is the same as the reactant pulse time.

[0038] In some embodiments, providing the molybdenum precursor and / or reactant into the reaction chamber includes pulsed molybdenum precursor and reactant over a substrate. In some embodiments, pulse durations ranging from several minutes may be used for the molybdenum precursor and / or reactant. In some embodiments, the molybdenum precursor may be pulsed more than once, such as two, three, or four times, before the reactant is pulsed into the reaction chamber. Similarly, more than one pulse of the reactant may be present before the molybdenum precursor is pulsed (i.e., provided) into the reaction chamber, such as two, three, or four pulses.

[0039] As used herein, the term "purge" refers to a process in which gaseous precursors and / or gaseous byproducts are removed from a substrate surface, for example by evacuating the reaction chamber with a vacuum pump and / or by replacing the gas inside the reaction chamber with an inert or substantially inert gas (such as argon or nitrogen). Purge can be performed between two gas pulses that react with each other. However, purging can also be performed between two gas pulses that do not react with each other. For example, purging can be provided between pulses of two precursors or between a precursor and a reactant. Purge can avoid or at least reduce gaseous interactions between two gases that react with each other. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, the purging steps can be used, for example, in the temporal sequence of providing a first precursor to the reaction chamber, providing a purge gas to the reaction chamber, and providing a second precursor to the reaction chamber, wherein the substrate on which the layer is deposited remains stationary. For example, in the case of space purging, the purging step can take the form of moving the substrate from a first position to a second position, continuously supplying a first precursor to the first position, and continuously supplying a second precursor to the second position by means of a purging curtain or another device separating the two spaces. The purging time can be, for example, from about 0.01 seconds to about 60 seconds, from about 0.05 seconds to about 50 seconds, or from about 1 second to about 40 seconds, or from about 0.5 seconds to about 30 seconds, or between about 1 second and about 45 seconds, such as 20 seconds, 30 seconds, or 40 seconds. However, other purging times can be used if desired, for example where highly conformal stepped coverage is required on structures with extremely high aspect ratios or other structures with complex surface morphologies, or a specific reactor type, such as a batch reactor, can be used.

[0040] CVD-type processes are characterized by non-self-limiting vapor deposition. They typically involve a vapor-phase reaction between two or more precursors and / or reactants. In some embodiments, CVD-type processes involve surface reaction or surface decomposition of two or more precursors and / or reactants. Precursors and reactants may be provided simultaneously to the reaction chamber or substrate, or in partially or completely separate pulses. However, CVD can be performed with a single precursor, or with two or more precursors that do not react with each other. A single precursor may decompose into reactive components deposited on the substrate surface. Decomposition can be achieved, for example, by plasma or thermal means. The substrate and / or reaction chamber may be heated to promote a reaction between the gaseous precursors and / or reactants. In some embodiments, precursors and reactants are provided until a layer of the desired thickness is deposited. In some embodiments, a cyclic CVD process may be used with multiple cycles to deposit a thin film of the desired thickness. In a cyclic CVD process, precursors and / or reactants may be provided to the reaction chamber in non-overlapping or partially or completely overlapping pulses.

[0041] As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous material, such as materials deposited by the methods disclosed herein. For example, layers and / or films can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partially or entirely molecular layers or partially or entirely atomic layers or atomic and / or molecular clusters. Films or layers can include materials or layers with pinholes, which can be at least partially continuous. In some embodiments, layers according to this disclosure are substantially continuous.

[0042] In this disclosure, "gas" can include materials that are gaseous at ambient temperature and pressure (NTP), evaporated solids, and / or evaporated liquids, and may consist of a single gas or a mixture of gases, depending on the circumstances. Passivation material precursors may be provided to the reaction chamber in the gaseous phase. Hard mask precursors may be provided to the reaction chamber in the gaseous phase. The term "inert gas" may refer to a gas that does not participate in the chemical reaction and / or does not, to an apparent degree, form part of the layer. Exemplary inert gases include He and Ar and any combination thereof. In some cases, molecular nitrogen and / or hydrogen may be inert gases. Gases other than process gases, i.e., gases not introduced via precursor injector systems, other gas distribution devices, etc., may be used, for example, to seal the reaction space, and may include sealing gases.

[0043] The method for depositing molybdenum-containing materials according to this disclosure includes providing a substrate in a reaction chamber. In other words, the substrate is located in a space where deposition conditions can be controlled. The reaction chamber may be a single-wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a vapor processing assembly for manufacturing semiconductor devices. The processing assembly may include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations in the multi-station processing chamber. The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. The various stages of the method may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a cluster tool, or the deposition station of a multi-station processing chamber.

[0044] In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a spray-head reactor. In some embodiments, the reaction chamber may be a hot-wall reactor. In some embodiments, the reaction chamber may be a spatially partitioned reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a high-volume manufacturing single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates.

[0045] The reaction chamber may form part of an atomic layer deposition (ALD) assembly. The reaction chamber may form part of a chemical vapor deposition (CVD) assembly. The semiconductor processing apparatus may be an ALD or CVD semiconductor processing apparatus. In some embodiments, the method is performed in a single reaction chamber of a cluster tool, but other, prior or subsequent fabrication steps of the structure or device are performed in a separate reaction chamber of the same cluster tool. Optionally, the assembly including the reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or reactants and / or precursors.

[0046] As used herein, the term "comprising" indicates the inclusion of certain features, but it does not exclude the presence of other features, provided they do not render the claim unfeasible. In some embodiments, the term "comprising" includes "consisting of".

[0047] As used herein, the term "composed of" indicates that no other features exist in the apparatus / method / product besides the features following the wording. When the term "composed of" is used to refer to a chemical compound, substance, or composition of substances, it indicates that the chemical compound, substance, or composition of substances contains only the listed components. Similarly, when the term "essentially composed of" is used to refer to a compound, substance, or composition of substances, it indicates that the compound, substance, or composition of substances contains the listed components, but may also contain trace elements and / or impurities that do not materially affect the properties of the compound, substrate, or composition of substances. Nevertheless, in some embodiments, the chemical compound, substance, or composition of substances may contain other components as trace elements or impurities in addition to the listed components.

[0048] Furthermore, in this disclosure, any two numbers of a variable may constitute a working range of the variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by “about”) may refer to an exact value or an approximate value and include equivalents, and may refer to an average, median, representative value, multi-value, etc. Furthermore, in this disclosure, the terms “comprising,” “consisting of,” and “having” independently mean “generally or broadly comprising,” “including,” “substantially consisting of,” or “consisting of” in some embodiments. The meaning of any definition in this disclosure does not necessarily exclude the common and conventional meaning in some embodiments.

[0049] "At least one," "one or more," and "and / or" are open-ended expressions that are both conjunction and disjunctive in operation. For example, each of the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," "one or more of A, B, or C," and "A, B, and / or C" means a single A, a single B, a single C, A and B together, A and C together, B and C together, or A, B, and C together. When each of A, B, and C in the above expressions refers to elements such as X, Y, and Z, or such as X1-X... n Y1-Y m and Z1-Z o When referring to element categories, this phrase is intended to mean a single element selected from X, Y, and Z; a combination of elements selected from the same category (e.g., X1 and X2); and a combination of elements selected from two or more categories (e.g., Y1 and Z). o ).

[0050] 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.

[0051] The term "basic" applied to compositions, methods, or systems generally refers to a proportion of values, properties, characteristics, etc., of at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or more, or any proportion between about 70% and about 100%, or conversely, the absence of such proportions. In some embodiments, the term "basic" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0052] The term “substantially” when applied to compositions, methods, or systems generally means that the addition of components does not substantially alter the properties and / or function of the composition, method, or system.

[0053] As used herein, a “molybdenum precursor” comprises a gas or a material that can be converted into a gaseous state and can be represented by a chemical formula containing molybdenum. In some embodiments, the molybdenum precursor comprises molybdenum halide. In some embodiments, the molybdenum precursor is selected from molybdenum pentachloride, molybdenum hexafluoride, molybdenum tetrachloride, and molybdenum dichloride. In some embodiments, the molybdenum precursor is provided as a mixture of two or more compounds. In the mixture, other compounds besides the molybdenum precursor are provided in the composition. A suitable composition may include a molybdenum compound and an effective amount of one or more stabilizers. The composition may be a solution or a gas under standard conditions.

[0054] In some embodiments, the molybdenum precursor is provided to the reactor chamber at a temperature from about 300°C to about 550°C. For example, the molybdenum-containing material may be deposited at a temperature from about 325°C to about 500°C, or at a temperature from about 350°C to about 450°C. In some embodiments of the invention, the molybdenum-containing material may be deposited at a temperature from about 360°C to about 430°C, or at a temperature from about 370°C to about 430°C. In some embodiments, the molybdenum-containing material may be deposited at a temperature from about 300°C to about 400°C, or at a temperature from about 350°C to about 400°C, or at a temperature from about 380°C to about 420°C. For example, the molybdenum-containing material may be deposited at a temperature of about 310°C, about 325°C, about 385°C, about 390°C, about 410°C, about 415°C, about 425°C, about 375°C, about 380°C, about 385°C, or about 390°C.

[0055] In some embodiments, the reactants are provided to the reactor chamber at a temperature of about 300°C to about 550°C. For example, the reactants may be provided at a temperature of about 325°C to about 500°C. In some embodiments of this disclosure, the reactants may be provided at a temperature of about 360°C to about 430°C or at a temperature of about 370°C to about 430°C. In some embodiments, the reactants may be provided at a temperature of about 300°C to about 400°C or at a temperature of about 350°C to about 400°C or at a temperature of about 380°C to about 420°C. For example, the reactants may be provided at a temperature of about 310°C or about 325°C or about 385°C, or about 390°C, or about 410°C, or about 415°C or about 425°C, or about 375°C, or about 380°C, or about 385°C, or about 390°C.

[0056] The pressure in the reaction chamber can be selected independently for different process steps. In some embodiments, a first pressure can be used during a molybdenum precursor pulse and a second pressure can be used during a reactant pulse. A third or additional pressure can be used during purging or other process steps. In some embodiments, the pressure in the reaction chamber during the deposition process is atmospheric pressure, or less than 760 Torr, or wherein the pressure in the reaction chamber during the deposition process is between 0.2 Torr and 760 Torr, or between 1 Torr and 100 Torr, or between 1 Torr and 10 Torr. In some embodiments, the pressure in the reaction chamber during the deposition process is less than about 0.001 Torr, less than 0.01 Torr, less than 0.1 Torr, less than 1 Torr, less than 10 Torr, less than 50 Torr, less than 100 Torr, or less than 300 Torr. In some embodiments, during at least a portion of the method according to this disclosure, the pressure in the reaction chamber is less than about 0.001 Torr, less than 0.01 Torr, less than 0.1 Torr, less than 1 Torr, less than 10 Torr, or less than 50 Torr, less than 100 Torr, or less than 300 Torr. For example, in some embodiments, the first pressure may be about 0.1 tor, about 0.5 tor, about 1 tor, about 5 tor, about 10 tor, about 20 tor, or about 50 tor. In some embodiments, the second pressure is about 0.1 tor, about 0.5 tor, about 1 tor, about 5 tor, about 10 tor, about 20 tor, or about 50 tor.

[0057] In some embodiments, the molybdenum precursor and reactant are supplied in pulses, the reactant is supplied in pulses, and the reaction chamber is purged between consecutive pulses of the molybdenum precursor and reactant. The length of the molybdenum precursor pulse or reactant pulse can be, for example, from about 0.01 s to about 120 s, for example, from about 0.01 s to about 5 s, or from about 1 s to about 20 s, or from about 0.5 s to about 10 s, or from about 5 s to about 15 s, or from about 10 s to about 30 s, or from about 10 s to about 60 s, or from about 20 s to about 60 s. The length of the molybdenum precursor or reactant pulse can be, for example, 0.03 s, 0.1 s, 0.5 s, 1 s, 1.5 s, 2 s, 2.5 s, 3 s, 4 s, 5 s, 8 s, 10 s, 12 s, 15 s, 25 s, 30 s, 40 s, 50 s, or 60 s. In some embodiments, the molybdenum precursor pulse duration may be at least 5 seconds, at least 10 seconds, at least 20 seconds, or at least 30 seconds. In some embodiments, the molybdenum precursor pulse duration may be at most 5 seconds, at most 10 seconds, at most 20 seconds, or at most 30 seconds. In some embodiments, the reactant pulse duration may be at least 20 seconds, at least 30 seconds, at least 45 seconds, or at least 60 seconds. In some embodiments, the reactant pulse duration may be at most 90 seconds, at most 100 seconds, at most 110 seconds, or at most 120 seconds.

[0058] The pulse times for the molybdenum precursor and reactants vary independently depending on the process under discussion. The appropriate pulse time may depend on the substrate topology. For structures with higher aspect ratios, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Furthermore, the chosen molybdenum precursor and reactant chemistry can influence the appropriate pulse time. For process optimization purposes, shorter pulse times may be preferred, provided that suitable layer properties are achieved. In some embodiments, the molybdenum precursor pulse time is longer than the reactant pulse time. In some embodiments, the reactant pulse time is longer than the molybdenum precursor pulse time. In some embodiments, the molybdenum precursor pulse time is the same as the reactant pulse time.

[0059] In some embodiments, the reactants are provided to the reaction chamber as a continuous stream, and the molybdenum precursor is provided to the reaction chamber as a pulse. This pulsed scheme may be referred to as half-CVD or pulsed CVD. The continuous stream and the pulses at least partially overlap. There are intervals between the pulses such that the substrate is exposed to the precursor during the pulse.

[0060] In some embodiments, the molybdenum precursor may be pulsed more than once, such as two, three, or four times, before the reactant is pulsed into the reaction chamber. Similarly, more than one pulse of the reactant, such as two, three, or four pulses, may be present before the molybdenum precursor is pulsed (i.e., provided) into the reaction chamber.

[0061] In some embodiments, the formed molybdenum-containing material may include molybdenum silicide. The silicide is formed when the molybdenum-containing material is deposited into the interstices and is thermally annealed, which causes the molybdenum to mix with the silicon surface at the bottom of the interstices. In other words, the deposited molybdenum-containing material is heated using silicon from a silicon substrate to form molybdenum silicide. In some embodiments, a layer of molybdenum silicide is deposited into the interstices. On top of the molybdenum silicide, a layer of metallic molybdenum is deposited into the interstices. Metallic molybdenum is deposited using the same molybdenum precursors and reactants as in the deposition of molybdenum silicide. The metallic molybdenum is deposited at a pressure approximately 50 Torr higher than that of the molybdenum silicide.

[0062] In some embodiments, the deposition process is selective. The gap is formed of two different materials, and the deposited molybdenum-containing material grows only on one of them. In some embodiments, at least one surface of the gap is formed of a material selected from silicon, silicon-germanium, and germanium, and at least one surface is formed of a dielectric material. In some embodiments, the material comprising silicon, silicon-germanium, or germanium is doped with an element selected from boron, phosphorus, arsenic, and gallium. In some embodiments, the molybdenum-containing material is grown on the silicon surface and not on the dielectric surface. In some embodiments, the bottom of the gap is silicon, and the two sidewalls are dielectric material. In some embodiments, the orientation of the gap may be horizontal. In some embodiments, the orientation of the gap may be vertical. Regardless of the orientation of the gap, the bottom of the gap is located opposite the opening of the gap, and the sidewalls are perpendicular to the bottom.

[0063] In some embodiments, the method includes removing excess molybdenum precursor from the reaction chamber with an inert gas before providing reactants in the reaction chamber. In some embodiments, the reaction chamber is purged between providing the molybdenum precursor in the reaction chamber and providing reactants in the reaction chamber. In some embodiments, a purging step exists between each pulse. Therefore, the reaction chamber may also be purged between two pulses of the same chemical substance (e.g., molybdenum precursor or reactant).

[0064] According to another aspect of the invention, a semiconductor processing apparatus is provided for filling gaps on a substrate with a molybdenum-containing material. The apparatus includes: one or more reaction chambers configured and arranged to hold a substrate; and a precursor injector system configured and arranged to provide a molybdenum precursor and reactants in the gas phase into the reaction chambers. The apparatus further includes a first precursor container configured and arranged to contain and evaporate molybdenum. The semiconductor processing apparatus also includes a second precursor container configured and arranged to contain and evaporate reactants. A deposition assembly includes a controller configured and arranged to provide the molybdenum precursor and reactants to the reaction chambers via the precursor injector system to fill gaps on the substrate with the molybdenum-containing material.

[0065] In some embodiments, the apparatus further includes a temperature controller for controlling the temperature of the reaction chamber. The temperature in the reaction chamber may be set between 350°C and 550°C, as described in the above disclosure. In some embodiments, the temperature controller is a heater configured and arranged to heat the substrate in the reaction chamber.

[0066] Figure 1A and Figure 1B An embodiment of method 100 according to this disclosure is shown. Reference Figure 1A Method 100 can be used to fill gaps with a material including molybdenum. This material can be used during the formation of the structure or device. However, unless otherwise stated, the method is not limited to such applications.

[0067] During step 102, a substrate is provided into the reaction chamber of the reactor. The reaction chamber may form part of an atomic layer deposition (ALD) reactor. The reactor may be a single-wafer reactor. Alternatively, the reactor may be a batch reactor. The various stages of method 100 may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a clustering tool. In some embodiments, method 100 is performed in a single reaction chamber of a clustering tool, but other, prior or subsequent fabrication steps of the structure or device are performed in another reaction chamber of the same clustering tool. Optionally, the reactor including the reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or reactants and / or precursors.

[0068] During step 102, the substrate can be brought to a desired temperature and pressure for providing the molybdenum precursor 104 and / or for providing the reactant 106 in the reaction chamber. The temperature within the reaction chamber (e.g., the temperature of the substrate or substrate support) can be, for example, from about 300°C to about 550°C, or from about 350°C to about 500°C. As another example, the temperature within the reaction chamber can be from about 375°C to about 425°C, or from about 380°C to about 420°C. Exemplary temperatures within the reaction chamber can be about 310°C, about 325°C, or about 385°C, or about 390°C, or about 410°C, or about 415°C, or about 425°C, or about 375°C, or about 380°C, or about 385°C, or about 390°C. If the temperature is below 300°C or 350°C, the growth rate of the deposited material decreases.

[0069] The pressure within the reaction chamber can be less than 760 Torr, for example 400 Torr, 100 Torr, 70 Torr, or 20 Torr, 5 Torr, or 0.1 Torr. Different pressures can be used for different process steps. In some embodiments, the pressure is maintained at a certain level for approximately 200 deposition cycles, and then the pressure is increased by approximately 50 Torr for approximately 400 deposition cycles. In some embodiments, this pressure variation enables the deposition of a bilayer, wherein the first deposited layer comprises molybdenum silicide, and the second deposited layer comprises metallic molybdenum.

[0070] A molybdenum precursor 104 is provided in a reaction chamber containing a substrate. Without limiting this disclosure to any particular theory, the molybdenum precursor may be chemisorbed onto the substrate during the provision of the molybdenum precursor in the reaction chamber. The duration of the provision of the molybdenum precursor in the reaction chamber (molybdenum precursor pulse time) may be, for example, 0.01 s, 0.5 s, 1 s, 1.5 s, 2 s, 2.5 s, 3 s, 3.5 s, 4 s, 4.5 s, or 5 s. In some embodiments, the duration of the provision of the molybdenum precursor in the reaction chamber (molybdenum precursor pulse time) may be greater than 0.01 s, greater than 0.5 s, or about 1 s.

[0071] When reactant 106 is provided in the reaction chamber, it can react with a chemisorbed molybdenum precursor or its derivative to form a molybdenum-containing material. The duration for which the reactant is provided in the reaction chamber (reactant pulse time) can be, for example, 0.5 s, 1 s, 2 s, 3 s, 3.5 s, 4 s, 5 s, 6 s, 7 s, 8 s, 10 s, 12 s, 15 s, 30 s, 40 s, 50 s, or 60 s. In some embodiments, the duration for which the reactant is provided in the reaction chamber can be less than 30 s, less than 20 s, or about 10 s.

[0072] In some embodiments, the molybdenum precursor may be heated before being provided to the reaction chamber. In some embodiments, the reactants may be heated before being provided to the reaction chamber. In some embodiments, the reactants may be maintained at ambient temperature before being provided to the reaction chamber.

[0073] Steps 104 and 106, performed in any order, can form a deposition cycle, resulting in the deposition of a molybdenum-containing material. In some embodiments, the two deposition steps (loop 108) of providing the molybdenum precursor and reactants (104 and 106) in the reaction chamber can be repeated. Such embodiments include multiple deposition cycles. The thickness of the deposited material can be adjusted by changing the number of deposition cycles, which (loop 108) can be repeated until the desired material thickness is achieved, for example, approximately 50, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 1200, or 1500 deposition cycles.

[0074] The amount of molybdenum-containing material deposited during a single cycle (growth per cycle) varies depending on the processing conditions and can be, for example, from about 0.1 Å / cycle to about 10 Å / cycle, such as from about 0.3 Å / cycle to about 4.5 Å / cycle, such as from about 0.5 Å / cycle to about 3.5 Å / cycle, or from about 1.2 Å / cycle to about 3.0 Å / cycle. For example, the growth rate can be about 1.0 Å / cycle, 1.2 Å / cycle, 1.4 Å / cycle, 1.6 Å / cycle, 1.8 Å / cycle, 2 Å / cycle, 2.2 Å / cycle, or 2.4 Å / cycle. Depending on the deposition conditions, the number of deposition cycles, etc., a material of variable thickness can be deposited. For example, the material thickness can be between about 0.2 nm and 60 nm, or between about 1 nm and 50 nm, or between about 0.5 nm and 25 nm, or between about 1 nm and 50 nm, or between about 10 nm and 60 nm. The material can have thicknesses of, for example, approximately 0.2 nm, 0.3 nm, 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, 6 nm, 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 50 nm, 70 nm, 85 nm, or 100 nm. The desired thickness can be selected based on the application discussed.

[0075] The molybdenum precursor and reactants can be provided in the reaction chamber in separate steps (104 and 106). Figure 1BAn embodiment according to this disclosure is shown, wherein steps 104 and 106 are separated by purging steps 105, 107. In such an embodiment, the deposition cycle includes one or more purging steps 105, 107. During the purging steps, the precursors may be separated from each other over time by an inert gas (e.g., argon (Ar), nitrogen (N2), or helium (He)) and / or vacuum pressure. Separation of the molybdenum precursor and reactants may alternatively be spatial separation.

[0076] Purging reaction chambers 103 and 105 prevents or mitigates gas-phase reactions between the molybdenum precursor and reactants, and enables possible self-saturating surface reactions. Excess chemicals and reaction byproducts (if any) can be removed from the substrate surface before the substrate comes into contact with the next reactive chemical, for example, by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate can be moved to contact the molybdenum precursor and reactants separately. Because the reaction can be self-saturating in some embodiments, strict temperature control of the substrate and precise dosage control of the precursor may not be required. However, the substrate temperature is preferably such that the incident gaseous material does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0077] When method 100 is performed, a material comprising molybdenum is deposited into gaps on a substrate. The deposition process can be a cyclic deposition process and can include cyclic CVD, ALD, or a hybrid cyclic CVD / ALD process. For example, in some embodiments, the growth rate of a particular ALD process may be lower than that of a CVD process. One way to increase the growth rate is to operate at a deposition temperature higher than that typically used in ALD processes, resulting in a portion of the chemical vapor deposition process, but still utilizing the sequential introduction of molybdenum precursors and reactants. Such a process may be referred to as cyclic CVD. In some embodiments, a cyclic CVD process may include introducing two or more precursors into a reaction chamber, wherein there may be overlapping time periods between the two or more precursors in the reaction chamber, resulting in both an ALD component and a CVD component being deposited. This is referred to as a hybrid process. According to another example, a cyclic deposition process may include a continuous flow of one reactant or precursor and a periodic pulse of another chemical component entering the reaction chamber. In some embodiments, the reactant is continuously supplied to the reaction chamber, and the molybdenum precursor is periodically pulsed. During step 104, the temperature and / or pressure in the reaction chamber can be the same as or similar to any of the pressures and temperatures mentioned above in conjunction with step 102.

[0078] In some embodiments, a molybdenum precursor is contacted with a substrate surface 104, excess molybdenum precursor is partially or substantially completely removed by an inert gas or vacuum 105, and a reactant is contacted with the substrate surface including the molybdenum precursor. The molybdenum precursor may be contacted with the substrate surface in one or more pulses 104. In other words, the pulses 104 of the molybdenum precursor may be repeated. The molybdenum precursor on the substrate surface may react with the reactant to form a molybdenum-containing material on the substrate surface. The pulses 106 of the reactant may also be repeated. In some embodiments, the reactant 106 may be provided in a first reaction chamber. Subsequently, the reaction chamber 105 may be purged, and the molybdenum precursor 104 may be provided in the reaction chamber in one or more pulses.

[0079] For example, if a material comprising molybdenum is deposited at a temperature between 370°C and 410°C, and the deposition cycle (providing molybdenum precursors and reactants, which are separated by purging) is repeated between 400 and 600 times, it is possible to obtain a material with a thickness between about 10 nm and 40 nm (e.g., 20 nm or 30 nm).

[0080] The properties of the film can be modified by using post-deposition annealing. Annealing can be performed directly after the material is deposited, i.e., without depositing an additional layer. Alternatively, annealing can be performed after an additional layer has been deposited. Annealing temperatures can be from about 600°C to about 800°C. For example, the annealing temperature can be 600°C, 630°C, 660°C, 700°C, 730°C, or 750°C. Annealing can be performed in a gas atmosphere containing argon, an argon-hydrogen mixture, hydrogen, nitrogen, or a nitrogen-hydrogen mixture, or a gas consisting of or substantially consisting of these gases. The duration of annealing can be from about 1 minute to about 60 minutes, for example, 5 minutes, 20 minutes, 30 minutes, or 45 minutes. Annealing can be performed at pressures from 0.05 to 760 Torr. For example, the pressure during annealing can be about 1 Torr, about 10 Torr, about 100 Torr, or about 500 Torr. When annealing molybdenum-containing materials, molybdenum silicide is formed using silicon from the substrate.

[0081] In some embodiments, the method further includes a pre-cleaning step. Pre-cleaning is performed prior to step 104, in which the molybdenum precursor is provided into the reaction chamber. The pre-cleaning step removes any native oxides from the surface of the substrate. In some embodiments, pre-cleaning is performed by remote plasma treatment, radical treatment, or hydrogen fluoride treatment. In some embodiments, radical treatment includes treating the surface with radicals obtained from NH3 gas and / or NF3 gas. In some embodiments, pre-cleaning includes hydrogen fluoride vapor and NH3 gas. In yet another embodiment, pre-cleaning includes sputter etching using argon gas or a mixture of argon and NH3 gas.

[0082] Figure 2A schematic diagram of a substrate 200 including a gap 210 is shown. The gap 210 includes sidewalls 211 and a bottom 212. The substrate also includes a proximal surface 220. In some embodiments, the sidewalls 211 and the bottom 212 comprise different materials. In some embodiments, the sidewalls 211 comprise a dielectric, such as a silicon-containing dielectric, such as silicon oxide, silicon nitride, silicon carbide, and mixtures thereof. In some embodiments, at least one of the sidewalls 211 comprises a metal, such as molybdenum, post-molybdenum, or a rare earth metal. In some embodiments, the metal comprises Cu, Co, W, Ru, Mo, Al, or alloys thereof. In some embodiments, the bottom 212 comprises silicon.

[0083] In some embodiments, the proximal surface 220 has the same composition as the sidewall 211. In some embodiments, the proximal surface 220 has a different composition than the sidewall 211. In some embodiments, the proximal surface 220 has a different composition than the bottom 212. In some embodiments, the proximal surface 220 has the same composition as the bottom 212.

[0084] Figure 3 A semiconductor processing apparatus 300 according to the present disclosure is illustrated schematically. The semiconductor processing apparatus 300 can be used to perform the methods described herein and / or form structures or devices or portions thereof as described herein.

[0085] In the example shown, the semiconductor processing apparatus 300 includes one or more reaction chambers 302, a precursor injector system 301, a molybdenum precursor 304, a reactant container 306, a purge gas source 308, an exhaust source 310, and a controller 312.

[0086] Reaction chamber 302 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber.

[0087] Molybdenum precursor container 304 may include a container and one or more molybdenum precursors as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). Reactant container 306 may include a container and one or more reactants as described herein—either alone or mixed with one or more carrier gases. Purge gas source 308 may include one or more inert gases as described herein. Although three source containers 304-308 are shown, the semiconductor processing apparatus 300 may include any suitable number of source containers. Source containers 304-308 may be coupled to reaction chamber 302 via lines 314-318, each of which may include a flow controller, valve, heater, etc. In some embodiments, the molybdenum precursor in the molybdenum precursor container may be heated. In some embodiments, the container is heated such that the molybdenum precursor reaches a temperature between about 60°C and about 160°C, for example between about 100°C and about 145°C, such as 85°C, 100°C, 110°C, 120°C, 130°C, or 140°C.

[0088] The emission source 310 may include one or more vacuum pumps.

[0089] Controller 312 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the semiconductor processing apparatus 300. Such circuitry and components operate to introduce precursor and purge gases from respective sources 304-308. Controller 312 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 302, the pressure within the reaction chamber 302, and various other operations to provide appropriate operation of the semiconductor processing apparatus 300. Controller 312 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursor and purge gases from the reaction chamber 302. Controller 312 may include modules, such as software or hardware components, to perform certain tasks. Modules may be configured to reside on addressable storage media of the control system and configured to perform one or more processes.

[0090] Other configurations of the semiconductor processing apparatus 300 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor sources, and purge gas sources exist to achieve the goal of selectively and in a coordinated manner feeding gases into the reaction chamber 302. Additionally, as a schematic representation of the semiconductor processing apparatus, many components have been omitted for simplicity, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0091] During operation of the semiconductor processing apparatus 300, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate transport system to a reaction chamber 302. Once the substrate is transferred to the reaction chamber 302, one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) from gas sources 304-308 are introduced into the reaction chamber 302.

[0092] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of this disclosure.

[0093] The specific embodiments shown and described are illustrative of the invention and its best mode, and are not intended to limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0094] It should be understood that the configurations and / or methods described herein are exemplary in nature, and these specific embodiments or examples should not be considered limiting, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted.

[0095] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems and configurations disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for selectively filling gaps with a molybdenum-containing material, the method comprising: A substrate is provided into a reaction chamber, wherein the substrate includes at least one gap, wherein the gap includes a silicon surface and a dielectric surface; as well as Perform at least one deposition cycle, wherein the deposition cycle includes: The molybdenum precursor is provided to the reaction chamber in the gas phase; and The reactants are provided to the reaction chamber in the gas phase. In this process, molybdenum-containing material is selectively deposited on the silicon surface of the gap to at least partially fill the gap.

2. The method according to claim 1, further comprising a thermal annealing step, wherein, The substrate is heated to a temperature of at least 550°C.

3. The method according to claim 1 or 2, wherein, During the deposition cycle, the substrate is heated to a temperature between 350°C and 550°C.

4. The method according to any one of the preceding claims, wherein, The molybdenum-containing material includes molybdenum silicide.

5. The method according to any one of the preceding claims further includes pre-cleaning the silicon-containing substrate to remove native oxides from the surface of the substrate.

6. The method according to claim 5, wherein, The pre-cleaning is performed by remote plasma treatment, free radical treatment, hydrogen fluoride treatment, or sputtering etching.

7. The method according to claim 6, wherein, The free radical treatment includes treating the surface with free radicals obtained from NH3 gas and / or NF3 gas.

8. The method according to any one of the preceding claims further includes a purging step after providing the molybdenum precursor and after providing the reactants.

9. The method according to any one of claims 1 to 7, wherein, The molybdenum precursor is pulsed into the reaction chamber, and the reactants are continuously fed into the reaction chamber.

10. The method according to any one of the preceding claims, wherein, The gap consists of a bottom and two sidewalls, wherein the bottom is composed of silicon and / or germanium, and the sidewalls comprise a dielectric material.

11. The method according to claim 10, wherein, The dielectric material is selected from silicon oxynitride, silicon oxide, silicon nitride, silicon carbide, and aluminum oxide.

12. The method according to any one of the preceding claims, wherein, The gap can be vertically or horizontally oriented.

13. The method according to any one of the preceding claims further comprises depositing a second material into the gap, wherein the second material comprises metallic molybdenum.

14. The method according to claim 13, wherein, The second material is deposited on top of the molybdenum-containing material.

15. The method according to claim 13 or 14, wherein, The second material is deposited by performing at least one deposition cycle, wherein the deposition cycle includes: The molybdenum precursor is provided to the reaction chamber in the gas phase. The reactants are provided to the reaction chamber in the gas phase. The pressure in the reaction chamber is greater during the deposition of the second material than during the deposition of the molybdenum-containing material.

16. The method according to any one of the preceding claims, wherein, The molybdenum precursor comprises molybdenum halide.

17. The method according to claim 16, wherein, The molybdenum halide includes molybdenum pentachloride.

18. The method according to any one of the preceding claims, wherein, The reactants contain hydrogen.

19. A semiconductor processing apparatus, comprising: The reaction chamber includes a substrate support for supporting the substrate; A heater, which is constructed and arranged to heat the substrate in the reaction chamber; A molybdenum precursor source, which is fluidly connected to the reaction chamber via one or more precursor valves; A reactant source, which is fluidly connected to the reaction chamber via one or more reactant valves; and A controller configured to cause a semiconductor processing device to perform the method according to claim 1.

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