Method for depositing molybdenum-containing material on a surface

Abstract

Methods and systems for depositing molybdenum-containing materials are disclosed. Exemplary methods can be used to form structures including conductive contacts, barrier layers, and / or spacers using deposited molybdenum-containing materials.

Description

Technical Field

[0001] This disclosure generally relates to methods for depositing materials on a substrate surface. More specifically, the present invention relates to methods for depositing molybdenum-containing materials on a substrate surface. Background Technology

[0002] Conductive features, such as contacts, conductive plugs, and circuits, are typically formed during the manufacturing of electronic devices, such as semiconductor devices. Conductive features are usually formed by depositing a layer of conductive material (such as tungsten or copper), which can be formed within vias and / or etched to create the conductive features.

[0003] Conductive features are typically formed on and / or within insulating or dielectric materials on a substrate. Tungsten and copper can diffuse through dielectric and insulating materials commonly used in the fabrication of electronic devices. Therefore, fabrication techniques employing tungsten or copper deposition often involve using barrier layers (such as titanium nitride) to mitigate the diffusion of tungsten, copper, etc., thereby improving device reliability and yield. However, barrier layers typically exhibit high resistivity, thus increasing the overall resistivity of the conductive features. Furthermore, the formation of barrier layers increases the complexity of forming conductive features and often requires additional equipment. For example, barrier layers are typically formed in one reaction chamber, and conductive layers or features (e.g., copper or tungsten) are formed in another reaction chamber. Therefore, improved methods for forming conductive features are desired.

[0004] Additionally, in some applications, it may be necessary to form low-resistance contacts with a semiconducting surface (such as silicon). Typical contacts may include titanium / titanium nitride contacts or nickel / nickel-platinum contacts. While such contacts can be used in a variety of applications, the techniques for forming contacts with this material may involve an undesirable number of steps and / or the contact resistance may be undesirably high. Therefore, improved techniques for forming contacts are needed.

[0005] Any discussion set forth in this section (including discussions of problems and solutions) is included in this disclosure and is for the purpose of providing background to this disclosure only. 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. Summary of the Invention

[0006] This synopsis is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the following detailed description of exemplary embodiments of this disclosure. This synopsis is not intended to necessarily identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0007] Various embodiments of this disclosure relate to methods for depositing molybdenum. For example, exemplary methods can be used to fill recesses on the surface of a substrate with a molybdenum-containing material, form a barrier layer, and / or form contacts with, for example, a semiconducting surface. Such methods can be used to form structures suitable for forming electronic devices, such as semiconductor devices.

[0008] While various embodiments of the invention address the shortcomings of prior methods in more detail below, in general, embodiments of the invention provide an improved method comprising performing plasma-assisted deposition at relatively low temperatures to obtain a molybdenum-containing material with desired properties. As explained in more detail below, in some cases, examples of this disclosure can be used to at least partially fill gaps or recesses on a substrate surface. Plasma-assisted deposition allows for selective or non-selective deposition of molybdenum and deposition of molybdenum with desired properties. Plasma-assisted deposition can be used to form molybdenum linings, fill gaps, both, etc.

[0009] According to embodiments of the present invention, a method is provided for filling a recess on the surface of a substrate with a molybdenum-containing material. The method includes providing a substrate in a reactor and forming a molybdenum-containing film by repeating a cycle comprising: supplying a first source gas containing molybdenum to the substrate, supplying a first reactant to the substrate, and applying a first power to the reactor to form a plasma, thereby forming an activated reactant substance that can react with the first source gas or a derivative thereof adsorbable onto the substrate. According to examples of these embodiments, the steps of supplying the first reactant and applying the first plasma power overlap in time. According to further examples of this disclosure, the first source gas includes one or more of molybdenum halide, molybdenum halide, organometallic compounds (e.g., β-diketones), or organometallic compounds. The first reactant may include at least one of hydrogen, nitrogen, or mixtures thereof. According to further examples, the method further includes, for example, supplying a second reactant before applying the first power to the reactor. According to further examples, the method may include pre-cleaning to remove native oxides from the substrate before forming the molybdenum-containing film. According to further examples, the method may include supplying a second source gas. The second source gas may include silicon. In these cases, the molybdenum-containing material may be a silicon- and molybdenum-containing film. Alternatively or concurrently, the method may include treating the substrate with hydrogen while applying a second power, before, after, or both of forming the molybdenum-containing film. An exemplary method may also include thermal annealing after forming the molybdenum-containing film; this step may then be followed by chemical mechanical polishing (CMP).

[0010] According to another embodiment of the present invention, a method for filling a recess on the surface of a substrate with a molybdenum-containing material comprises: providing the substrate in a reactor; performing pre-cleaning to clean the surface of the substrate; and conformally forming a molybdenum-containing film on the surface of the recess. The step of forming the molybdenum-containing film may include repeating a cycle comprising: supplying a first source gas containing molybdenum to the substrate, supplying a first reactant to the substrate, and providing a first power to form an activating substance from the first reactant. The method may further include forming a metallic film on the molybdenum-containing film to fill the recess. The step of forming the metallic film may include: supplying a metallic source gas to the substrate and supplying a second reactant to the substrate. The first reactant may be or include at least one of hydrogen, nitrogen, or mixtures thereof. The second reactant may be or include at least one of H2, diiodoethane (C2H2I2), silane, alkylsilane, alkyliodine, silicon iodide, or mixtures thereof. The method may further include performing thermal annealing after filling the recess; CMP may be performed after annealing. In some cases, the method may include forming a capping layer on the molybdenum-containing film and then performing thermal annealing.

[0011] According to another embodiment of this disclosure, a method for forming a molybdenum-containing film on the surface of a recess on a substrate surface includes forming the molybdenum-containing film by repeating a cycle comprising: supplying a source gas containing molybdenum to the substrate, supplying reactants to the substrate, and forming plasma by applying power to a reactor, wherein the source gas is halogen-free. The reactants may be or include at least one of hydrogen, nitrogen, or mixtures thereof.

[0012] These and other embodiments will be readily understood by those skilled in the art from the following detailed description of specific embodiments with reference to the accompanying drawings. The invention is not limited to any of the specific embodiments disclosed. Attached Figure Description

[0013] Exemplary embodiments of this disclosure can be more fully understood when considered in conjunction with the following illustrative drawings, and by referring to the detailed description and claims.

[0014] Figure 1 A method according to an exemplary embodiment of the present disclosure is shown.

[0015] Figure 2 Another method according to an exemplary embodiment of this disclosure is shown.

[0016] Figure 3 Another method according to an exemplary embodiment of this disclosure is shown.

[0017] Figure 4 Another method according to an exemplary embodiment of this disclosure is shown.

[0018] Figures 5 to 8 Timings suitable for use with various methods according to other exemplary embodiments are shown.

[0019] Figures 9 to 12 The structure according to another embodiment of this disclosure is shown.

[0020] Figure 13 A substrate according to an exemplary embodiment of the present disclosure is shown.

[0021] Figure 14 (a) and (b) in the figure show TEM images of structures according to exemplary embodiments of the present disclosure.

[0022] Figure 15 The relationship between the film properties of molybdenum-containing materials deposited according to examples of this disclosure and plasma power turn-on time is shown.

[0023] Figure 16 The effect of nitrogen gas flow on the crystallinity of molybdenum-containing materials deposited according to examples of this disclosure is shown.

[0024] Figure 17 A system according to another exemplary embodiment of this disclosure is shown.

[0025] 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 may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. Furthermore, the illustrations presented herein are not necessarily intended to be actual views of any particular material, structure, or device, but are merely representations for describing embodiments of this disclosure. Detailed Implementation

[0026] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Furthermore, the description of multiple embodiments having the described features is not intended to exclude other embodiments having additional features or other embodiments comprising different combinations of the described features. Unless otherwise stated, exemplary embodiments or components thereof may be combined in various combinations or may be applied separately from each other. For example, while pre-cleaning, treatment, annealing, and / or polishing steps may be described in conjunction with specific examples, such processes may be used in conjunction with other illustrative examples.

[0027] As described in more detail below, embodiments of this disclosure relate to methods for filling recesses on the surface of a substrate with a molybdenum-containing material and / or for forming a molybdenum-containing film on the surface of recesses on the substrate surface. Exemplary methods can be used to at least partially fill gaps on the surface of a substrate. The exemplary embodiments described herein are particularly applicable to front-end (FEOL), middle-end (MOL), and / or back-end (BEOL) processes for forming electronic devices. For example, the method can be used to deposit molybdenum suitable for an application, such as a low-resistivity gap-filling layer for logic and memory devices. Exemplary methods provide molybdenum exhibiting relatively low effective resistivity and / or other desired properties mentioned herein (e.g., in gaps). The deposited molybdenum can be used, for example, to form contacts within vias and / or as barrier layers and / or as spacers.

[0028] In this disclosure, the gas may 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. Gases other than process gases, i.e., gases not introduced via gas distribution components, other gas distribution devices, etc., may be used, for example, to seal the reaction space, and may include sealing gases, such as rare gases. In some cases, the term precursor may refer to a compound that participates in a chemical reaction to produce another compound, particularly a compound constituting the membrane matrix or the membrane backbone; the term reactant may be used to refer to a gas that reacts with the precursor or its derivatives to form a desired material (e.g., a molybdenum-containing material). In some cases, the term reactant may be used interchangeably with the term precursor. Source gas may be synonymous with precursor. The term inert gas may refer to a gas that does not participate in a chemical reaction and / or does not become part of the membrane matrix to a perceptible degree. Exemplary inert gases include helium, argon, and any combination thereof.

[0029] 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 are formed. 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. Furthermore, a substrate may include various features formed within or on at least a portion of the substrate layers, such as recesses, protrusions, etc. 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. As described in more detail below, the dielectric layer may include one or more recesses.

[0030] As used herein, the terms film and / or layer can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete 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 cases, films or layers can form conductive features, such as contacts, on the surface of a substrate.

[0031] As used herein, a structure may be or include a substrate as described herein. A structure may include features (e.g., recesses) and one or more layers covering the features, such as one or more layers formed according to the methods described herein. A device may include or be formed using a structure.

[0032] As used herein, chemical vapor deposition (CVD) can refer to a vapor deposition process in which volatile precursors and / or reactants react and / or decompose on the surface of a substrate. During a typical CVD process, precursors and reactants can flow into the reaction chamber during an overlap period, during which both precursors and reactants are supplied to the reaction chamber.

[0033] As used herein, the term cyclic deposition can refer to the sequential introduction of one or more precursors and / or reactants into a reaction chamber to deposit a film on a substrate, and includes deposition techniques such as atomic layer deposition and cyclic chemical vapor deposition. In some cases, a cyclic deposition process may include continuously supplying plasma power, precursors, reactants, and / or inert gases to the reaction chamber, and pulses of other components of the precursors, reactants, inert gases, and / or plasma power into the reaction chamber. Such a process may be referred to as cyclic chemical vapor deposition or pulsed chemical vapor deposition. Various examples of cyclic processes are described in more detail below.

[0034] As used herein, the term molybdenum precursor refers to a precursor containing molybdenum. Halogen-free source gases do not include halogens.

[0035] As used herein, the term molybdenum halide precursor refers to a precursor comprising molybdenum and at least one halogen. The halogen may include one or more of chlorine, iodine, and bromine.

[0036] As used herein, the terms molybdenum sulfide halides refer to precursors that include molybdenum, halogens, and sulfide elements. Sulfide elements may include one or more of oxygen (O), sulfur (S), selenium (Se), and tellurium (Te).

[0037] As used herein, the term molybdenum halide refers to a precursor comprising molybdenum, oxygen, and at least one halogen.

[0038] As used in this article, the term reducing agent can refer to a reactant that donates electrons to another substance in a chemical reaction.

[0039] As used herein, the term recess can refer to an opening or cavity disposed between surfaces of a non-planar structure. A recess can also refer to an opening or cavity disposed between opposing inclined sidewalls of two protrusions extending vertically from a substrate surface, or within a notch (e.g., having a single sidewall) extending vertically into the substrate surface; such a recess may be referred to as a vertical recess. The sidewalls may be substantially perpendicular to the surface (e.g., bottom and / or top) or may be inclined. A recess can also refer to an opening or cavity disposed between two opposing substantially horizontal surfaces or between two opposing substantially horizontal portions of a surface, the horizontal surfaces defining at least a portion of the horizontal opening or cavity; such a recess may be referred to as a horizontal gap. The sidewalls between opposing substantially horizontal surfaces or portions may be perpendicular to the surface or portion or may be inclined.

[0040] In this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any range indicated may include or exclude endpoints. Furthermore, 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. Additionally, in this disclosure, the terms “comprising,” “consisting of,” and “having,” as well as related words, may independently mean “generally or broadly comprising,” “including,” “substantially composed of,” or “consisting of” in some embodiments. The meaning of any definition in this disclosure does not necessarily exclude the common and customary meanings in some embodiments. In some cases, percentages indicated herein may be relative or absolute percentages. The term “about” may represent + / - 20%, 10%, 5%, 2%, 1%, or 0.5% of the stated size, orientation, shape, value, etc.

[0041] Although 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 construed as limiting, and the non-limiting example materials given should not be limited by the given example stoichiometry.

[0042] Now turn to the attached diagram. Figure 1 A method 100 according to an exemplary embodiment of the present invention is shown (e.g., filling a recess on the surface of a substrate with a molybdenum-containing material and / or forming a molybdenum-containing film on the surface of the recess). Method 100 includes the steps of providing a substrate 102 and forming a molybdenum-containing film 104.

[0043] During step 102, a substrate is provided in the reaction chamber. The substrate may include any substrate as described herein. As a specific example, the substrate includes a surface that includes recesses. The substrate may be suitable for FEOL, MOL, and / or BEOL processes.

[0044] The reaction chamber used during step 102 may be or include a reaction chamber of a plasma-enhanced chemical vapor deposition reactor system configured to perform the methods described herein. The reaction chamber may be a standalone reaction chamber or part of a cluster of tools or modules. (See below for further details.) Figure 17 An exemplary reaction chamber suitable for use with method 100 is described in more detail.

[0045] Step 102 may include heating the substrate to a desired deposition temperature within the reaction chamber. In some embodiments of this disclosure, step 102 includes heating the substrate to a temperature below 450°C, below 400°C, below 325°C, or below 300°C. Alternatively or additionally, step 102 may include heating the substrate to a temperature greater than 200°C, greater than 275°C, or greater than 300°C. For example, the temperature may be between about 200°C and 450°C, between about 250°C and 400°C, or between about 200°C and about 400°C.

[0046] In addition to controlling the temperature of the substrate, the pressure inside the reaction chamber can also be adjusted. For example, in some embodiments of this disclosure, the pressure inside the reaction chamber during step 102 may be less than 760 Torr or between about 1 Torr and about 10 Torr.

[0047] According to examples of this disclosure, the substrate includes a surface comprising a first material and a second material. In some cases, the first material and the second material may be the same. In other cases, the second material may be different from the first material. In some cases, the first material and the second material may define a feature portion, such as a recess on the substrate surface.

[0048] Figure 13 A substrate 1300 is shown, including a recess 1302 suitable for use during step 102. In the illustrated example, the recess 1302 includes a first surface 1304 containing a first material (e.g., at the bottom of the recess), a second surface 1306 containing a second material (e.g., on the sidewalls 1320 of the recess and the top surface 1318 of the substrate 1300), and a volume 1316. In the illustrated example, the volume 1316 is defined by the first surface 1304, the second surface 1306, and an imaginary line 1314 spanning the top of the gap 1302.

[0049] Recess 1302 is shown as a vertical gap or recess. The aspect ratio (height:width) of recess 1302 can be greater than 2:1, or greater than 5:1, or greater than 10:1, or greater than 25:1, or greater than 50:1, or even greater than 100:1. In some embodiments of this disclosure, the substrate may include one or more substantially horizontal gaps or recesses, wherein the aspect ratio (height:width) of the horizontal gaps can be greater than 2:1, or greater than 5:1, or greater than 10:1, or greater than 25:1, or greater than 50:1. In some cases, the aspect ratio is less than 200:1, less than 150:1, less than 100:1, or less than 50:1.

[0050] exist Figure 13 In the example shown, substrate 1300 includes an insulating (e.g., dielectric) material 1310. According to examples of this disclosure, the insulating material 1310 may be or include a dielectric material, such as an oxide, or a nitride (e.g., silicon oxide or silicon nitride), or a low-k dielectric material (e.g., a metal oxide). In some embodiments, the insulating material 1310 may be or include one or more of silicon dioxide (SiO2), nonstoichiometric silicon oxide, silicon nitride (Si3N4), nonstoichiometric silicon nitride, silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon oxycarbon nitride (SiOCN), silicon carbonitride (SiCN), etc. In some embodiments, the insulating material 1310 may be or include a low-dielectric-constant dielectric material, such as alumina (Al2O3), hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiO2), etc. x One or more of the following: lanthanum oxide (La2O3), etc.

[0051] As shown in the figure, the second surface 1306 may be the surface of the insulating material 1310. Furthermore, the second surface 1306 may extend to the top surface 1318 of the insulating material 1310 and / or the substrate 1300. In other words, the second material may be or include the insulating material 1310.

[0052] The substrate 1300 also includes a material 1308 at the bottom of the recess 1302. Material 1308 may be or include, for example, a semiconductor material. The semiconductor material may be or include, for example, silicon or silicon germanium doped with at least one of phosphorus (P), boron (B), gallium (Ga), arsenic (As), antimony (Sb), or mixtures thereof. In other cases, material 1308 may be conductive. In these cases, material 1308 may include, for example, a metal (such as tungsten, molybdenum, etc.) and / or a metal nitride (such as tungsten nitride, titanium nitride, etc.). The first surface 1304 may be or include the same material as material 1308. In other words, the first material including the first surface 1304 may be or include a semi-conductive or conductive material.

[0053] Refer again Figure 1 According to examples of this disclosure, step 104 includes forming a molybdenum-containing film. The molybdenum-containing film can be formed, for example, by supplying a first source gas containing molybdenum to a substrate, supplying a first reactant to the substrate, and applying a first power to a reactor to form a plasma, thereby forming an activated reactant substance that reacts with the first source gas or its derivatives in the gas phase and / or adsorbed on the substrate. According to examples of these embodiments, the steps of supplying the first reactant and applying the first plasma power overlap in time.

[0054] According to examples of this disclosure, step 104 is non-selective and / or conformal, such that molybdenum is deposited relatively uniformly to cover and contact the first material (e.g., material 1308) and the second material (e.g., material 1310). The selectivity of the process can be expressed as the ratio of the amount of material (e.g., layer thickness) deposited on the first surface to the amount of material (e.g., layer thickness) formed on the combined first and second surfaces. For example, if 10 nm of molybdenum is deposited on the first surface 1304 and 10 nm of molybdenum is deposited on the second surfaces 1306 / 1318, the selective deposition process would be considered non-selective, with a selectivity of 50%. According to examples of this disclosure, the selectivity of the molybdenum-containing material deposited on the first material relative to the second material is between about 40% and about 60% or between about 45% and about 55%. Alternatively or additionally, the selectivity of plasma-deposited molybdenum on the first and second surfaces may be greater than 70%, greater than 80%, greater than 90%, or greater than 95% conformally. As described in more detail below, according to other examples, the deposition may be selective and / or non-conformal.

[0055] During step 104, the temperature and pressure in the reaction chamber can be as described above in conjunction with step 102.

[0056] An exemplary first source gas suitable for use with step 104 comprises a molybdenum precursor, such as a molybdenum halide precursor and / or an organometallic or organometallic molybdenum metal. The molybdenum halide precursor may include one or more of molybdenum chloride precursors, molybdenum iodide precursors, molybdenum bromide precursors, etc. For example, the first source gas may be or include at least one of the following: MoO2Cl2, MoCl4, MoCl5, MoF5, MoCO6, MoO2Br2, tris(2,2,6,6-tetramethylheptane-3,5-diketoic acid)molybdenum [Mo(thd)3], bis(ethylphenyl)molybdenum [Mo(EtBz)2], amide molybdenum source, cyclopentadienylmolybdenum [MoCp] molybdenum source, dicarbonyl [(1,2,3,4,5-η)-1-methyl-2,4-cyclopentadien-1-yl]nitrosomolybdenum [CH3C5H4Mo(CO)2NO], or mixtures thereof.

[0057] The flow rate of the first source gas to the reaction chamber can be controlled and can be greater than zero and less than 1000 sccm, or less than 500 sccm, or less than 100 sccm, or less than 10 sccm, or even less than 1 sccm. For example, the flow rate can be between about 1 and 2000 sccm, between about 5 and 1000 sccm, or between about 10 and about 500 sccm. In some embodiments of this disclosure, such as in the case of a circulating process, the first source gas can be pulsed to the reaction chamber. In this case, the reactants and / or inert gases can be supplied continuously or can be pulsed. The duration of each first source gas pulse can be, for example, between about 0.1 and about 10 seconds.

[0058] According to examples of this disclosure, a first source gas can be purged from the reaction chamber—for example, after each pulse and / or upon completion of the deposition step. Purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, a purging step can be used, for instance, in the sequence of supplying the first source gas to the reactor chamber, stopping the flow of the first source gas to the reaction chamber, supplying a purge gas to the reactor chamber, and supplying reactants to the reactor chamber, wherein the substrate on which the material is deposited does not move. As described herein, in some cases, the reactants can be used as the purge gas when the reactants do not flow to the reaction chamber. In the case of spatial purging, the purging step can take the form of moving the substrate from a first location to which the first source gas (e.g., continuously) is supplied via a purge gas curtain to a second location to which the reactants (e.g., continuously) are supplied. The purging time can be, for example, about 0.01 seconds to about 20 seconds, about 0.05 seconds to about 20 seconds, or about 1 second to about 20 seconds, or about 0.5 seconds to about 10 seconds, or between about 1 second and about 7 seconds.

[0059] Exemplary (e.g., first) reactants suitable for use with step 104 include reactants containing at least one of hydrogen, nitrogen, or mixtures thereof. For example, the first reactant may be or include at least one of the following: Ar, H2, NH3, NH4, N2H4, B2H6, N2, silane, alone, or any mixture thereof.

[0060] (For example, the first) The flow rate of reactant to the reaction chamber can be greater than zero and less than 100 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 1 slm, or even less than 0.1 slm. For example, the flow rate can be between about 0.1 and 30 slm, about 5 to 15 slm, or equal to or greater than 10 slm. In the case of a cyclic deposition process, the reactant can be pulsed—for example, with a duration between about 0.01 seconds and about 180 seconds, between about 0.05 seconds and about 60 seconds, or between about 0.1 seconds and about 30 seconds. As described herein, in some cases, the reactant can flow continuously through one or more deposition cycles.

[0061] In some cases, such as after a reactant pulse and / or at the completion of a deposition step, purging may be employed to remove any excess reactants and / or reaction byproducts from the reaction chamber. Purging may be performed as described above.

[0062] According to an example of this disclosure, during step 104, a plasma is formed in the reaction chamber. The plasma can be formed simultaneously with the provision of the molybdenum precursor and / or the provision of the first reactant and / or the provision of an inert gas. An inert gas, such as argon and / or helium, can be provided during step 104 to facilitate plasma formation. The flow rate of the inert gas can be between about 500 sccm and about 5000 sccm, or between about 1000 sccm and about 3000 sccm.

[0063] Figures 5 to 8 Various examples of applications according to the illustrated embodiments are shown. Figure 1 Step 104 and the following description Figure 2 Method 200 Figure 3 Method 300 and Figure 4 The exemplary timing of method 400. Methods such as methods 100-400 can be used to deposit Mo metal, MoN, MoC, MoCN, or mixtures thereof.

[0064] As described in more detail below, according to some examples of exemplary embodiments, the supply of a first source gas and the supply of a first reactant are performed sequentially. For example, the method may include a PEALD-type sequence comprising pulsed supply of a first source gas (e.g., MoO2Cl2), followed by purging, followed by (e.g., a first) reactant plasma (e.g., hydrogen plasma), followed by purging. This cycle may be repeated X times until the desired thickness is achieved. Alternatively, the method may include a pulsed PECVD-type sequence comprising forming a reactant (e.g., hydrogen) plasma; pulsed supply of a first source gas (e.g., MoO2Cl2) while the hydrogen plasma is activated; maintaining the reactant (e.g., hydrogen) plasma on for a period of time; and repeating the pulsed supply of the first source gas step until the desired thickness is achieved; and then shutting off the plasma. According to another example, a pulsed PECVD-type sequence may be used. For example, the sequence may include: activating a continuous flow of a first source gas (e.g., MoO2Cl2); performing a pulsed reactant (e.g., hydrogen) plasma while the first source gas is flowing; maintaining the continuous flow of the first source gas for a period of time and repeating the step of pulsed plasma flow X times until the desired thickness is achieved, and then shutting off the plasma. In some cases, the first reactant is supplied in a pulsed manner, while the first source gas is supplied simultaneously (e.g., continuously). In other cases, the first source gas is supplied in a pulsed manner, while the first reactant is supplied simultaneously (e.g., continuously). As described herein, the plasma can be a capacitively coupled plasma (CCP) generated between the base and the spray head. Alternatively or additionally, the plasma can be a plasma generated further upstream of the substrate above the spray head. This can be an ICP plasma, a microwave-generated plasma, a CCP plasma, or other types of plasma.

[0065] Figure 5 A timing sequence 500 according to an example of this disclosure is shown. Sequence 500 is a plasma-enhanced cyclic deposition process, such as a PEALD process. In the illustrated example, sequence 500 includes continuously supplying inert gas 502 through one or more deposition cycles 504, supplying a first source gas for a first gas source pulse 506, supplying a first reactant for a first reactant pulse 508, and applying a first power to the reactor for a first power pulse 510. The flow rates, applied power, time, etc., of steps 502 and 506-508 can be as described above. In the illustrated example, the first gas source pulse 506 does not overlap with the first reactant pulse 508 or the first power pulse 510. According to an example of this disclosure, the steps of supplying the first reactant and applying the first plasma power overlap in time. For example, as shown, the start and / or end times of the first reactant pulse 508 and the first power pulse 510 can be substantially the same. As shown, sequence 500 may include a purge cycle 512 and / or a purge cycle 514 during which the inert gas continues to flow.

[0066] Figure 6 A timing sequence 600 according to another plasma-enhanced cyclic deposition process is shown. Timing 600 includes continuously supplying inert gas 602 through one or more deposition cycles 604, supplying a first source gas up to a first gas source pulse 606, continuously supplying a first reactant 608 through one or more deposition cycles 604, and applying a first power to the reactor up to a first power pulse 610. The flow rates, applied power, and time of steps 602 and 606-608 can be as described above. In the illustrated example, the first gas source pulse 606 does not overlap with the first power pulse 610. According to an example of this disclosure, the steps of supplying the first reactant and applying the first plasma power overlap in time. For example, as shown, step 608 can begin before the first deposition cycle and end after the last deposition cycle. As shown, sequence 600 may include purge cycles 612 and / or purge cycles 614 during which the inert gas continues to flow. Timing 600 is similar to timing 500, except that the flow of the first reactant is continuous during one or more deposition cycles.

[0067] Figure 7 Another timing sequence 700 according to an example of this disclosure is shown. Timing sequence 700 includes thermal deposition and plasma processing. Timing sequence 700 includes continuously supplying inert gas 702 through one or more deposition cycles 704, supplying a first source gas to a first gas source pulse 706, supplying a first reactant to a first reactant pulse 708, applying a first power to the reactor to a first power pulse 710, and supplying a second reactant to a second reactant pulse 716. The flow rates, applied power, and times of steps 702 and 706-710 can be as described above. In the illustrated example, the first gas source pulse 706 does not overlap with the first reactant pulse 708, the first power pulse 710, or the second reactant pulse 716. According to an example of this disclosure, the steps of supplying the first reactant and applying the first plasma power overlap in time. For example, as shown, the start and / or end times of the first reactant pulse 708 and the first power pulse 710 can be substantially the same. Sequence 700 may include a purge cycle 712 and / or a purge cycle 714 during which the inert gas continues to flow. According to another example, the method includes supplying a second reactant and stopping the supply of the second reactant before applying a first power to the reactor. An exemplary second reactant is described below. The pulse time and flow rate of the second reactant may be the same as or similar to the pulse time and flow rate of the first reactant.

[0068] Figure 8Another timing sequence 800 according to an example of this disclosure is shown. Timing sequence 800 illustrates a repeatable CVD cycle. Timing sequence 800 includes continuously supplying inert gas 802 through one or more deposition cycles, supplying a first source gas to a first gas source pulse 806, supplying a first reactant to a first reactant pulse 808, and applying a first power to the reactor to a first power pulse 810. The flow rates, applied power, time, etc., of steps 802 and 806-810 can be as described above. In the illustrated example, the first gas source pulse 806 overlaps with the first reactant pulse 808 and the first power pulse 810. According to an example of this disclosure, the steps of supplying the first reactant and applying the first plasma power overlap in time. For example, as shown, the start and / or end times of the first reactant pulse 808 and the first power pulse 810 can be substantially the same. The first gas source pulse 806 can start after the start of the first reactant pulse 808 and the first power pulse 810 and / or end before the end of the first reactant pulse 808 and the first power pulse 810. Sequence 800 may include a purging cycle 812 during which the inert gas continues to flow.

[0069] Figure 2 Another method 200 according to an example of this disclosure is shown. Method 200 may be a conformal deposition process, a zone-selective deposition process, or a topography-selective deposition process. Method 200 may be used to completely fill recesses on a substrate. In some cases, method 200 may include additional deposition steps to fill the recesses.

[0070] Method 200 includes the following steps: providing a substrate 202; optionally performing pre-cleaning 204; optionally performing a pre-deposition treatment 206; supplying one or more source gases 208; supplying reactants 210; optionally supplying a second reactant 212; supplying a first deposition power 214; optionally performing a post-deposition treatment 216; optionally annealing 218; and optionally chemical mechanical polishing 220. Method 200 can be suitably used to form contacts within an insulating material on a substrate surface.

[0071] Step 202 can be as described above in conjunction with step 102 of method 100. For example, the substrate may include a recess formed in an insulating (e.g., dielectric) material and having a bottom surface, the bottom surface being or comprising a semiconductive material or a natural oxide formed directly on the semiconductive material.

[0072] During step 204, native oxides can be removed from the surface of the substrate. For example, native oxides can be removed from the semiconductive surface at the bottom of the recess. Native oxides can be removed using, for example, a fluorinated gas, a fluorinated radical, or a mixture thereof, such as NF3 radicals (e.g., generated using remote plasma) and / or NH3-based cleaning. Alternatively or additionally, step 204 may include immersing the substrate in a fluorinated liquid, such as dilute HF acid, to remove native oxides and / or HF vapor-based cleaning. Alternatively or additionally, step 204 may include an atomic layer etching process. According to examples of this disclosure, the pre-cleaning step 204 includes a drying or vapor-based process performed in a reaction chamber grouped with (e.g., different from) the deposition reaction chamber, such that any air exposure to the pre-cleaned surface is reduced between pre-cleaning and the subsequent deposition process. Pre-cleaning may include a wet pre-cleaning process followed by a dry or vapor-based process. Pre-cleaning can ensure that the interface between the substrate surface and the subsequently deposited molybdenum-containing material is substantially oxygen-free (e.g., less than 1 e) at the interface. 15 or less than 1e 14 oxygen atoms / cm 2 The process can be performed with a concentration of oxygen that is substantially less than the amount of natural oxides on the surface. Step 204 may be performed appropriately prior to the deposition process 207.

[0073] The pre-deposition treatment step 206 can be performed in the same reaction chamber used for deposition. According to an example of this disclosure, the pre-deposition treatment step 206 includes a hydrogen plasma treatment, which includes supplying a hydrogen-containing gas to the reaction chamber and applying plasma power to form an activated material from the hydrogen-containing gas within the reaction chamber. The hydrogen-containing gas can be, or includes, for example, hydrogen or other hydrogen-containing gases described herein. The power used to form the plasma during step 206 and / or step 216 can be at least one of high-frequency power, low-frequency power, or a mixture thereof, with an intensity of about 500 W or less. The power during step 206 and / or step 216 can be applied in pulses with a duty cycle of about 70% or less (e.g., about 10% to about 70%). According to an example of this disclosure, the method may include treatment using hydrogen plasma before, after, or both of forming a molybdenum-containing film.

[0074] According to the example of method 200, deposition process 207 is a plasma-assisted deposition process, which may be the same as or similar to step 104 described above. Deposition process 207 can be used to deposit at least one of, for example, Mo metal, MoN, MoC, MoCN, MoSi, or mixtures thereof. Figure 5 Timing 500 in Figure 6 Timing 600 in Figure 7 Timing 700 or Figure 8 The timing sequence 800 can be used in the deposition process 207.

[0075] During step 208, one or more source gases comprising a first source gas including molybdenum are supplied to the substrate. The first source gas may be a molybdenum precursor as described above and may be supplied using the conditions mentioned above. In some cases, method 200 may also include providing at least a second source gas.

[0076] During step 210, a first reactant is supplied to the substrate. The first reactant may be combined as described above. Figure 1 The process described in step 104 can be supplied under the conditions described above. For example, the first reactant includes at least one of hydrogen, nitrogen, or mixtures thereof, such as at least one of H2, NH3, NH4, N2H4, B2H6, N2, silane, or mixtures thereof.

[0077] In some cases, a second reactant may be provided during step 212. According to examples of these embodiments, the second reactant is or includes at least one of H2, diiodoethane (C2H2I2), silane, diisothane, propane, alkylsilane, alkyliodide, silicon iodide, or mixtures thereof.

[0078] During step 214, deposition power is applied to form a plasma within the reaction chamber. According to examples of these embodiments, the power is at least one of high-frequency power, low-frequency power, or a mixture thereof, with an intensity of about 500 W or less. According to another example, the power is applied in pulses with a duty cycle of about 70% or less, or between about 10% and about 70%. The duty cycle can be defined as a percentage of plasma power on time / (on time + off time).

[0079] Post-deposition processing step 216 can be used to densify and / or modify the material deposited during deposition process 207. Although no bonding... Figure 2 Shown separately, but alternatively, the deposition process could be a thermal ALD process, followed by a post-deposition treatment step 216. Step 216 can be performed after one or more deposition cycles and / or after deposition is complete. A specific example is a thermal ALD process using MoEtBz2 and diiodoethane, wherein argon and hydrogen plasma treatment is performed after one or more thermal ALD cycles. Figure 7 An exemplary timing diagram for this process is shown in the figure.

[0080] Annealing 218 can be used to form a contact between the substrate surface and the deposited molybdenum-containing material. In some cases, the annealing process is a thermal annealing process. During the annealing process, the substrate temperature can be 500°C or higher, or between about 400°C and about 650°C. During this step, the deposited molybdenum-containing film can be mixed with the substrate material at the interface between the deposited molybdenum-containing material and the substrate surface.

[0081] During step 220, chemical mechanical planarization can be used to planarize the surface of the substrate. Step 220 can be performed appropriately after step 218 (e.g., directly).

[0082] Figure 3 Another method 300 according to an example of this disclosure is shown. Method 300 includes the steps of: providing a substrate 302, optionally performing pre-cleaning 304, forming a molybdenum-containing film 306, optionally forming a capping layer 308, annealing 310, forming a metallic film 312, and optionally chemically mechanically polishing 314.

[0083] Steps 302-306 can be combined with the above. Figure 2 Steps 202, 204, and 207 are described as identical or similar and may optionally include the surface treatments described above. For example, step 306 may include forming a film comprising at least one of Mo, MoN, MoCN, MoSi, or mixtures thereof. The molybdenum-containing film formed during step 306 may partially fill recesses (e.g., contact openings) on the substrate.

[0084] Step 308 of forming the capping layer may include, for example, depositing a layer containing a metal nitride (such as TiN, MoN, or TaN). The thickness of the capping layer may be from about 2 nm to about 20 nm.

[0085] After the capping layer is formed, a thermal annealing process may be performed during step 310. The temperature during the thermal annealing process may be as described above in conjunction with step 218. For example, the thermal annealing temperature may be about 500°C or higher. Alternatively, thermal annealing as described herein may be performed after step 312.

[0086] During step 312, a metallic film is deposited, which covers the molybdenum-containing film (e.g., a capping layer and a molybdenum-containing film) to fill the recess. The metallic film may include at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), titanium (Ti), nickel (Ni), platinum (Pt), tantalum (Ta), niobium (Nb), scandium (Sc), or mixtures thereof. Step 312 may suitably include supplying a metallic source gas to the substrate and supplying a second reactant to the substrate.

[0087] The metallic source gas includes at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), titanium (Ti), nickel (Ni), platinum (Pt), tantalum (Ta), niobium (Nb), scandium (Sc), or mixtures thereof. For example, the metallic source gas may be or include metal halides, metal halide oxides, organometallic compounds (e.g., β-diketones), or organometallic compounds similar to those described above in connection with molybdenum precursors. The second reactant may include the reactants described herein (e.g., the first or second reactant).

[0088] After the recess is filled with a metallic film, the excess metallic film material can be removed by chemical mechanical polishing step 314.

[0089] Figure 4 Another method 400 according to an example of this disclosure is shown. Method 400 includes the steps of: providing a substrate 402, optionally pre-cleaning 404, forming a molybdenum-containing film 406, forming a metallic film 408, optionally annealing 410, and optionally chemically mechanically polishing 412.

[0090] Steps 402 and 404 may be the same as or similar to steps 202 and 204, 302 and 304 described above. Step 406 may be the same as or similar to step 306 described above, except that step 406 is performed using only a halogen-free molybdenum precursor. For example, the source gas used during step 406 may be or include at least one of MoCO6, tris(2,2,6,6-tetramethylheptane-3,5-diketoic acid)molybdenum [Mo(thd)3], bis(ethylphenyl)molybdenum [Mo(EtBz)2], amide molybdenum source, cyclopentadienylmolybdenum [MoCp] molybdenum source, dicarbonyl [(1,2,3,4,5-η)-1-methyl-2,4-cyclopentadien-1-yl]nitrosomolybdenum [CH3C5H4Mo(CO)2NO], or mixtures thereof. Reactants may include any of the above-described (e.g., the first) reactants. According to examples, molybdenum-containing films include at least one of Mo, MoN, MoC, MoCN, or mixtures thereof. The molybdenum-containing film can partially fill the recesses.

[0091] Step 406 can be suitably used to form a barrier layer between the substrate and the metallic film deposited during step 408. The above combination can be used. Figure 5-8 Step 406 may be performed at any of the described timings. The thickness of the molybdenum-containing film may be less than 10 nm, less than 7 nm, or less than 5 nm.

[0092] During step 406, the temperature and pressure within the reaction chamber can be as described above. In some cases, step 406 is carried out at a temperature of about 350°C or lower, or about 320°C or lower.

[0093] Step 408 can be related to the above. Figure 3 Step 312 is the same as or similar to step 408. For example, step 408 may include forming a metallic film on a molybdenum-containing film containing at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), copper (Cu), or mixtures thereof, to fill recesses or contact openings in the substrate after the molybdenum-containing film is formed. In some cases, step 408 may be a thermal ALD process.

[0094] During step 410, the metallic film may be annealed. Step 410 can be combined with the above... Figure 3The steps in step 310 are the same as or similar to those in the previous steps.

[0095] During step 412, chemical mechanical polishing is used to planarize the surface of the substrate.

[0096] Figures 9 to 12 The structures formed during various method steps according to examples of this disclosure are shown.

[0097] Figure 9 A structure 902 is shown comprising a semiconductive surface 904 within a recess 906 on a surface of a substrate 901. The recess 906 may be formed within an insulating material 908. Structure 902 includes a native oxide 910 covering the semiconductive surface 904 of a semiconductor material 905. Structure 902 may also include a semiconductor (e.g., Si) pillar 903. During a pre-cleaning step (e.g., step 404), the native oxide 910 is removed, thereby forming structure 912. Figure 9 An example is shown in which a molybdenum-containing film 916 is conformally and non-selectively formed within a recess 906 to form structure 914. As described above, optional annealing can be performed prior to the CMP process to form annealed material 917. Structure 918 is formed during or after the annealing process. Structure 920 is formed after the CMP process. The above-described method 100 can be used to form, for example. Figure 9 The structure shown.

[0098] Figure 10 A structure 1002 is shown comprising a semiconducting surface 1004 on a semiconductor material 1005 within a recess 1006 on the surface of a substrate 1001. The recess 1006 may be formed within an insulating material 1008. Structure 1002 includes a native oxide 1010 covering the semiconducting surface 1004. During a pre-cleaning step (e.g., step 404), the native oxide 1010 is removed, thereby forming structure 1012. Figure 10 Another example is shown in which a molybdenum-containing film 1016 is conformally and non-selectively formed within a recess 1006 to form structure 1014. In this case, the molybdenum-containing film 1016 can be a barrier layer as described herein. After the barrier layer is formed, a subsequent metallic film 1018 can be formed on layer 1016 (e.g., directly) to fill the recess 1006, for example, to form a contact within the recess 1006. As described above, optional annealing (to form annealed material 1019) and / or CMP processes can be performed. Structure 1022 is formed during or after the annealing process (e.g., annealing step 410). Figure 10 The structure shown can be formed using, for example, the method 400 described above.

[0099] Figure 11A structure 1102 is shown comprising a semiconductive surface 1104 within a recess 1106 on the surface of a substrate 1101. The recess 1106 may be formed within an insulating material 1108. Structure 1102 includes a native oxide 1110 covering the semiconductive surface 1104. During a pre-cleaning step (e.g., step 304), the native oxide 1110 is removed, thereby forming structure 1112. Figure 11 Another example is shown in which a molybdenum-containing film 1116 is conformally and non-selectively formed within a recess 1106 to form structure 1114. After forming the molybdenum-containing film 1116, a capping layer 1118 is formed on the molybdenum-containing film 1116 (e.g., directly) to form structure 1120. The capping layer 1118 can be formed as described above in conjunction with step 308. Structure 1122 is formed during or after the annealing process. Structure 1124 is formed after the metal filling process to deposit a metallic film 1126, such as metallic film 1018, as described above. It can be formed using, for example, the method 300 described above. Figure 11 The structure shown.

[0100] Figure 12 A structure 1202 is shown comprising a semiconductive surface 1204 within a recess 1206 on the surface of a substrate 1201. The recess 1206 may be formed within an insulating material 1208. Structure 1202 includes a native oxide 1210 covering the semiconductive surface 1204. During a pre-cleaning step (e.g., step 204), the native oxide 1210 is removed, thereby forming structure 1212. Figure 12 This illustration describes an example in which a molybdenum-containing film 1215 is selectively formed within the recess 1206 to form structure 1214. Structure 1216, including an annealed film 1217, is formed during or after the annealing process. Structure 1218 is formed after the CMP process. It can be formed using, for example, the methods 100 and / or 200 described above. Figure 12 The structure shown.

[0101] Figure 14 (a) and (b) in the figure respectively show the results based on Figure 1 TEM images of structures with target thicknesses of 10 nm and 5 nm were generated using this method. As shown in the figure, the molybdenum-containing film exhibits good conformability.

[0102] Figure 15 The sheet resistivity, refractive index (n), extinction coefficient (k), 3 sigma non-uniformity percentage (3S NU%), growth rate per cycle (GPC), and thickness as a function of RF power on-time are shown during the deposition process of molybdenum-containing films: MoC, MoCN, and MoN. As shown, increasing the plasma power on-time leads to a decrease in resistivity for MoC and MoCN films. The increasing trends of n and k result in lower resistivity, indicating improved crystallinity, crystalline phase, and more metallic bonding.

[0103] Figure 16 The resistivity, refractive index (n), extinction coefficient (k), three-sigma non-uniformity percentage (3S NU%), and thickness as a function of nitrogen flow (e.g., N2) are shown. Low flow rates of N2 provide molybdenum-containing films with low resistivity. Furthermore, the low flow rate of N2 further reduces resistivity due to improved crystallinity and longer RF power on-time.

[0104] Now go to Figure 17 The present invention illustrates a system 1700 according to an exemplary embodiment of the present disclosure. The system 1700 can be used to perform the methods described herein and / or various method steps as described herein.

[0105] In the illustrated example, system 1700 includes one or more reactors 1713 (each including one or more reaction chambers 1714), a precursor source 1702 in fluid communication with one or more reaction chambers 1714 via a first flow control valve 1703 and line 1708, a reactant source 1704 in fluid communication with one or more reaction chambers 1714 via a second flow control valve 1705 and line 1710, a purge source 1706 in fluid communication with one or more reaction chambers 1714 via a third flow control valve 1707 and line 1712, an exhaust source 1716, and a controller 1718. System 1700 may optionally include a remote plasma source 1720 and / or a direct device 1736, including a plasma power source 1738 to excite gases from one or more sources 1702, 1704, and 1706 or another gas source (e.g., during a cleaning or deposition step). Furthermore, as shown in the figure, system 1700 may include one or more pressure flow controllers or mass flow controllers 1728, 1730, and 1732, respectively, associated with lines 1708, 1710, and 1712. Additionally, to facilitate rapid, relatively large doses of molybdenum precursors, system 1700 may include an accumulator 1734 in fluid communication between the precursor source 1702 and the reaction chamber 1714. Accumulator 1734 can allow for higher precursor dose delivery compared to conventional reactor systems. In one example, the accumulator may be an LDS (Liquid Delivery System).

[0106] The reaction chamber 1714 may include any suitable reaction chamber, such as a plasma-enhanced atomic layer deposition (ALD) or chemical vapor deposition (CVD) reaction chamber. The reaction chamber 1714 may include a gas distribution system 1722, such as a spray head (which may form part of a direct or indirect plasma electrode), and a base 1724 for holding the substrate 1726.

[0107] Exhaust source 1716 may include one or more vacuum pumps to remove gases from reaction chamber 1714. Substrate 1726 may be any substrate or structure described herein.

[0108] Precursor source 1702 may include a container and a molybdenum precursor, such as one or more molybdenum precursors described herein.

[0109] The reactant source 1704 may include a container and reactants. The reactants may be or include the first or second reactants as described herein.

[0110] The purge source 1706 may include a container and one or more purge gases. For example, the purge source 806 may include one or more of nitrogen, argon, etc.

[0111] Controller 1718 may include electronic circuitry and software to selectively operate flow control valves 1703-1707, manifolds, heaters, pumps, and other components included in system 1700. Such circuitry and components can be operated to introduce precursors, reactants, and purge gases from respective sources 1702-1706. Controller 1718 may control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chambers, the pressure within one or more reaction chambers 1714, and various other operations to provide appropriate operation of system 1700. Controller 1718 may include software to electrically or pneumatically operate the flow control valves to supply precursors from precursor source 1702 and reactants from reactant source 1704 to one or more reaction chambers 1714. Controller 1718 may also include software to provide purge gases into and out of one or more reaction chambers 1714.

[0112] The controller 1718 may include modules, such as software or hardware components like an FPGA or ASIC, that perform certain tasks. These modules may be advantageously configured to reside on an addressable storage medium of the control system and to perform one or more processes.

[0113] For example, controller 1718 may be configured to operate the flow control valve and heater to non-selectively or conformally deposit plasma-deposited molybdenum on a first surface of the substrate (e.g., at the bottom of the gap) relative to a second surface (e.g., on the sidewall of the gap) to at least partially fill the gap, and subsequently deposit additional molybdenum on both the first and second surfaces. Alternatively, controller 1718 may be configured to selectively deposit molybdenum and subsequently use a plasma-assisted process to non-selectively or conformally deposit molybdenum on the selectively deposited molybdenum.

[0114] Other configurations of system 1700 are possible, including different numbers and types of precursor and reactant sources, as well as purge gas sources. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor sources, and purge gas sources exist to achieve the objective of selectively supplying gases to one or more reaction chambers 1714. Additionally, for illustrative purposes and to simplify the description, many components have been omitted; such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0115] The exemplary embodiments described above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, the scope of which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to fall within the scope of the invention. In fact, various modifications to this disclosure, such as alternative useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. These modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for filling a recess on the surface of a substrate with a molybdenum-containing material, comprising: Provide a substrate in the reactor; and A molybdenum-containing film is formed by repeating the following cycle: A first source gas, including molybdenum, is supplied to the substrate; Supplying the first reactant to the substrate; and A first power is applied to the reactor to form plasma, thereby generating activated reactant material that reacts with a first source gas or its derivatives adsorbed on the substrate. The steps of supplying the first reactant and applying the first plasma power overlap in time.

2. The method according to claim 1, wherein, The first source gas includes at least one of the following: MoO2Cl2, MoCl4, MoCl5, MoF5, MoCO6, MoO2Br2, tris(2,2,6,6-tetramethylheptane-3,5-diketoic acid)molybdenum [Mo(thd)3], bis(ethylphenyl)molybdenum [Mo(EtBz)2], amide molybdenum source, cyclopentadienylmolybdenum [MoCp] molybdenum source, dicarbonyl [(1,2,3,4,5-η)-1-methyl-2,4-cyclopentadien-1-yl]nitrosylmolybdenum [CH3C5H4Mo(CO)2NO] or a mixture thereof.

3. The method according to claim 1, wherein, The first reactant contains at least one of hydrogen, nitrogen, or a mixture thereof.

4. The method according to claim 3, wherein, The first reactant contains at least one of H2, NH3, NH4, N2H4, B2H6, N2, silane, or any mixture thereof.

5. The method according to claim 1, wherein, The method also includes supplying a second reactant before applying the first power to the reactor.

6. The method according to claim 5, wherein, The second reactant includes at least one of the following: H2, diiodoethane (C2H2I2), silane, diisothiazoline, propane, alkylsilane, alkyliodide, silicon iodide, or a mixture thereof.

7. The method according to claim 1, wherein, The method further includes performing pre-cleaning to remove native oxides from the substrate before forming the molybdenum-containing film.

8. The method according to claim 7, wherein, The pre-cleaning is performed while supplying at least one of a fluorine-containing gas, a fluorine-containing free radical, or a mixture thereof.

9. The method according to claim 7, wherein, The pre-cleaning is performed via an atomic layer etching process.

10. The method according to claim 7, wherein, The pre-cleaning is performed by immersing the substrate in a fluorine-containing liquid.

11. The method according to claim 7, wherein, The pre-cleaning is carried out in a different reactor than the one in which the molybdenum-containing film is formed, in order to reduce the exposure of the substrate to air.

12. The method according to claim 1, wherein, The substrate comprises at least one of the following: silicon, silicon germanium doped with at least one of phosphorus (P), boron (B), gallium (Ga), arsenic (As), and antimony (Sb), or a mixture thereof, and wherein the molybdenum-containing film contacts the substrate through the recess.

13. The method according to claim 1, wherein, The method further includes supplying a second source gas containing silicon to the reactor to form a membrane containing silicon and molybdenum.

14. The method of claim 1, wherein the processing is performed using hydrogen plasma before, after, or both of forming the molybdenum-containing film.

15. The method according to claim 1, wherein, The method is performed in a temperature range between approximately 200°C and approximately 400°C.

16. The method according to claim 1, wherein, The first power is at least one of high-frequency power, low-frequency power, or a combination thereof, having an intensity of about 500W or less.

17. The method according to claim 16, wherein, The first power is applied in pulses with a duty cycle of about 70% or less.

18. The method according to claim 14, wherein, The second power is at least one of high-frequency power, low-frequency power, or a combination thereof, having an intensity of about 500W or less.

19. The method according to claim 18, wherein, The second power is applied in pulses with a duty cycle of about 70% or less.

20. The method according to claim 1, wherein, The supply of the first source gas and the supply of the first reactant are carried out sequentially.

21. The method according to claim 1, wherein, The first reactant is supplied in a pulse while the first source gas is being supplied.

22. The method according to claim 1, wherein, The first source gas is supplied in a pulse while the first reactant is being supplied.

23. The method according to claim 1, wherein, The method further includes performing thermal annealing after forming the molybdenum-containing film, followed by chemical mechanical polishing (CMP).

24. The method according to claim 23, wherein, The heat annealing is performed at a temperature of approximately 500°C or higher.

25. The method according to claim 1, wherein, The molybdenum-containing film comprises at least one of Mo metal, MoN, MoC, MoCN, MoSi, or a mixture thereof.

26. A method for filling a recess on the surface of a substrate with a molybdenum-containing material, comprising: Provide a substrate in the reactor; Perform pre-cleaning to clean the surface of the substrate; A molybdenum-containing film is conformally formed on the surface of the recess by repeating the following cycle: A first source gas, including molybdenum, is supplied to the substrate; The first reactant is supplied to the substrate; and Provides a first deposition power to form an activating substance from the first reactants; as well as Forming a metallic film on a molybdenum-containing film to fill the recess includes: Supply metallic source gas to the substrate; and The second reactant is supplied to the substrate.

27. The method according to claim 26, wherein, The metallic source gas includes at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), titanium (Ti), nickel (Ni), platinum (Pt), tantalum (Ta), niobium (Nb), scandium (Sc), or mixtures thereof.

28. The method according to claim 26, wherein, The first reactant contains at least one of hydrogen, nitrogen, or a mixture thereof.

29. The method according to claim 28, wherein, The first reactant contains at least one of H2, NH3, NH4, N2H4, B2H6, N2, silane, or any mixture thereof.

30. The method according to claim 26, wherein, The second reactant includes at least one of the following: H2, diiodoethane (C2H2I2), silane, diisothiazoline, propane, alkylsilane, alkyliodide, silicon iodide, or a mixture thereof.

31. The method according to claim 26, wherein, The method further includes performing thermal annealing after filling the recess, followed by chemical mechanical polishing (CMP).

32. The method according to claim 31, wherein, The heat annealing is performed at a temperature of approximately 500°C or higher.

33. The method of claim 26, further comprising forming a capping layer on the molybdenum-containing film and then performing thermal annealing.

34. The method of claim 33, further comprising performing chemical mechanical polishing (CMP) after filling the recess in the substrate.

35. The method according to claim 33, wherein, The coating layer comprises a metal nitride.

36. The method according to claim 33, wherein, The heat annealing is performed at a temperature of approximately 500°C or higher.

37. The method according to claim 26, wherein, The molybdenum-containing film contains at least one of Mo, MoN, MoCN, or a mixture thereof.

38. The method according to claim 26, wherein, The molybdenum-containing film partially fills the recess.

39. The method according to claim 26, wherein, The metallic film includes at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), titanium (Ti), nickel (Ni), platinum (Pt), tantalum (Ta), niobium (Nb), scandium (Sc), or mixtures thereof.

40. A method for forming a molybdenum-containing film on the surface of a recess on a substrate surface, the method comprising: Provide a substrate in the reactor; and A molybdenum-containing film is formed by repeating the following cycle: Supply a source gas containing molybdenum to the substrate; Supplying reactants to the substrate; and Plasma is formed by applying power to a reactor in which the source gas is halogen-free.

41. The method according to claim 40, wherein, The source gas includes at least one of the following: MoCO6, tris(2,2,6,6-tetramethylheptane-3,5-diketoic acid)molybdenum [Mo(thd)3], bis(ethylphenyl)molybdenum [Mo(EtBz)2], amide molybdenum source, cyclopentadienylmolybdenum [MoCp] molybdenum source, dicarbonyl [(1,2,3,4,5-η)-1-methyl-2,4-cyclopentadien-1-yl]nitrosomolybdenum [CH3C5H4Mo(CO)2NO], or a mixture thereof.

42. The method according to claim 40, wherein, The reactants include at least one of hydrogen, nitrogen, or a mixture thereof.

43. The method according to claim 42, wherein, The reactants include at least one of H2, NH3, NH4, N2H4, B2H6, N2, silane, or mixtures thereof.

44. The method of claim 40, wherein, The method is performed at a temperature of approximately 350°C or lower.

45. The method according to claim 40, wherein, The power is at least one of high-frequency power, low-frequency power, or a combination thereof, and has an intensity of about 500W or less.

46. ​​The method according to claim 45, wherein, The power is applied in pulses with a duty cycle of approximately 70% or less.

47. The method of claim 40, wherein, The method further includes forming a metallic film on the molybdenum-containing film, comprising at least one of molybdenum (Mo), tungsten (W), cobalt (Co), ruthenium (Ru), copper (Cu), or a mixture thereof, to fill the recess, and then performing chemical mechanical polishing (CMP).

48. The method of claim 40, wherein, The molybdenum-containing film contains at least one of Mo, MoN, MoC, MoCN, or a mixture thereof.

49. The method according to claim 40, wherein, The molybdenum-containing film partially fills the recess.

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