Method of reducing deposition rate

Abstract

A deposition method exhibiting a slower growth rate is disclosed. Some embodiments of the present disclosure provide a CVD method utilizing a halide-containing growth inhibitor as a co-reactant with metal halide precursors and reactants. Some embodiments of the present disclosure are directed to CVD and ALD methods including exposing a substrate surface to a pretreatment comprising a halide-containing growth inhibitor.

Description

Technical Field

[0001] Embodiments of this disclosure generally relate to methods for reducing the deposition rate of metallic materials. In particular, embodiments of this disclosure relate to methods for inhibiting growth by exposure to halide-containing growth inhibitors. Background Technology

[0002] Controlling the deposition rate is a recurring goal in semiconductor manufacturing. One application of particular interest in controlling the deposition rate is filling substrate features (e.g., vias, trenches, etc.) with gap-filling materials.

[0003] Traditional deposition methods can produce excessively high deposition rates, causing material to accumulate near the openings of the feature without filling the bottom. If these openings are not kept open, the feature may become closed, resulting in porosity within the feature. Typical gap-filling methods can also create seams in the deposited material near the center of the feature.

[0004] These defects (e.g., seams and porosity) can cause problems during downstream processing. These problems are often most clearly demonstrated through etching processes, which affect defects differently than the surrounding gap fill. These defects can also cause the pattern / device, including the gap fill, to deteriorate over time, leading to device failure.

[0005] For some metal gap filling applications (such as 3D NAND, DRAM and MEOL logic), in complex recessed structures where conventional ALD (with conformal coverage) fails, superconformal growth or bottom-up gap filling is required to complete the gap filling.

[0006] Therefore, there is a need for deposition processes that provide lower deposition rates for metallic materials, ultraconformal deposition, and / or bottom-up gap filling. Summary of the Invention

[0007] One or more embodiments of this disclosure relate to a deposition method that includes exposing a substrate surface to a halide-containing growth inhibitor and exposing the substrate surface to a metal halide precursor and reactants to form a metal-containing layer. The growth rate of the metal-containing layer is lower than that of a similar deposition method that does not expose the substrate surface to the halide-containing growth inhibitor.

[0008] Further embodiments of this disclosure relate to a deposition method comprising exposing a dielectric surface in which features are formed to HCl, MoO2Cl2, and hydrogen (H2) to form a molybdenum layer within a trench. The molybdenum layer is deposited to have a greater thickness at the bottom of the trench than at the outside of the trench.

[0009] Further embodiments of this disclosure relate to a deposition method comprising exposing a dielectric surface in which features are formed to tert-butyl chloride to form a treated surface. The treated surface is then exposed to a molybdenum halide precursor to chemisorb molybdenum species onto the treated surface within a trench. The treated surface is further exposed to a reactant to react with the molybdenum species, and a molybdenum layer is formed on the treated surface within the trench. The molybdenum layer is deposited to have a greater thickness at the bottom of the trench than at the outside of the trench. Attached Figure Description

[0010] To gain a more detailed understanding of the foregoing features of this disclosure, a more specific description of the disclosure, briefly outlined above, can be obtained by referring to embodiments, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings illustrate only typical embodiments of this disclosure and are therefore not intended to limit the scope of the disclosure, as other equally effective embodiments are permissible.

[0011] Figure 1 A process flow diagram illustrating a method according to one or more embodiments of the present disclosure is shown;

[0012] Figure 2 A substrate is shown during processing according to one or more embodiments of the present disclosure; and

[0013] Figure 3 A process flow diagram of a method according to one or more embodiments of the present disclosure is shown. Detailed Implementation

[0014] Before describing several exemplary embodiments of this disclosure, it should be understood that this disclosure is not limited to the details of the construction or process steps set forth in the following description. This disclosure can have other embodiments and can be practiced or implemented in various ways.

[0015] As used in this specification and the appended claims, the term "substrate" means a surface or part thereof on which a process is performed. It should also be understood by those skilled in the art that reference to a substrate may also refer only to a portion of a substrate, unless the context clearly indicates otherwise. Additionally, reference to deposition on a substrate may mean both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0016] As used herein, “substrate” refers to any substrate on which a film treatment is performed during a manufacturing process, or a material surface formed on a substrate. For example, depending on the application, substrate surfaces on which treatments can be performed include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials such as metals, metal nitrides, metal alloys, and other conductive materials. Substrates include, but are not limited to, semiconductor wafers. Substrates may be exposed to pretreatment processes such as polishing, etching, reduction, oxidation, hydroxylation, annealing, ultraviolet (UV) curing, electron beam curing, and / or baking of the substrate surface. In addition to film treatments performed directly on the surface of the substrate itself, any of the film treatment steps disclosed in this disclosure may also be performed on an underlayer formed on the substrate, as disclosed in more detail below, and the term “substrate surface” is intended to include such an underlayer as indicated by the context. Thus, for example, where a film / layer or a portion of a film / layer has already been deposited onto the substrate surface, the exposed surface of the most recently deposited film / layer becomes the substrate surface.

[0017] According to one or more embodiments, the term "on" regarding a film or layer includes a film or layer directly on a substrate (e.g., a substrate surface), and a film or layer with one or more underlying layers between it and a surface (e.g., a substrate surface). Therefore, in one or more embodiments, the phrase "on a substrate surface" is intended to include one or more underlying layers. In other embodiments, the phrase "directly on" represents a layer or film in contact with a surface (e.g., a substrate surface) without an intermediate layer. Therefore, the phrase "a layer directly on a substrate surface" represents a layer in direct contact with the substrate surface without any layer between the layer and the substrate surface.

[0018] One or more embodiments of this disclosure relate to deposition methods that utilize halide-containing growth inhibitors to reduce the growth rate of the deposited film. Some embodiments of this disclosure utilize chemical vapor deposition or atomic layer deposition. In some embodiments, the halide-containing growth inhibitors include hydrogen halides or haloalkanes. In some embodiments, the deposition material includes molybdenum.

[0019] Some embodiments of this disclosure advantageously provide bottom-up gap filling without seams or pores. Some embodiments of this disclosure advantageously provide superconformal deposition within the feature. As used in this regard, "superconformal" means a layer with a greater average thickness near the bottom of the feature than near the top of the feature.

[0020] See Figure 1 and Figure 2One or more embodiments of this disclosure provide a deposition method 100. Method 100 begins at operation 110, exposing a substrate 200 having a substrate surface 205 to a halide-containing growth inhibitor. In some embodiments, the substrate 200 includes a dielectric material 220. In some embodiments, the substrate surface 205 is an oxide surface.

[0021] In some implementations, such as Figure 2 As shown, substrate 200 has at least one feature 210 formed therein. Feature 210 extends from top surface 212 outside feature 210 to bottom surface 214. Feature 210 has an average width W between sidewalls 216 and 218. For the avoidance of doubt, the cross-section of substrate 200 shown in 200 shows two sidewalls, but in practice, feature 210 may have any number of different sidewalls (e.g., one sidewall for a cylindrical through-hole, two sidewalls for a trench, etc.).

[0022] Halogenated growth inhibitors comprise suitable halide species. In some embodiments, halideated growth inhibitors comprise hydrogen halides. In some embodiments, halideated growth inhibitors comprise HCl or are substantially composed of HCl. As used in this regard, halideated growth inhibitors substantially composed of said species comprise greater than or equal to 95%, greater than or equal to 98%, greater than or equal to 99%, or greater than or equal to 99.5% of said species in moles, and do not contain any inert diluents or carrier gases.

[0023] In some embodiments, the halide-containing growth inhibitor is substantially free of fluorine. As used in this regard, the halide-containing growth inhibitor is substantially free of fluorine when it contains less than or equal to 1 atomic percent, less than or equal to 0.5 atomic percent, or less than or equal to 0.1 atomic percent of fluorine per atomic number.

[0024] In some embodiments, the halide-containing growth inhibitor comprises a haloalkane. In some embodiments, the haloalkane comprises one to four, one to six, one to eight, four to eight, or six to eight carbon atoms. In some embodiments, the halide-containing growth inhibitor comprises or is substantially composed of tert-butane halo. In some embodiments, the halide-containing growth inhibitor comprises, or is substantially composed of, tert-butane chloride, tert-butane bromide, or tert-butane iodide.

[0025] See you again Figure 1 and Figure 2 Method 100 continues at operation 120, exposing the substrate surface 205 to the metal halide precursor and reactants to form a metal-containing layer 250.

[0026] In some embodiments, method 100 is performed by chemical vapor deposition (CVD). In these embodiments, the substrate surface is exposed to a metal halide precursor and reactants as a combined reactive gas. In some embodiments, the substrate surface may be exposed to a halide-containing growth inhibitor before exposure to the combined reactive gas. In these embodiments, exposing the substrate surface 205 to the halide-containing growth inhibitor produces a treated surface. In some embodiments, the substrate surface may be exposed to a halide-containing growth inhibitor as part of the combined reactive gas.

[0027] The metal halide precursor can be any suitable metal precursor containing at least one halide ligand. In some embodiments, the metal halide precursor is homoleptic and the halide ligand is the only ligand present (e.g., TiCl4). In some embodiments, the metal halide precursor is heteroleptic and the halide ligand is present along with other ligands (e.g., WOCl4).

[0028] In some embodiments, the metal halide precursor includes one or more of W, Ti, Ta, Ru, Mo, Cu, or Co. In some embodiments, the metal of the metal halide precursor includes molybdenum or is substantially composed of molybdenum. In some embodiments, the metal halide precursor includes MoO₂Cl₂, MoCl₅, MoOCl₄, WCl₅, or TaCl₅, or is substantially composed of MoO₂Cl₂, MoCl₅, MoOCl₄, WCl₅, or TaCl₅. In some embodiments, the metal halide precursor substantially does not include TiCl₄.

[0029] Both the halide-containing growth inhibitor and the metal halide precursor comprise species containing one or more halide groups. In some embodiments, the halide of the halide-containing growth inhibitor is the same halide as the halide of the metal halide precursor. For example, in some embodiments, the halide-containing growth inhibitor comprises HCl, and the metal halide precursor comprises MoO2Cl2 (both comprising chlorides).

[0030] According to one or more embodiments, method 100 uses a chemical vapor deposition (CVD) process. Chemical vapor deposition (CVD) is one of the most common deposition processes used to deposit layers on a substrate. CVD is a throughput-dependent deposition technique that requires precise control of the substrate temperature and the precursors introduced into the processing chamber to produce a layer of the desired uniform thickness. As substrate size increases, these requirements become more critical, necessitating more sophisticated chamber designs and airflow techniques to maintain sufficient uniformity.

[0031] Cyclic deposition, or atomic layer deposition (ALD), is a variant of CVD exhibiting excellent step coverage. Cyclic deposition is based on atomic layer epitaxy (ALE) and employs chemisorption techniques to deliver precursor molecules to the substrate surface in continuous cycles. This cycle exposes the substrate surface to a first precursor, a purge gas, a second precursor, and another purge gas. The first and second precursors react to form product compounds as a film on the substrate surface. This cycle is repeated to form a layer of the desired thickness.

[0032] According to one or more embodiments, method 100 uses an atomic layer deposition (ALD) process. In these embodiments, the substrate surface is exposed to the precursor (or reactive gas) sequentially or substantially sequentially. As used throughout the specification, “substantially sequentially” means that the majority of the duration of precursor exposure does not overlap with the exposure to the co-reactant, although some overlap may exist.

[0033] As used in this specification and the appended claims, the terms “precursor,” “reactant,” “reactive gas,” and similar terms are used interchangeably to represent any gaseous species that can react with the substrate surface.

[0034] As used herein, “atomic layer deposition” or “cyclic deposition” refers to sequential exposure to two or more reactive compounds to deposit a layer of material on a substrate surface. As used in this specification and the appended claims, the terms “reactive compound,” “reactive gas,” “reactive species,” “precursor,” “process gas,” and similar terms are used interchangeably to refer to substances having species capable of reacting with the substrate surface or material on the substrate surface in surface reactions (e.g., chemisorption, oxidation, reduction). The substrate, or a portion of the substrate, is sequentially exposed to two or more reactive compounds introduced into a reaction region of the processing chamber. In time-domain ALD processes, exposure to each reactive compound is separated by a time delay to allow each compound to adhere to and / or react with the substrate surface. In spatial ALD processes, the substrate surface or different portions of the material on the substrate surface are simultaneously exposed to two or more reactive compounds so that any given point on the substrate is not substantially exposed to more than one reactive compound at the same time. As used in this specification and the appended claims, and as will be understood by those skilled in the art, the term "generally" as used in this respect means that a small portion of the substrate may be attributed to diffusion and simultaneously exposed to multiple reactive gases, and that such simultaneous exposure is undesirable.

[0035] In one aspect of the time-domain ALD process, a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction region, followed by a first time delay. Next, a second precursor or compound B is pulsed into the reaction region, followed by a second delay. During each time delay, a purge gas, such as argon, is introduced into the processing chamber to purge the reaction region or otherwise remove any residual reactive compounds or reaction byproducts from the reaction region. Alternatively, the purge gas may flow continuously throughout the deposition process so that only the purge gas flows during the time delay between reactive compound pulses. The reactive compounds are pulsed alternately until the desired film or film thickness is formed on the substrate surface. In either case, the ALD process of pulsed compound A, purge gas, compound B, and purge gas is a cycle. The cycle can begin with compound A or compound B and continue in a corresponding sequence until a film with the desired thickness is achieved.

[0036] In one aspect of the space ALD process, a first reactant gas and a second reactant gas (e.g., hydrogen radicals) are simultaneously delivered to the reaction region, but isolated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas delivery device so that any given point on the substrate is exposed to the first reactant gas and the second reactant gas.

[0037] For many applications, metal-containing layers can be grown via atomic layer deposition or chemical vapor deposition. One or more embodiments of this disclosure advantageously provide processes for atomic layer deposition or chemical vapor deposition to form metal-containing layers with lower growth rates. As used in this specification and the appended claims, the term "metal-containing layer" means a layer or film comprising metal atoms and having a metal content greater than or equal to about 1 atomic percent, greater than or equal to about 2 atomic percent, greater than or equal to about 3 atomic percent, greater than or equal to about 4 atomic percent, greater than or equal to about 5 atomic percent, greater than or equal to about 10 atomic percent, greater than or equal to about 15 atomic percent, greater than or equal to about 20 atomic percent, greater than or equal to about 25 atomic percent, greater than or equal to about 30 atomic percent, greater than or equal to about 35 atomic percent, greater than or equal to about 40 atomic percent, greater than or equal to about 45 atomic percent, greater than or equal to about 50 atomic percent, or greater than or equal to about 60 atomic percent. In some embodiments, the metal layer includes one or more of a metal layer (elemental metal), a metal oxide (MOx), a metal carbide (MCx), a metal silicide (MSix), or a metal nitride (MNx). Those skilled in the art will recognize that the use of a molecular formula such as MSix does not imply a specific stoichiometric relationship between elements, but merely an identification of the principal components of the membrane. For example, MSix represents a membrane whose principal components include one or more metal and silicon atoms. In some embodiments, the principal components of the membrane (i.e., the sum of the atomic percentages of specified atoms) are specified as greater than or equal to about 95%, 98%, 99%, or 99.5% of the membrane on an atomic basis.

[0038] See Figure 3 One or more embodiments of this disclosure pertain to a method 300 for depositing a metal-containing layer at a relatively low deposition rate, method 300 representing an atomic layer deposition (ALD) process (in which a substrate or substrate surface is sequentially exposed to reactive gases in a manner that prevents or minimizes gas-phase reactions of the reactive gases). In other embodiments (not illustrated), method 100 includes a chemical vapor deposition (CVD) process, in which reactive gases are mixed in a processing chamber to allow for gas-phase reactions of the reactive gases and deposition of the metal-containing layer.

[0039] In some embodiments, method 300 includes a pretreatment operation 305. The pretreatment can be any suitable pretreatment known to those skilled in the art. Suitable pretreatments include, but are not limited to, preheating, cleaning, soaking, removal of native oxides, or deposition of an adhesive layer (e.g., titanium nitride (TiN)). In one or more embodiments, operation 305 includes exposing the substrate surface to a halide-containing growth inhibitor.

[0040] Unbound by theory, it is believed that exposing the substrate surface to a halide-containing growth inhibitor before deposition 310 reduces the number of reaction sites available for the chemisorption of metal halide precursors. Therefore, pretreatment 305 reduces the growth rate of the metal-containing layer by decreasing the number of metal halide precursors available for reaction on the substrate surface.

[0041] At deposition 310, a process is performed to deposit a metal-containing layer on a substrate (or substrate surface). The deposition process may include one or more operations to form a film on the substrate. In operation 312, the substrate (or substrate surface) is exposed to a metal halide precursor to deposit a film on the substrate (or substrate surface). As described above, the metal halide precursor may be any suitable compound that can react with the substrate surface (i.e., adsorb or chemisorb onto the substrate surface) to leave a metal-containing species on the substrate surface.

[0042] At operation 314, the processing chamber may optionally be purged to remove unreacted metal halide precursors, reaction products, and byproducts. When used in this manner, the term "processing chamber" also includes the portion of the processing chamber adjacent to the substrate surface, but not the entire internal volume of the processing chamber. For example, in a spatially separated section of the processing chamber, the portion of the processing chamber adjacent to the substrate surface is purged of metal halide precursors by any suitable technique, including but not limited to moving the substrate through a gas curtain to a portion or section of the processing chamber that does not or substantially does not contain metal halide precursors. In one or more embodiments, purging the processing chamber includes applying a vacuum. In some embodiments, purging the processing chamber includes flowing a purge gas through the substrate. In some embodiments, this portion of the processing chamber represents a micro-volume or small-volume process station within the processing chamber. The term "adjacent" with respect to the substrate surface refers to the physical space immediately adjacent to the substrate surface that provides sufficient space for surface reactions (e.g., precursor adsorption) to occur. In one or more embodiments, the purifying gas is selected from one or more of nitrogen (N2), helium (He) and argon (Ar).

[0043] At operation 316, a substrate (or substrate surface) is exposed to a reactant to form a metal-containing layer on the substrate surface. The reactant may react with a metal-containing precursor species on the substrate surface to form the metal-containing layer. In some embodiments, the reactant includes a reducing agent. In one or more embodiments, the reducing agent may include any reducing agent known to those skilled in the art. In other embodiments, the reactant includes an oxidizing agent. In one or more embodiments, the oxidizing agent may include any oxidizing agent known to those skilled in the art. In a further embodiment, the reactant includes one or more oxidizing and reducing agents.

[0044] In certain embodiments, the reactants are selected from one or more of 1,1-dimethylhydrazine (DMH), alkylamines, hydrazine, alkylhydrazines, allylhydrazine, hydrogen (H2), ammonia (NH3), alcohols, water (H2O), oxygen (O2), ozone (O3), nitrous oxide (N2O), nitrogen dioxide (NO2), peroxides, and plasmas of the foregoing. In some embodiments, the alkylamine is selected from one or more of tert-butylamine (tBuNH2), isopropylamine (iPrNH2), ethylamine (CH3CH2NH2), diethylamine ((CH3CH2)2NH), or butylamine (BuNH2). In some embodiments, the reactants include one or more compounds having the chemical formula R'NH2, R'2NH, R'3N, R'2SiNH2, (R'3Si)2NH, (R'3Si)3N; wherein each R' is independently H or an alkyl group having 1 to 12 carbon atoms. In some embodiments, the alkylamine is essentially composed of one or more of tert-butylamine (tBuNH2), isopropylamine (iPrNH2), ethylamine (CH3CH2NH2), diethylamine ((CH3CH2)2NH), and butylamine (BuNH2).

[0045] At operation 318, the processing chamber is optionally cleaned after exposure to the reactants. Cleaning the processing chamber in operation 318 can be performed using the same or a different process as the cleanup in operation 314. This cleansing removes unreacted reactants, reaction products, and byproducts from the area adjacent to the substrate surface.

[0046] At decision 320, the thickness of the deposited metal-containing layer, or the number of cycles of the metal halide precursor and reactants, is considered. If the metal-containing layer has reached a predetermined thickness or a predetermined number of process cycles have been performed, method 300 proceeds to an optional post-processing operation 330. If the thickness of the deposited film or the number of process cycles has not reached a predetermined threshold, method 300 returns to operation 310 to expose the substrate surface to the metal halide precursor again in operation 312, and continues. In some embodiments, method 300 repeats pre-processing operation 305 before continuing to operation 310. In some embodiments, pre-processing operation 305 is repeated only at regular intervals (e.g., after 5, 10, or 20 deposition cycles).

[0047] Optional post-treatment operation 330 may be, for example, a process for altering film properties (e.g., annealing) or a further film deposition process for growing additional films (e.g., additional ALD or CVD processes). In some embodiments, optional post-treatment operation 330 may be a process for altering the properties of the deposited film. In some embodiments, optional post-treatment operation 330 includes annealing the deposited metal-containing layer. In some embodiments, annealing is performed at temperatures in the range of about 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, or 1000°C. The annealing environment in some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N2), argon (Ar)) or a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)) or an oxidizing agent such as, but not limited to, oxygen (O2), ozone (O3), or a peroxide. Annealing may be performed for any suitable length of time. In some embodiments, the metal-containing layer may be annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the deposited film increases density, reduces resistivity, and / or increases film purity. In one or more embodiments, annealing may also be performed using a gas under plasma conditions. In one or more embodiments, in the case of plasma, the annealing temperature may be lowered.

[0048] Method 300 can be performed at any suitable temperature based on, for example, the thermal budget of the metal halide precursor, reactant, or device. In one or more embodiments, the use of high-temperature processing may not be desirable for temperature-sensitive substrates such as logic devices. In some embodiments, exposure to the metal halide precursor (operation 312) and reactant (operation 316) occurs simultaneously. In some embodiments, the substrate is maintained at a temperature ranging from about 20°C to about 400°C, or from about 50°C to about 650°C.

[0049] In some embodiments, exposure to the metal halide precursor (operation 312) occurs at a different temperature than exposure to the reactant (operation 316). In some embodiments, for exposure to the metal halide precursor, the substrate is maintained at a first temperature ranging from about 20°C to about 400°C, or from about 50°C to about 650°C; and for exposure to the reactant, the substrate is maintained at a second temperature ranging from about 20°C to about 400°C, or from about 50°C to about 650°C.

[0050] exist Figure 3In the embodiment shown, at deposition operation 310, the substrate (or substrate surface) is sequentially exposed to the metal halide precursor and reactants. In another embodiment (not shown), the substrate (or substrate surface) is simultaneously exposed to the metal halide precursor and reactants during the CVD reaction. During the CVD reaction, the substrate (or substrate surface) may be exposed to a gaseous mixture of the metal halide precursor and reactants to deposit a metal-containing layer of a predetermined thickness.

[0051] In some embodiments, the halide growth inhibitor is mixed with the metal halide precursor and reactants for simultaneous exposure to the substrate. In other embodiments, the halide growth inhibitor is exposed to the substrate prior to exposure to the mixture of metal halide precursor and reactants (similar to the pretreatment described above). In the CVD reaction, the metal-containing layer may be deposited in a single exposure to the mixed reaction gas (metal halide precursor and reactants), or it may be deposited in multiple exposures to the mixed reaction gas with degassing between these multiple exposures.

[0052] In some embodiments, the formed metal-containing layer comprises elemental metals. In other words, in some embodiments, the metal-containing layer is substantially composed of one or more metals. As used in this manner, the term "substantially composed of one or more metals" means that the metal-containing layer is composed of metals at a concentration of 95%, 98%, 99%, or 99.5% on an atomic basis. The measurement of the composition of the metal-containing layer refers to the bulk portion of the film, excluding interfacial regions where elemental diffusion from adjacent films may occur.

[0053] In other embodiments, the metal-containing layer comprises a metal oxide (MO) having an oxygen content of more than or equal to about 5%, 7.5%, 10%, 12.5%, or 15% on an atomic basis. X In some embodiments, the metal layer includes an oxygen content ranging from about 2% to about 30% on an atomic basis, or from about 3% to about 25%, or from about 4% to about 20%.

[0054] In other embodiments, the metal-containing layer comprises a metal carbide (MC) having a carbon content of more than or equal to about 5%, 7.5%, 10%, 12.5%, or 15% on an atomic basis. X In some embodiments, the metal layer comprises a carbon content ranging from about 2% to about 30% on an atomic basis, or from about 3% to about 25%, or from about 4% to about 20%.

[0055] Deposition operation 310 can be repeated to form one or more of a metal oxide film, metal carbide film, metal silicide film, or metal nitride film having a predetermined thickness. In some embodiments, deposition operation 310 is repeated to provide one or more of a metal oxide film, metal carbide film, metal silicide film, or metal nitride film having a thickness in the range of about 0.3 nm to about 100 nm, or about to approximately Thickness within the range.

[0056] One or more embodiments of this disclosure relate to a method for depositing a metal-containing layer in a high aspect ratio feature. A high aspect ratio feature is a trench, via, or the like with a depth-to-width ratio greater than or equal to about 10, 20, 50, or greater.

[0057] In some embodiments, a metal-containing layer is conformally deposited on the feature. If used in this manner, the conformal film has a thickness near the top of the feature that is in the range of about 100 to 120% or 100 to 110% of the thickness at the bottom of the feature.

[0058] In some embodiments, the metal-containing layer is conformally deposited on the feature. When used in this manner, the conformal film has a thickness near the bottom of the feature in the range of about 100 to 120% or 100 to 110% of the thickness at the top of the feature. In other words, in some embodiments, the metal-containing film is deposited to have a greater thickness at the bottom of at least one feature than at the exterior of at least one feature.

[0059] Some embodiments of this disclosure pertain to a bottom-up gap-filling method for features. Bottom-up gap-filling processes primarily fill the feature from the bottom, while conformal processes primarily fill the feature from the bottom and sides. In some embodiments, super-conformal deposition in the feature results in more deposition near the bottom of the feature than near the top, thereby producing bottom-up gap filling.

[0060] According to one or more embodiments, the substrate can be processed before and / or after the formation of the metal-containing layer. This processing can be performed in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is moved from a first chamber to a separate second chamber for further processing. The substrate can be moved directly from the first chamber to the separate processing chamber, or the substrate can be moved from the first chamber to one or more transfer chambers and then to the separate processing chamber. Therefore, the processing apparatus may include multiple chambers communicating with transfer stations. Such an apparatus may be referred to as a "clustering tool" or a "clustering system" and the like.

[0061] Typically, clustering tools are modular systems comprising multiple chambers that perform various functions, including substrate centering and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, the clustering tool includes at least a first chamber and a central transfer chamber. The central transfer chamber can house a robot capable of moving the substrate back and forth between or within a plurality of processing chambers and a loading and locking chamber. The transfer chamber is typically maintained under vacuum conditions and provides an intermediate platform for moving the substrate back and forth from one chamber to another and / or the loading and locking chamber, located at the front end of the clustering tool. It can be adapted for use with two well-known clustering tools of this disclosure. and Both of the aforementioned tools are available from Applied Materials, Inc., Santa Clara, California. However, the precise arrangement and combination of chambers can be modified for the purpose of performing specific steps of the processes described herein. Other processing chambers that can be used include, but are not limited to, circulating layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments (such as rapid thermal processing (RTP)), plasma nitriding, degassing, orientation, hydroxylation, and other substrate processes. By performing the process in chambers on clustered tools, surface contamination of the substrate by atmospheric impurities can be avoided without oxidation prior to the deposition of subsequent films.

[0062] According to one or more embodiments, as the substrate moves from one chamber to the next, the substrate is continuously under vacuum or "load-locked" conditions and is not exposed to ambient air. The transfer chamber is thus "evacuated" under vacuum and vacuum pressure. An inert gas may be present in the processing chamber or the transfer chamber. In some embodiments, the inert gas is used as a purge gas for removing some or all of the reactants (e.g., reactants). According to one or more embodiments, purge gas is injected at the outlet of the deposition chamber to prevent reactants (e.g., reactants) from moving from the deposition chamber to the transfer chamber and / or additional processing chambers. Thus, the flow of inert gas forms an air curtain at the outlet of the chamber.

[0063] Substrates can be processed in a single substrate deposition chamber, wherein a single substrate is loaded, processed, and unloaded before processing another substrate. Substrates can also be processed continuously, similar to a transport system, wherein multiple substrates are individually loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The shape of the chamber and associated transport system can form a straight path or a curved path. Alternatively, the processing chamber can be a rotating rack in which multiple substrates move about a central axis and are exposed to deposition, etching, annealing, cleaning, etc., throughout the rotating rack path.

[0064] During processing, the substrate may be heated or cooled. This heating or cooling can be accomplished by any suitable means, including but not limited to, changing the temperature of the substrate support and allowing heating or cooling gases to flow to the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas used (either a reactive gas or an inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is positioned adjacent to the substrate surface within a chamber to conductively change the substrate temperature.

[0065] The substrate can be stationary or rotating during processing. A rotating substrate can rotate continuously (around its axis) or in stages. For example, the substrate can rotate throughout the entire process, or it can rotate slightly between exposures to different reaction or purge gases. Rotating the substrate (continuously or distributedly) during processing can help produce more uniform deposition or etching by minimizing the effects of local variability, such as in the gas flow geometry.

[0066] Throughout this specification, references to "one embodiment," "some embodiments," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of this disclosure. Therefore, the appearance of phrases such as "in one or more embodiments," "in some embodiments," "in one embodiment," or "in one embodiment" in various places in this specification does not necessarily represent the same embodiment of this disclosure. Furthermore, specific features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0067] Although the disclosure herein has been described with reference to specific embodiments, those skilled in the art will understand that the described embodiments are merely illustrative of the principles and applications of this disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the methods and apparatus of this disclosure without departing from the spirit and scope of this disclosure. Therefore, this disclosure may include modifications and variations within the scope of the appended claims and their equivalents.

Claims

1. A deposition method, comprising: The substrate surface is exposed to a halide-containing growth inhibitor, the substrate surface having at least one feature formed therein, the at least one feature extending a depth from a top surface outside the at least one feature to a bottom and having a width defined by an average distance between two sidewalls; as well as The substrate surface is exposed to metal halide precursors and reactants to form a metal-containing layer. The growth rate of the metal-containing layer is reduced compared to a similar deposition method that does not expose the substrate surface to the halide growth inhibitor, wherein the metal-containing layer is deposited such that the bottom of the at least one feature has a greater thickness than the top surface outside the at least one feature, and wherein the metal-containing layer has a thickness in the range of 100 to 120% of the thickness of the top surface outside the at least one feature near the bottom of the at least one feature.

2. The method of claim 1, wherein the halide-containing growth inhibitor does not include fluorine.

3. The method of claim 1, wherein the halide-containing growth inhibitor comprises hydrogen halide.

4. The method of claim 1, wherein the halide-containing growth inhibitor comprises a haloalkane.

5. The method of claim 4, wherein the haloalkane comprises tert-butane halo.

6. The method of claim 1, wherein the halide containing the halide growth inhibitor is the same halide as the halide of the metal halide precursor.

7. The method of claim 1, wherein the metal-containing layer is formed by chemical vapor deposition (CVD).

8. The method of claim 7, wherein the substrate surface is exposed to the halide-containing growth inhibitor to form a treated substrate surface, and the treated substrate surface is exposed to the metal halide precursor and the reactants.

9. The method of claim 7, wherein each of the halide growth inhibitor, the metal halide precursor, and the reactant is simultaneously exposed on the substrate surface.

10. The method of claim 1, wherein the metal-containing layer is formed by atomic layer deposition.

11. The method of claim 10, wherein the substrate surface is exposed to the halide-containing growth inhibitor to form a substrate surface treated with the halide growth inhibitor, and the treated substrate surface is sequentially exposed to the metal halide precursor and the reactant.

12. The method of claim 1, wherein the metal-containing layer is formed as a bottom-up gap-filling material.

13. The method of claim 12, wherein the bottom-up gap-filling material has no pores or seams.

14. The method of claim 1, wherein the metal-containing layer comprises molybdenum.

15. The method of claim 1, wherein the metal-containing layer comprises a metal layer or a metal oxide layer.

16. The method of claim 1, wherein the metal-containing layer is formed on the dielectric material.

17. A deposition method, comprising: A dielectric surface having at least one feature is exposed to HCl, MoO2Cl2, and hydrogen (H2) to form a molybdenum layer within the at least one feature, wherein the molybdenum layer is deposited such that the bottom of the at least one feature has a greater thickness than the top surface outside the at least one feature, and wherein the molybdenum layer near the bottom of the at least one feature has a thickness in the range of 100 to 120% of the thickness of the top surface outside the at least one feature.

18. A deposition method, comprising: A dielectric surface having at least one feature is exposed to a tert-butane chloro growth inhibitor to form a treated surface on a top surface outside the at least one feature, the at least one feature extending a depth to the bottom from the top surface outside the at least one feature and having a width defined by the average distance between two sidewalls. as well as The treated surface and the at least one feature are exposed to a molybdenum halide precursor to chemically adsorb molybdenum species onto the treated surface and into the at least one feature; The treated surface and the at least one feature are exposed to reactants to react with the molybdenum species and form a molybdenum layer on the treated surface and within the at least one feature. The molybdenum layer is deposited such that the bottom of the at least one feature has a greater thickness than the top surface outside the at least one feature, and the molybdenum layer near the bottom of the at least one feature has a thickness in the range of 100 to 120% of the thickness of the top surface outside the at least one feature.

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