Molybdenum(VI) precursor for molybdenum film deposition

Abstract

This invention provides a molybdenum precursor that does not contain halogen groups or carbonyl groups, which react to form molybdenum metal and molybdenum-based films. [Solution] A metal coordination complex containing molybdenum(VI) and substantially free of halogens and carbonyls is provided.

Description

[Technical Field]

[0001]

[0001] Embodiments of the present disclosure relate to molybdenum precursors and methods for depositing molybdenum-containing films. More specifically, embodiments of the present disclosure relate to molybdenum(VI) precursors containing a group XV donor and methods for using the same. [Background technology]

[0002]

[0002] The semiconductor processing industry continues to strive for higher production yields while increasing the uniformity of layers deposited on substrates with larger surface areas. Combining these same elements with new materials also improves the density of circuits per unit area of ​​the substrate. As the density of circuits increases, the need for uniformity and processing control of layer thickness increases. As a result, various technologies have been developed to deposit layers on substrates in a cost-effective manner while maintaining control over the layer properties.

[0003]

[0003] Chemical vapor deposition (CVD) is one of the most common deposition processes used to deposit layers on a substrate. CVD is a flux-dependent deposition technique that requires precise control of the substrate temperature and the precursor introduced into the processing chamber to produce the desired layer of uniform thickness. These requirements become more important as the substrate size increases, leading to the need for more complex chamber designs and gas flow techniques to maintain proper uniformity.

[0004]

[0004] One type of CVD that exhibits excellent process coverage is periodic deposition or atomic layer deposition. Periodic deposition is based on atomic layer epitaxy (ALE) and uses chemisorption techniques to supply precursor molecules onto the substrate surface in sequential cycles. The cycle exposes the substrate surface to a first precursor, a purge gas, a second precursor, and a purge gas. The first and second precursors react to form a product compound as a film on the substrate surface. The cycle is repeated to form a layer of the desired thickness.

[0005]

[0005] The increasing complexity of advanced microelectronic devices places demanding requirements on currently used deposition technologies. Unfortunately, the number of viable chemical precursors available that possess the essential properties of robust thermal stability, high reactivity, and vapor pressure suitable for film growth is limited. Furthermore, precursors that often meet these requirements still have poor long-term stability, resulting in thin films containing high concentrations of contaminants such as oxygen, nitrogen, and halides, which are often detrimental to the target film application.

[0006]

[0006] Molybdenum and molybdenum-based films possess attractive material and conductivity properties. These films have been proposed and tested for applications ranging from the front-end to the back-end portions of semiconductor and microelectronic devices. Processing of molybdenum precursors often involves the use of halogen and carbonyl-based substituents. These ligands provide sufficient stability at the expense of reduced reactivity and increased processing temperature. Other molybdenum precursors contain amide ligands, which can lead to nitride impurities. Therefore, there is a need in the art for molybdenum precursors that do not contain halogen and carbonyl groups and react to form molybdenum metal and molybdenum-based films. [Overview of the Initiative]

[0007]

[0007] One or more embodiments of the present disclosure relate to metal coordination complexes. In one or more embodiments, the metal coordination complex comprises molybdenum(VI) and is substantially free of halogens and carbonyls.

[0008]

[0008] One or more embodiments of the present disclosure relate to a method for depositing a film. In one or more embodiments, the method for depositing a film includes exposing a substrate to a molybdenum(VI) precursor and exposing the substrate to a reactant to form a molybdenum-containing film on the substrate.

[0009]

[0009] Further embodiments of the present disclosure relate to a method for depositing a film. In one or more embodiments, the method for depositing a film includes forming a molybdenum-containing film in a processing cycle comprising sequential exposure of a substrate to a molybdenum(VI) precursor, a purge gas, a reactant, and the purge gas.

[0010]

[0010] In order to allow for a more detailed understanding of the above-mentioned features of the Disclosure, a more detailed description of the Disclosure, which has been briefly summarized above, can be given by reference to embodiments, some of which are shown in the accompanying drawings. However, it should be noted that the accompanying drawings show only typical embodiments of the Disclosure and should therefore not be considered to limit its scope. [Brief explanation of the drawing]

[0011] [Figure 1]

[0011] A processing flow diagram of a method according to one or more embodiments of the present disclosure is shown. [Modes for carrying out the invention]

[0012]

[0012] Before describing some exemplary embodiments of the present invention, it should be understood that the present invention is not limited to the details of the configuration or processing steps described below. Other embodiments of the present invention are possible and can be implemented or carried out in various ways.

[0013]

[0013] Embodiments of the present disclosure provide precursors and processes for depositing molybdenum-containing films. The precursors comprise metal coordination complexes. The metal coordination complexes of one or more embodiments are substantially halogen- and carbonyl-free. Using monodentate ligands and chelate-neutral group 15 donors, highly reactive and heat-sensitive molybdenum(VI) species are stabilized and supplied under ALD and CVD conditions. The processes of the various embodiments provide molybdenum films using deposition techniques such as atomic layer deposition (ALD) or chemical vapor deposition (CVD). The molybdenum precursors of one or more embodiments are volatile and thermally stable, making them suitable for deposition.

[0014]

[0014] The molybdenum coordination complexes of one or more embodiments substantially do not contain halogen groups and carbonyl groups. As used herein, the term "substantially does not contain" means that in the molybdenum coordination complex, on an atomic basis, there is less than about 5% halogen, including less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5%. In some embodiments, the molybdenum coordination complex substantially does not contain carbonyl groups, and in the molybdenum coordination complex, on an atomic basis, there is less than about 5% carbonyl groups, including less than about 4%, less than about 3%, less than about 2%, less than about 1%, and less than about 0.5%.

[0015]

[0015] As used herein, "substrate" refers to any substrate or material surface formed on a substrate on which film processing is performed during manufacturing. For example, the substrate surface on which processing can be performed can 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, etc., as well as any other materials such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. The substrate includes, but is not limited to, semiconductor wafers. The substrate can be exposed to a pretreatment process for polishing, etching, reducing, oxidizing, hydroxylating, annealing, and / or baking the substrate surface. In addition to directly performing film processing on the surface of the substrate itself, in the present invention, any of the disclosed film processing steps can also be performed on a lower layer formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include the lower layer as indicated by the context. Thus, for example, when a film / layer or a partial film / layer is deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0016] According to one or more embodiments, the method uses atomic layer deposition (ALD) processing. In such embodiments, the substrate surface is exposed to precursors (or reactive gases) sequentially or substantially sequentially. As used throughout this specification, "substantially sequentially" means that there may be some overlap, but most of the precursor exposure period does not overlap with the exposure to co-reactants.

[0017] As used in this specification and the appended claims, terms such as "precursor", "reactant", "reactive gas", etc. are used interchangeably to refer to any gas species that can react with a film formed on the substrate surface.

[0018] As used herein, "atomic layer deposition" or "cyclic deposition" refers to sequentially exposing two or more reactive compounds to deposit a layer of material on the substrate surface. As used in this specification and the appended claims, terms such as "reactive compound", "reactive gas", "reactive species", "precursor", "processing gas", etc. are used interchangeably to mean a substance having a species that can react with the substrate surface or a material on the substrate surface in a surface reaction (e.g., chemisorption, oxidation, reduction). The substrate or a part of the substrate is sequentially exposed to two or more reactive compounds introduced into the reaction zone of the processing chamber. In time-domain ALD processing, the exposure to each reactive compound is separated by a time delay so that each compound can adhere to and / or react with the substrate surface. In spatial ALD processing, different parts of the substrate surface or materials on the substrate surface are simultaneously exposed to two or more reactive compounds, so any point on the substrate is not substantially simultaneously exposed to a plurality of reactive compounds. As used in this specification and the appended claims, the term "substantially" used in this context means that, as would be understood by a person skilled in the art, a very small part of the substrate may be simultaneously exposed to a plurality of reactive gases by diffusion, and there may be a possibility that the simultaneous exposure is not intended.

[0019]

[0019] In one embodiment of time-domain ALD processing, a first reactive gas (i.e., a first precursor or compound A) is pulsed into the reaction zone, followed by a first time delay. Next, a second precursor or compound B is pulsed into the reaction zone, followed by a second delay. During each delay time, a purge gas, such as argon, is introduced into the processing chamber to purge the reaction zone or remove residual reactive compounds or by-products from the reaction zone. Alternatively, the purge gas may flow sequentially throughout the entire deposition process so that only the purge gas flows during the time delays between pulses of the reactive compounds. The reactive compounds are pulsed alternately until a desired film or thickness is formed on the substrate surface. In either scenario, one cycle consists of compound A, purge gas, compound B, and the ALD processing of pulsed purge gas. A cycle begins with either compound A or compound B, and each sequence of cycles continues until a film of the desired thickness is obtained.

[0020]

[0020] In one aspect of spatial ALD processing, a first reactive gas and a second reactive gas (e.g., hydrogen radicals) are supplied to the reaction zone simultaneously but separated by an inert gas curtain and / or a vacuum curtain. The substrate is moved relative to the gas supply device so that any point on the substrate is exposed to the first and second reactive gases.

[0021]

[0021] While not intended to be bound by theory, it is thought that the presence of halogens, carbonyl groups, and in some cases, oxygen in the structure of the molybdenum (Mo) precursor may present challenges, as halogen and oxygen contamination may affect the performance of the device and may require additional removal procedures. Carbonyl (CO) strongly binds to metals, so its removal requires a higher amount of heat or the use of additional reagents. Carbonyl (CO) can also contaminate other metal surfaces by redepositing them.

[0022]

[0022] Molybdenum (Mo) can be grown by atomic layer deposition or chemical vapor deposition in many applications. One or more embodiments of the present disclosure advantageously provide atomic layer deposition or chemical vapor deposition processes for forming molybdenum-containing films. As used in this specification and the appended claims, the term “molybdenum-containing film” means a film containing molybdenum atoms, having about 1 atomic% or more molybdenum, about 2 atomic% or more molybdenum, about 3 atomic% or more molybdenum, about 4 atomic% or more molybdenum, about 5 atomic% or more molybdenum, about 10 atomic% or more molybdenum, about 15 atomic% or more molybdenum, about 20 atomic% or more molybdenum, about 25 atomic% or more molybdenum, about 30 atomic% or more molybdenum, about 35 atomic% or more molybdenum, about 40 atomic% or more molybdenum, about 45 atomic% or more molybdenum, about 50 atomic% or more molybdenum, or about 60 atomic% or more molybdenum. In some embodiments, the molybdenum-containing film comprises one or more of the following: molybdenum metal (molybdenum element), molybdenum oxide (MoO2, MoO3), molybdenum carbide (MoC, Mo2C), molybdenum silicide (MoSi2), or molybdenum nitride (Mo2N). Those skilled in the art will know that MoSi x You will notice that the use of molecular formulas like this does not imply any specific stoichiometric relationship between elements, but simply signifies the identity of the main components of the film. For example, MoSi x This refers to a film whose main components are molybdenum atoms and silicon atoms. In some embodiments, the main composition of a particular film (i.e., the sum of the atomic percentages of a particular atom) is approximately 95%, 98%, 99%, or 99.5% or more of the film on an atomic basis.

[0023]

[0023] Referring to Figure 1, one or more embodiments of the present disclosure relate to a method 100 for depositing a film. The method shown in Figure 1 represents an atomic layer deposition (ALD) process in which a substrate or substrate surface is sequentially exposed to a reactive gas in a manner that prevents or minimizes the gas-phase reaction of the reactive gas. In some embodiments, the method includes a chemical vapor deposition (CVD) process in which the reactive gas is mixed in a processing chamber to enable the gas-phase reaction of the reactive gas and the deposition of a thin film.

[0024]

[0024] In some embodiments, method 100 includes a pretreatment operation 105. The pretreatment may be any suitable pretreatment known to those skilled in the art. Suitable pretreatments include, but are not limited to, preheating, washing, immersion, removal of native oxides, or deposition of an adhesive layer (e.g., titanium nitride (TiN)). In one or more embodiments, an adhesive layer such as titanium nitride is deposited in operation 105. In other embodiments, molybdenum can be integrated without requiring an adhesive liner.

[0025]

[0025] In deposition 110, a process is performed to deposit a molybdenum-containing film on the substrate (or substrate surface). The deposition process may include one or more operations for forming a film on the substrate. In operation 112, the substrate (or substrate surface) is exposed to a molybdenum precursor to deposit a film on the substrate (or substrate surface). The molybdenum precursor may be any suitable molybdenum-containing compound that can react with the substrate surface (i.e., adsorb or chemiadsorb) to leave molybdenum-containing species on the substrate surface.

[0026]

[0026] Current molybdenum precursors for ALD of metal films use halogen and carbonyl-based ligands, providing sufficient stability at the expense of reduced reactivity and increased processing temperature. Amide ligands can cause nitride impurities. Therefore, one or more embodiments use neutral nitrogen and phosphorus ligands. These ligands produce molybdenum-containing films with minimal impurities while maintaining high volatility, while improving the thermal stability of the molybdenum precursor.

[0027]

[0027] Unless otherwise specified, the terms “lower alkyl,” “alkyl,” or “alk” used herein, either alone or as part of another group, include both linear and branched hydrocarbons, typically having 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms in a chain, such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and their various branched isomers. Such groups may optionally contain 1 to 4 substituents. Alkyls may be substituted or unsubstituted.

[0028]

[0028] As used herein, the term "alkoxy" includes any of the alkyl groups described above bonded to an oxygen atom. The alkoxy may be substituted or unsubstituted.

[0029]

[0029] In one or more embodiments, the molybdenum precursor is of formula (I)

[0030] The structure is TIFF2026076186000002.tif36170. In the formula, E is independently selected from an oxo group, an imide group, and a sulfide group; X is independently selected from O, SiR2, and CR2; L is a nitrogen or phosphorus ligand; and R is independently unsubstituted or substituted C1-C 10 It is an alkyl group.

[0030]

[0031] While not intended to be theoretically constrained, bulky alkyl groups such as, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and CH2-t-butyl, are thought to provide stereochemistry, protect against and prevent "pi-pi stacking" of the aromatic ring of ligand L, lower the melting point, and improve the volatility of the molybdenum(VI) precursor.

[0031]

[0032] In one or more embodiments, chelated N,N- and P,P--based ligands L are used to prevent ligand dissociation (as a potential decomposition pathway) and enhance the thermal stability of the molybdenum precursor. Furthermore, the interaction between these electron-rich ligands and adjacent R groups can be controlled by varying the degree of substitution around the X atoms (i.e., one substituent on oxygen (O) compared to three substituents on silicon (Si) and carbon (C)), as well as the atomic radius.

[0032]

[0033] In certain embodiments, E independently comprises O, N-tBu, or S. In some embodiments, the molybdenum precursor has the structure of formula (I), where L is the following Selected from the group consisting of TIFF2026076186000003.tif19170. In one or more embodiments, R is Me-, Et-, iPr-, tBu-, and TIFF2026076186000004.tif8170 substituents can be selected independently.

[0033]

[0034] In other embodiments, the molybdenum precursor is given by formula (II)

[0035] It has the structure of TIFF2026076186000005.tif36170. In the formula, E is independently selected from an oxo group, an imide group, and a sulfide group; X is independently selected from O, SiR2, and CR2; L is a nitrogen-containing ligand; and R is independently unsubstituted or substituted C1-C 10 It is an alkyl group.

[0034]

[0036] In certain embodiments, E independently comprises O, N-tBu, or S. In some embodiments, the molybdenum precursor has the structure of formula (I), TIFF2026076186000006.tif14170 is the following Selected from the group consisting of TIFF2026076186000007.tif24170. In one or more embodiments, R is Me-, Et-, iPr-, tBu-, and It can be selected independently from TIFF2026076186000008.tif8170.

[0035]

[0037] In further embodiments, the molybdenum precursor is of formula (I) or formula (II)

[0038] The structure is TIFF2026076186000009.tif37170. In the formula, E is independently selected from an oxo group, an imide group, and a sulfide group; X is independently selected from O, SiR2, and CR2; L is a nitrogen or phosphorus ligand; and R is independently unsubstituted or substituted C1-C 10 It is an alkyl group. In certain embodiments, E independently comprises O, N-tBu, or S. In some embodiments, the molybdenum precursor has the structure of formula (I), where L is the following Selected from the group consisting of TIFF2026076186000010.tif19170. In some embodiments, the molybdenum precursor has the structure of formula (II), TIFF2026076186000011.tif14170 is the following Selected from the group consisting of TIFF2026076186000012.tif24170. In one or more embodiments, R is Me-, Et-, iPr-, tBu-, and It can be selected independently from TIFF2026076186000013.tif8170.

[0036]

[0039] As used herein, “substrate surface” means any substrate surface on which a layer can be formed. A substrate surface may have one or more features formed thereon, one or more layers formed thereon, and combinations thereof. The substrate (or substrate surface) may be pretreated before the deposition of the molybdenum-containing layer by, for example, polishing, etching, reduction, oxidation, halogenation, hydroxide, annealing, baking, etc.

[0037]

[0040] The substrate can be any substrate on which material can be deposited, such as silicon substrates, III-V compound substrates, silicon germanium (SiGe) substrates, epitaxial substrates, silicon-on-insulator (SOI) substrates, display substrates such as liquid crystal displays (LCDs), plasma displays, and electroluminescent (EL) lamp displays, solar arrays, solar panels, light-emitting diode (LED) substrates, and semiconductor wafers. In some embodiments, one or more additional layers can be placed on the substrate such that a molybdenum-containing layer is formed at least partially thereon. For example, in some embodiments, layers containing metals, nitrides, oxides, or combinations thereof can be placed on the substrate, and a molybdenum-containing layer can be formed on such layers.

[0038]

[0041] In operation 114, the processing chamber is optionally purged to remove unreacted molybdenum precursors, reaction products, and by-products. When used in this way, the term “processing chamber” includes portions of the processing chamber adjacent to the substrate surface, without encompassing the entire internal region of the processing chamber. For example, in a spatially separated sector of the processing chamber, portions of the processing chamber adjacent to the substrate surface are purged of the molybdenum precursor by any suitable technique, including but not limited to moving the substrate through a gas curtain into a portion or sector of the processing chamber that contains no or substantially no molybdenum precursor. In one or more embodiments, purging the processing chamber includes applying reduced pressure. In some embodiments, purging the processing chamber includes flowing a purge gas over the substrate. In some embodiments, a portion of the processing chamber refers to a minute volume or small volume processing station within the processing chamber. The term “adjacent” with respect to the substrate surface means the physical space adjacent to the substrate surface that can provide sufficient space for surface reactions (e.g., precursor adsorption) to occur. In one or more embodiments, the purge gas is selected from one or more of nitrogen (N2), helium (He), and argon (Ar).

[0039]

[0042] In operation 116, the substrate (or substrate surface) is exposed to the reactant to form one or more molybdenum films on the substrate. The reactant can react with molybdenum-containing species on the substrate surface to form a molybdenum-containing film. 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 further embodiments, the reactant includes one or more oxidizing agents and a reducing agent.

[0040]

[0043] In certain embodiments, the reactants are selected from one or more of 1,1-dimethylhydrazine (DMH), alkylamines, hydrazines, alkylhydrazines, allylhydrazines, hydrogen (H2), ammonia (NH3), alcohols, water (H2O), oxygen (O2), ozone (O3), nitrous oxide (N2O), nitrogen dioxide (NO2), peroxides, and plasmas thereof. 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 comprise one or more compounds having the formulas R'NH2, R'2NH, R'3N, R'2SiNH2, (R'3Si)2NH, and (R'3Si)3N, where each R' is independently H or an alkyl group having 1 to 12 carbon atoms. In some embodiments, the alkylamine is substantially composed of one or more of tert-butylamine (tBuNH2), isopropylamine (iPrNH2), ethylamine (CH3CH2NH2), diethylamine ((CH3CH2)2NH), or butylamine (BuNH2).

[0041]

[0044] In operation 118, the processing chamber is optionally purged after exposure to the reactants. The purging of the processing chamber in operation 118 may be the same as the purging in operation 114, or it may be a different process. Purging the processing chamber, a part of the processing chamber, or an area adjacent to the substrate surface removes unreacted reactants, reaction products, and by-products from the area adjacent to the substrate surface.

[0042]

[0045] In decision 120, the thickness of the deposited film or the number of cycles of the molybdenum precursor and reactant is taken into consideration. If the deposited film reaches a predetermined thickness or a predetermined number of processing cycles have been performed, method 100 proceeds to an optional post-processing operation 130. If the deposited film thickness or the number of processing cycles has not reached a predetermined threshold, method 100 returns to operation 110, and in operation 112, the substrate surface is exposed to the molybdenum precursor again and the process continues.

[0043]

[0046] Optional post-processing operations 130 may be, for example, processes to modify film properties (e.g., annealing) or further film deposition processes to grow additional films (e.g., additional ALD or CVD processes). In some embodiments, optional post-processing operations 130 may be processes to modify the properties of the deposited film. In some embodiments, optional post-processing operations 130 include annealing the as-deposited film. 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 an inert gas (e.g., molecular nitrogen (N2), argon (Ar)) or a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)), or one or more oxidizing agents such as oxygen (O2), ozone (O3), or peroxides, but not limited to these. Annealing can be performed for any suitable time. In some embodiments, the film is 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 as-deposited film increases the film's density, decreases its resistivity, and / or increases its purity. In one or more embodiments, annealing can also be performed using a gas under a plasma. In one or more embodiments, the annealing temperature may be lower than when using a plasma.

[0044]

[0047] In one or more embodiments, the plasma comprises one or more of nitrogen (N2), argon (Ar), helium (He), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and ammonia (NH3). In some embodiments, the plasma is a remote plasma. In other embodiments, the plasma is a direct plasma.

[0045]

[0048] In one or more embodiments, the plasma may be generated remotely or within the processing chamber. In one or more embodiments, the plasma is inductively coupled plasma (ICP) or inductively coupled plasma (CCP). For example, any suitable power can be used depending on the reactants or other processing conditions. In some embodiments, the plasma is generated with a plasma power in the range of about 10 W to about 3000 W. In some embodiments, the plasma is generated with a plasma power of about 3000 W or less, about 2000 W or less, about 1000 W or less, about 500 W or less, or about 250 W or less.

[0046]

[0049] Method 100 can be carried out at any suitable temperature, depending, for example, the molybdenum precursor, reactants, or the heat output of the apparatus. In one or more embodiments, the use of high-temperature processing may be undesirable for temperature-sensitive substrates such as logic devices. In some embodiments, exposure to the molybdenum precursor (operation 112) and exposure to the reactants (operation 116) are carried out at the same temperature. In some embodiments, the substrate is maintained at a temperature in the range of about 20°C to about 400°C, or about 50°C to about 650°C.

[0047]

[0050] In some embodiments, exposure to the molybdenum precursor (operation 112) is performed at a different temperature than exposure to the reactants (operation 116). In some embodiments, the substrate is maintained at a first temperature in the range of about 20°C to about 400°C or about 50°C to about 650°C for exposure to the molybdenum precursor, and at a second temperature in the range of about 20°C to about 400°C or about 50°C to about 650°C for exposure to the reactants.

[0048]

[0051] In the embodiment shown in Figure 1, the substrate (or substrate surface) is sequentially exposed to the molybdenum precursor and reactants during the deposition operation 110. In another embodiment not shown, the substrate (or substrate surface) is simultaneously exposed to the molybdenum precursor and reactants during the CVD reaction. In the CVD reaction, a molybdenum-containing film of a predetermined thickness can be deposited by exposing the substrate (or substrate surface) to a gaseous mixture of the molybdenum precursor and reactants. In the CVD reaction, the molybdenum-containing film can be deposited in a single exposure to the mixed reactive gas, or it can be deposited by multiple exposures to the mixed reactive gas with purging in between.

[0049]

[0052] In some embodiments, the formed molybdenum-containing film contains elemental molybdenum. In other words, in some embodiments, the molybdenum-containing film contains a molybdenum-containing metal film. In some embodiments, the metal film consists essentially of molybdenum. When used in this way, the term "consistently of molybdenum" means that the molybdenum-containing film is approximately 80%, 85%, 90%, 95%, 98%, 99%, or 99.5% or more molybdenum on an atomic basis. The measurement of the composition of a molybdenum-containing film refers to the bulk portion of the film, excluding the interfacial region where elemental diffusion from adjacent films may occur.

[0050]

[0053] In other embodiments, the molybdenum-containing film is molybdenum oxide (MoO) having an oxygen content of about 5%, 7.5%, 10%, 12.5%, or 15% or more on an atomic basis. x ) includes. In some embodiments, the molybdenum-containing film contains 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%.

[0051]

[0054] In other embodiments, the molybdenum-containing film is molybdenum carbide (MoC) having an atomic carbon content of approximately 5%, 7.5%, 10%, 12.5%, or 15% or more. x) includes. In some embodiments, the molybdenum-containing film contains 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%.

[0052]

[0055] By repeating the deposition operation 110, one or more of the molybdenum oxide film, molybdenum carbide film, molybdenum silicide film, and molybdenum nitride film having a predetermined thickness can be formed. In some embodiments, the deposition operation 110 is repeated to form one or more of the molybdenum oxide film, molybdenum carbide film, molybdenum silicide film, and molybdenum nitride film having a thickness in the range of about 0.3 nm to about 100 nm, or in the range of about 30 Å to about 3000 Å.

[0053]

[0056] One or more embodiments of the present disclosure relate to a method for depositing a molybdenum-containing film within a high aspect ratio feature. High aspect ratio features are trenches, vias, or pillars with a height-to-width ratio of approximately 10, 20, or 50 or greater. In some embodiments, the molybdenum-containing film is deposited conformally on the high aspect ratio feature. When used in this manner, the conformal film has a thickness near the top of the feature that ranges from approximately 80 to 120% of the thickness at the bottom of the feature.

[0054]

[0057] Some embodiments of this disclosure relate to methods for bottom-up gap filling of features. Bottom-up gap filling processes fill features from the bottom, whereas conforming processes fill features from the bottom and sides. In some embodiments, a feature has a first material (e.g., a nitride) at the bottom and a second material (e.g., an oxide) on the sidewalls. A molybdenum-containing film is selectively deposited on the first material relative to the second material so that the molybdenum film fills the feature in a bottom-up manner.

[0055]

[0058] According to one or more embodiments, the substrate is processed before and / or after layer formation. 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 another second chamber for further processing. The substrate can be moved directly from the first chamber to another processing chamber, or it can be moved from the first chamber to one or more transport chambers and then to another processing chamber. Thus, the processing apparatus can include multiple chambers communicating with transport stations. This type of apparatus is sometimes called a "cluster tool" or "cluster system."

[0056]

[0059] Generally, a cluster tool is a modular system comprising multiple chambers that perform various functions, including substrate center detection and orientation, degassing, annealing, deposition, and / or etching. According to one or more embodiments, a cluster tool includes at least a first chamber and a central transport chamber. The central transport chamber can accommodate a robot that can reciprocate the substrate between the processing chamber and the load lock chamber. The transport chamber is typically maintained under reduced pressure and provides an intermediate stage for reciprocating the substrate from one chamber to another and / or to the load lock chamber located at the front end of the cluster tool. Two well-known cluster tools that can be adapted to this disclosure are Centura® and Endura®, both available from Applied Materials, Inc. in Santa Clara, California. However, the exact arrangement and combination of chambers can be modified for the purpose of performing specific steps of the processing described herein. Other processing chambers that may be used include, but are not limited to, periodic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitriding, degassing, orientation, hydroxide, and other substrate processing. Performing processing within the cluster tool chamber avoids surface contamination of the substrate by atmospheric impurities without oxidation before depositing the next film.

[0057]

[0060] According to one or more embodiments, the substrate is continuously under reduced pressure or “load-lock” conditions and is not exposed to ambient air when moving from one chamber to the next. Thus, the transport chamber is under reduced pressure and is “pumped down” under reduced pressure. An inert gas may be present in the processing chamber or transport chamber. In some embodiments, an inert gas is used as a purge gas to remove some or all of the reactants (e.g., reactants). According to one or more embodiments, a purge gas is injected into the outlet of the deposition chamber to prevent the reactants (e.g., reactants) from moving from the deposition chamber to the transport chamber and / or additional processing chambers. Thus, the flow of inert gas forms a curtain at the chamber outlet.

[0058]

[0061] Substrates can be processed within a single-substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed sequentially, similar to a conveyor system, where multiple substrates are individually loaded into a first section of the chamber, move within the chamber, and unloaded from a second section. The shape of the chamber and associated conveyor system can form a straight or curved path. Furthermore, the processing chamber may be a carousel where multiple substrates move around a central axis and are exposed to processes such as deposition, etching, annealing, and washing along the entire carousel path.

[0059]

[0062] During processing, the substrate may be heated or cooled. Such heating or cooling can be achieved by any suitable means, including but not limited to changing the temperature of the substrate support and flowing a heated or cooled gas over the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductionally change the substrate temperature. In one or more embodiments, the gas used (either a reactive or inert gas) is heated or cooled to locally change the substrate temperature. In some embodiments, the heater / cooler is placed in a chamber adjacent to the substrate surface to convectively change the substrate temperature.

[0060]

[0063] The substrate can also be stationary or rotated during processing. The rotating substrate can be rotated (around the substrate axis) sequentially or in individual steps. For example, the substrate may be rotated throughout the process, or the substrate may be rotated slightly during exposure to different reactive or purge gases. Rotating the substrate during processing helps, for example, to minimize the effects of local variations in the gas flow pattern and to produce more uniform deposition or etching.

[0061]

[0064] Here, the present disclosure will be described with reference to the following examples. Before describing some exemplary embodiments of the present disclosure, it should be understood that the present disclosure is not limited to the details of the configurations or processing steps described in the following description. The present disclosure is capable of other embodiments and can be implemented or executed in various ways.

[0062]

[0065] Examples

[0066] Example 1: Preparation of 2,2'-bipyridine ditert-butoxodioxomolybdenum(VI), [MoO2(O t Bu)2(bipy)]

[0067] A solution of MoO2Cl2 in tetrahydrofuran (THF) was treated with the corresponding potassium potassium potassium alkoxide salt and the reaction mixture was stirred for 2 hours. The solvent was removed under reduced pressure and the target compound was extracted with n-hexane. Removal of the solvent followed by filtration gave [MoO2(O t Bu)2] as a pale yellow oil.

[0063]

[0068] [MoO2(O t Bu)2] was dissolved in hexane and 2,2'-bipyridine was added. Stirring the reaction mixture at ambient temperature for 2 hours formed a white precipitate. The solid was isolated by filtration and dried in vacuo.

[0064]

[0069] Example 2: Preparation of 2,2'-bipyridine tert-pentoxodioxomolybdenum(VI)

[0070] [MoO2(O t The preparation of [MoO2(O t [MoO2(O t Pent)2(bipy) was isolated as a white solid.

[0065]

[0071] [MoO2(O t The NMR characteristics of Pent)2] are as follows: 1 1H NMR (C6D6, 500 MHz): δ H 1.44 (q, 3 J HH =7.5 Hz, 4H), 1.15 (s, 6H), 0.75 (t, 3 J HH (=7.5 Hz, 3H)

[0066]

[0072] 13 C{ 1 H} (C6D6, 125 MHz): δ C 87.8 (s, O C (CH3)2CH2CH3), 35.9 (s, OC(CH3)2 C H2CH3), 27.8 (s, OC( C H3)2CH2CH3, 8.4 (s, OC(CH3)2CH2 C H3)

[0067]

[0073] [MoO2(O t The NMR feature x of Pent)2(bipy) is as follows: 1 1H NMR (C6D6, 500 MHz): δ H 8.66 (br d, 1H), 8.58 (br d, 1H), 7.19 (m, 1H), 6.68 (m, 1H), 1.44 (q, 3 J HH = 10 Hz, 2H), 1.16 (s, 6H), 0.75 (t, 3 J HH(= 10 Hz, 3H)

[0068]

[0074] 13 C{ 1 H} (C6D6, 125 MHz): δ C 156.1 (s, Ar C C), 149.1 (s, ArC), 136.3 (s, ArC), 123.4 (s, ArC), 120.8 (s, ArC), 87.5 (s, O C (CH3)2CH2CH3), 35.9 (s, OC(CH3)2 C H2CH3), 27.8 (s, OC( C H3)2CH2CH3, 8.4 (s, OC(CH3)2CH2 C H3)

[0069]

[0075] Example 2: Atomic layer deposition of molybdenum-containing film

[0076] General procedure: Position the silicon substrate in the processing chamber. Introduce the molybdenum precursor into the processing chamber in a nitrogen (N2) gas atmosphere on the silicon substrate, leaving a surface terminated with the molybdenum precursor. Purge unreacted precursor and by-products from the chamber. Next, introduce co-reactants into the chamber and react with the molybdenum species bound to the surface. Again, remove excess co-reactants and by-products from the chamber. The resulting material on the substrate is a molybdenum-containing film.

[0070]

[0077] Spatially relative terms such as "beneath," "below," "lower," "above," and "upper" may be used here to describe the relationship between one element or feature shown in the drawing and another, for the sake of clarity. It will be understood that spatially relative terms are intended to encompass different orientations of the device in use or operation, in addition to the orientation shown in the drawing. For example, if the device in the drawing is upside down, an element described as "below" or "directly below" another element or feature will therefore be oriented "above" the other element or feature. Thus, the exemplary term "below" may encompass both up and down orientations. The device may be oriented in other ways (rotated 90 degrees or in other directions), and the spatially relative descriptors used here may be interpreted accordingly.

[0071]

[0078] In the context describing the materials and methods discussed herein (particularly in the context of the following claims), the terms “a,” “an,” and “the,” and similar references, should be interpreted as covering both singular and plural forms, unless otherwise stated herein or unless clearly contradicted by the context. The enumeration of value ranges herein is merely intended to serve as a shorthand notation for referring individually to each individual value within the range, unless otherwise stated herein, and each individual value is incorporated into the specification as if it were individually stated herein. All methods described herein may be performed in any suitable order, unless otherwise stated herein or unless clearly contradicted by the context. The use of any examples or illustrative language provided herein (e.g., “etc.”) is merely intended to better illustrate the materials and methods and does not impose any limitation on their scope unless otherwise specified in the claims. Nothing in this specification should be interpreted as indicating an element that is not claimed as essential to the implementation of the disclosed materials and methods.

[0072]

[0079] Throughout this specification, any reference to “one embodiment,” “a particular embodiment,” “one or more embodiments,” or “embodiment” means that any particular feature, structure, material, or property described in relation to an embodiment is included in at least one embodiment of this disclosure. Therefore, any occurrence of phrases such as “in one or more embodiments,” “a particular embodiment,” “in one embodiment,” or “in an embodiment” in various places throughout this specification does not necessarily refer to the same embodiment of this disclosure. In one or more embodiments, the particular feature, structure, material, or property is combined in any suitable manner.

[0073]

[0080] While the disclosure herein has been described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the 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 the disclosure without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is intended to include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A metal coordination complex containing molybdenum (VI) and substantially free of halogens and carbonyls.

2. Formula (I) or Formula (II) [In the formula, E is independently selected from an oxo group, an imide group, and a sulfide group, and X is O, SiR] ２ , and CR ２ Independently selected from, L is a ligand that coordinates to nitrogen or phosphorus, and R is independently unsubstituted or substituted C. １ ~C １０ The metal coordination complex according to claim 1, having the structure of an alkyl group.

3. The metal coordination complex according to claim 2, wherein E independently comprises O, N-tBu, or S.

4. The above structure is of formula (I), and L is the following A metal coordination complex according to claim 2, selected from the group consisting of the following.

5. The above structure is of formula (II), However, the next A metal coordination complex according to claim 2, selected from the group consisting of the following.

6. R is Me-, Et-, iPr-, tBu-, and A metal coordination complex according to claim 2, independently selected from substituents.

7. Exposing the substrate to a molybdenum (VI) precursor, The substrate is exposed to the reactant to form a molybdenum film on the substrate. A method for depositing a film, including [a specific element].

8. The molybdenum (VI) precursor is of formula (I) or formula (II) [In the formula, E is independently selected from an oxo group, an imide group, and a sulfide group, and X is O, SiR] ２ , and CR ２ Independently selected from, L is a ligand that coordinates to nitrogen and phosphorus, and R is independently unsubstituted or substituted C １ ~C １０ The method according to claim 7, having the structure of an alkyl group.

9. The method according to claim 8, wherein E independently comprises O, N-tBu, or S.

10. The above structure is of formula (I), and L is the following The method according to claim 8, selected from the group consisting of the following.

11. The above structure is of formula (II), However, the next The method according to claim 8, selected from the group consisting of the following.

12. The method according to claim 7, wherein the reactant comprises one or more of an oxidizing agent and a reducing agent.

13. The method according to claim 7, wherein the molybdenum film comprises one or more of the following: a molybdenum metal (element Mo) film, a molybdenum oxide film, a molybdenum carbide film, a molybdenum silicide film, and a molybdenum nitride film.

14. The method according to claim 7, wherein the substrate is sequentially exposed to the molybdenum (VI) precursor and the reactant.

15. The method according to claim 7, wherein the substrate is simultaneously exposed to the molybdenum (VI) precursor and the reactant.

16. The method according to claim 7, further comprising purging the substrate for a molybdenum (VI) precursor before exposing the substrate to the reactant.

17. The method according to claim 16, wherein purging includes one or more of applying a reduced pressure or flowing a purge gas over the substrate.

18. The method according to claim 7, further comprising repeating the above method to provide a molybdenum film having a thickness in the range of approximately 0.3 nm to approximately 100 nm.

19. A method for depositing a film, comprising forming a molybdenum-containing film in a processing cycle including sequential exposure of a substrate to a molybdenum (VI) precursor, a purge gas, a reactant, and the purge gas.

20. The molybdenum (VI) precursor is of formula (I) or formula (II) [Wherein, E is independently selected from an oxo group, an imide group, and a sulfide group, X is O, SiR ２ , and CR ２ independently selected from, L is a ligand that coordinates to nitrogen or phosphorus, and R is independently an unsubstituted or substituted C １ -C １０ alkyl group], the method according to claim 19.

Images