Stress tuning of molybdenum

Abstract

Methods and apparatuses for tuning stress of molybdenum films during deposition are provided. Methods include combining thermal atomic layer deposition with plasma-enhanced atomic layer deposition, using plasma-enhanced atomic layer deposition and modulating plasma power during deposition, and / or using a dopant during the deposition.

Description

STRESS TUNING OF MOLYBDENUM CROSS-REFERENCES

[0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in their entireties and for all purposes. BACKGROUND

[0002] Semiconductor fabrication processes involve metallization. Metallization in, for example, logic back-end-of-line (“BEOL”) processing that often involves formation of copper, but as devices shrink, other materials may be considered.

[0003] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure. SUMMARY

[0004] One aspect involves a method for processing substrates, the method including: depositing a molybdenum film by one or more plasma-enhanced atomic layer deposition cycles, a plasma- enhanced atomic layer deposition cycle including: exposing a semiconductor substrate to a molybdenum-containing precursor, and exposing the semiconductor substrate to a reducing agent in a plasma environment, the plasma environment generated by igniting a plasma at a plasma power; and pulsing the plasma between either (1) an ON state and OFF state, or (2) a LOW state or HIGH state to modulate stress of the molybdenum film, whereby the exposing of the semiconductor substrate to the molybdenum-containing precursor and exposing the semiconductor substrate to the reducing agent in the plasma environment are performed in temporally separated pulses.

[0005] In various embodiments, the plasma power is about 50W to about 2000W.

[0006] In various embodiments, the method also includes selecting different plasma powers for at least two of the one or more plasma-enhanced atomic layer deposition cycles to modulate stress of the molybdenum film.

[0007] In various embodiments, the LOW state involves using a plasma power of about 0W to about 100W. 1 LAMRP953WO_11461-1WO

[0008] In various embodiments, the HIGH state involves using a plasma power of about 50W to about 2000W.

[0009] In various embodiments, the reducing agent is one of hydrogen and diborane.

[0010] Another aspect involves a method for depositing a molybdenum film including a first molybdenum layer and a second molybdenum layer, the method including: depositing the first molybdenum layer to a first thickness at a first deposition temperature by: exposing a semiconductor substrate to a first molybdenum-containing precursor, and exposing the semiconductor substrate to a first reducing agent in a plasma environment; and depositing the second molybdenum layer to a second thickness at a second deposition temperature by: exposing a semiconductor substrate to a second molybdenum-containing precursor, and exposing the semiconductor substrate to a second reducing agent in a thermal environment.

[0011] In various embodiments, the method also includes adjusting at least one of the following process conditions to modulate stress of the molybdenum film: plasma power during exposing of the semiconductor substrate in the plasma environment, the first deposition temperature, a duration of the exposing of the semiconductor substrate to the first molybdenum-containing precursor, a duration of the exposing of the semiconductor substrate to the first reducing agent, the second deposition temperature, a duration of the exposing of the semiconductor substrate to the second molybdenum-containing precursor, and a duration of the exposing of the semiconductor substrate to the second reducing agent.

[0012] In various embodiments, the first thickness has tensile stress.

[0013] In various embodiments, the second thickness has compressive stress.

[0014] In various embodiments, the first thickness and second thickness are modulated to achieve zero stress in the molybdenum film.

[0015] In various embodiments, the method also includes performing one or more cycles of (1) depositing a first set of molybdenum layers by exposing the semiconductor substrate to the first molybdenum-containing precursor, and exposing the semiconductor substrate to the first reducing agent in the plasma environment; and (2) depositing a second set of molybdenum layers by exposing the semiconductor substrate to the second molybdenum-containing precursor, and exposing the semiconductor substrate to the second reducing agent in the thermal environment, wherein the first set of molybdenum layers includes at least 1 or greater number of layers and the second set of molybdenum layers includes at least 1 or greater number of layers.

[0016] In various embodiments, the first thickness is about 20Å to about 250Å. In some embodiments, the first thickness is about 1Å to about 20Å. 2 LAMRP953WO_11461-1WO

[0017] In various embodiments, the second thickness is about 20Å to about 250Å. In some embodiments, the second thickness is about 1Å to about 20Å.

[0018] In various embodiments, the method also includes purging before or after at least one of: exposing the semiconductor substrate to the first molybdenum-containing precursor, exposing the semiconductor substrate to the first reducing agent in the plasma environment, exposing the semiconductor substrate to the second molybdenum-containing precursor, and exposing the semiconductor substrate to the second reducing agent in the thermal environment.

[0019] In various embodiments, exposing the semiconductor substrate to the first molybdenum- containing precursor and exposing the semiconductor substrate to the first reducing agent in the plasma environment are performed simultaneously.

[0020] In various embodiments, exposing the semiconductor substrate to the first molybdenum- containing precursor and exposing the semiconductor substrate to the first reducing agent in the plasma environment are performed in temporally separated pulses.

[0021] In various embodiments, a co-reactant is flowed during at least one of exposing the semiconductor substrate to the first molybdenum-containing precursor, exposing the semiconductor substrate to the first reducing agent in the plasma environment, exposing the semiconductor substrate to the second molybdenum-containing precursor, and exposing the semiconductor substrate to the second reducing agent in the thermal environment.

[0022] In various embodiments, the co-reactant is selected from the group consisting of argon, nitrogen, and helium.

[0023] In various embodiments, at least one of the first deposition temperature and the second deposition temperature is about 200°C to about 700°C. In some embodiments, at least one of the first deposition temperature and the second deposition temperature is about 250°C to about 500°C.

[0024] In various embodiments, the plasma environment is generated by igniting a plasma at a plasma power of about 350W to about 950W.

[0025] In various embodiments, the first molybdenum-containing precursor and second molybdenum-containing precursor are the same.

[0026] In various embodiments, the reducing agent is one of hydrogen and diborane.

[0027] Another aspect involves a method for processing substrates, the method including: exposing a semiconductor substrate to a molybdenum-containing precursor, exposing the semiconductor substrate to a reducing agent to form at least a molybdenum-containing film; and exposing the semiconductor substrate to a dopant-containing precursor to modulate stress of the molybdenum-containing film. 3 LAMRP953WO_11461-1WO

[0028] In various embodiments, the dopant-containing precursor includes a metal, carbon, silicon, or combinations thereof. In some embodiments, the metal is selected from the group consisting of vanadium, lanthanum, titanium, tungsten, chromium, tantalum, manganese, niobium, iron, mercury, thallium, indium, gallium, germanium, tin, rhenium, nickel, boron, zirconium, ruthenium, and hafnium. In various embodiments, the dopant-containing precursor comprises carbon or silicon.

[0029] In various embodiments, at least two or more of exposing the semiconductor substrate to the molybdenum-containing precursor, exposing the semiconductor substrate to the reducing agent, and exposing the semiconductor substrate to the dopant-containing precursor are performed in temporally separated pulses.

[0030] In various embodiments, exposing the semiconductor substrate to the dopant-containing precursor includes exposing the molybdenum-containing film to the dopant-containing precursor.

[0031] In various embodiments, the reducing agent is one of hydrogen and diborane.

[0032] In various embodiments, the molybdenum-containing film has a stress of about -2000 MPa to about 5000 MPa.

[0033] In various embodiments, the molybdenum-containing film has compressive stress. In some embodiments, the molybdenum-containing film is doped with tantalum.

[0034] In various embodiments, the molybdenum-containing film has tensile stress. In some embodiments, molybdenum-containing film is doped with vanadium or tungsten.

[0035] In various embodiments, the molybdenum-containing film has a first thickness and exposing the semiconductor substrate to a dopant-containing precursor forms a dopant-containing layer on the semiconductor substrate to a second thickness.

[0036] In various embodiments, stress of the molybdenum-containing film is modulated by varying a ratio of the first thickness to the second thickness.

[0037] In various embodiments, the method also includes annealing the semiconductor substrate.

[0038] In various embodiments, the dopant-containing precursor is exposed for a duration of about 0.1 seconds to about 600 seconds.

[0039] In various embodiments, the dopant-containing precursor is selected from the group consisting of vanadium tetrachloride and tantalum pentachloride.

[0040] In various embodiments, at least one or more of exposing the semiconductor substrate to the molybdenum-containing precursor, exposing the semiconductor substrate to the reducing agent, and exposing the semiconductor substrate to the dopant-containing precursor are performed 4 LAMRP953WO_11461-1WOin a plasma environment.

[0041] In various embodiments, the exposing the semiconductor substrate to the molybdenum- containing precursor, and exposing the semiconductor substrate to the reducing agent are performed simultaneously.

[0042] In various embodiments, the method also includes purging a process chamber housing the semiconductor substrate before or after at least one of exposing the semiconductor substrate to the molybdenum-containing precursor, exposing the semiconductor substrate to the reducing agent, and exposing the semiconductor substrate to the dopant-containing precursor.

[0043] In various embodiments, the molybdenum-containing film is deposited at a temperature of about 200°C to about 700°C. In some embodiments, the temperature is about 250°C to about 400°C.

[0044] In various embodiments, the molybdenum-containing film is deposited at a chamber pressure of less than about 500 Torr. In some embodiments, the molybdenum-containing film is deposited at a chamber press of less than about 80 Torr.

[0045] In various embodiments, the plasma environment is generated by igniting a plasma at a plasma power of about 50W to about 2000W.

[0046] In any of the above embodiments, the molybdenum-containing precursor (or at least one of the first molybdenum-containing precursor and second molybdenum-containing precursor) includes a structure of Formula (I), Formula (II), or Formula (III): MoLn (I), Mo2Ln(II), or LnMo(L’)mMoLn (III), whereby each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3.

[0047] In various embodiments, the molybdenum-containing precursor (or at least one of the first molybdenum-containing precursor and second molybdenum-containing precursor) is molybdenum oxychloride.

[0048] In various embodiments, the molybdenum-containing precursor (or at least one of the first molybdenum-containing precursor and second molybdenum-containing precursor) is molybdenum pentachloride. 5 LAMRP953WO_11461-1WO

[0049] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; a plasma generator; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer- executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a molybdenum-containing precursor to the one or more process chambers, cause generation of a plasma, cause introduction of a reducing agent to the one or more process chambers, cause pulsing of the plasma between either (1) an ON state and OFF state, or (2) a LOW state or HIGH state.

[0050] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; a plasma generator; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer- executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a first molybdenum-containing precursor to the one or more process chambers, cause introduction of a first reducing agent to the one or more process chambers, cause generation of a plasma during the at least one of the introduction of the first reducing agent or the introduction of the first molybdenum-containing precursor to form a first molybdenum layer to a first thickness, cause introduction of a second molybdenum-containing precursor to the one or more process chambers, and cause introduction of a second reducing agent without generating a plasma to form a second molybdenum layer to a second thickness.

[0051] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a molybdenum-containing precursor to the one or more process chambers, 6 LAMRP953WO_11461-1WOcause introduction of a reducing agent, and cause introduction of a dopant-containing precursor to the one or more process chambers.

[0052] In various embodiments, the apparatus also includes a plasma generator, such that the controller further includes instructions for causing generation of a plasma.

[0053] Another aspect involves a device including: two or more alternating layers of: a tensile molybdenum layer having a thickness of about 5Å to about 250Å, and a compressive molybdenum layer having a thickness of about 5Å to about 250Å.

[0054] Another aspect involves a device including: a molybdenum layer doped with a dopant selected from the group consisting of vanadium, lithium, titanium, tungsten, chromium, tantalum, manganese, silicon, niobium, iron, mercury, thallium, indium, gallium, germanium, tin, rhenium, nickel, boron, zirconium, hafnium, carbon, and ruthenium, such that dopant concentration of the dopant is selected to modulate stress without substantially affecting resistivity of the molybdenum layer.

[0055] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figures 1 and 2 are process flow diagrams for methods performed in accordance with certain disclosed embodiments.

[0057] Figures 3, 4, and 5 are schematic illustrations of example films deposited using certain disclosed embodiments.

[0058] Figures 6 and 7 are process flow diagrams for methods performed in accordance with certain disclosed embodiments.

[0059] Figure 8 is a timing schematic diagram depicting operations that may be performed in accordance with certain disclosed embodiments.

[0060] Figure 9 is a schematic diagram of an example process chamber for performing certain disclosed embodiments.

[0061] Figures 10 and 11 are schematic diagrams of example process tools for performing certain disclosed embodiments.

[0062] Figure 12 is a graph depicting stress of molybdenum films deposited by thermal atomic layer deposition and molybdenum films deposited by plasma-enhanced atomic layer deposition (PEALD).

[0063] Figure 13 is a graph depicting stress of molybdenum films deposited by PEALD using various plasma powers in accordance with certain disclosed embodiments.

[0064] Figure 14 is a graph depicting bow change of molybdenum films deposited by PEALD 7 LAMRP953WO_11461-1WOusing various plasma powers in accordance with certain disclosed embodiments.

[0065] Figure 15 is a graph depicting stress of molybdenum films deposited using thermal ALD and using PEALD.

[0066] Figure 16 is a graph depicting molybdenum deposition thickness per deposition cycle when using hydrogen or diborane as a reducing agent in accordance with certain disclosed embodiments.

[0067] Figure 17 is a graph depicting molybdenum roughness of molybdenum films deposited using hydrogen or diborane as a reducing agent in accordance with certain disclosed embodiments. DETAILED DESCRIPTION

[0068] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.

[0069] Semiconductor substrate fabrication processes involve deposition of metal films and metal-containing films. Metal film stress is relevant to many applications to maintain structural integrity of the device and avoid defects caused by line bending, cracking and other issues. It can also be used beneficially as part of strain engineering strategy to enhance carrier mobility in a transistor channel.

[0070] In some cases, molybdenum (Mo) may be used as a metal. Molybdenum film stress can be highly sensitive to substrate, thickness, and process conditions. The stress can vary from a highly compressive film to a highly tensile film. A highly tensile film may be one that has a stress of about 1 GPa or greater. A tensile film has a stress of greater than 0 MPa and a compressive film has a stress of less than 0 MPa. A tensile film may be curved upward (concave) and a compressive film may be curved downward (convex). Being able to modulate Mo film stress can be advantageous to a variety of applications in logic and memory fabrication.

[0071] One of the potential applications includes Mo as a metal gate fill material in gate all- around (GAA) transistor architecture. Molybdenum film stress can play a role in modulating carrier mobility and improving or degrading p-channel metal—oxide—semiconductor logic (PMOS) and N-type metal—oxide—semiconductor logic (NMOS) device performance. Another potential application is usage of Mo as a NAND wordline material, as being able to control Mo in such applications reduces line bending and prevents device failure. 8 LAMRP953WO_11461-1WO

[0072] Provided are methods of depositing Mo and modulating film stress of Mo. The methods involve combining thermal atomic layer deposition (ALD) of Mo with plasma-enhanced atomic layer deposition (PEALD) of Mo, modulating plasma power during PEALD, incorporating dopants during deposition of Mo, incorporating a seed layer having particular composition or being deposited by a particular technique to be a template for subsequent Mo grain formation during Mo deposition, and combinations thereof.

[0073] ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis in cycles. As an example, an ALD cycle may include the following operations: (i) delivery / adsorption of a precursor, (ii) purging of precursor from the chamber, (iii) delivery of a second reactant and optionally igniting plasma, and (iv) purging of byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of a substrate affects the film composition and properties, such as nonuniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc.

[0074] Unlike a chemical vapor deposition (CVD) technique, ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface that includes a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as a Mo-containing precursor, in a dose provided to a chamber housing a substrate. Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and / or physisorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, an adsorbed layer of a Mo-containing precursor may include the Mo-containing precursor as well as derivatives of the Mo-containing precursor. After a first precursor dose, the chamber is then evacuated to remove most or all of first precursor remaining in gas phase so that mostly or only the adsorbed species remain. In some implementations, the chamber may not be fully evacuated. For example, the reactor may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction. A second reactant, which may be a reducing agent, such as a hydrogen-containing gas, is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a source of activation is 9 LAMRP953WO_11461-1WOapplied temporally. In some embodiments activation is thermal which may be performed by heating the substrate. In some embodiments activation is performed by using a plasma. The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness. While the example described involves a first dose of Mo-containing precursor followed by the second reactant, it will be understood that in some embodiments, the reverse may be performed, such that the hydrogen-containing reactant adsorbs onto the surface and the Mo-containing precursor reacts with the adsorbed hydrogen- containing reactant to form Mo metal. In various embodiments, the Mo-containing precursor dose and the reducing agent exposures are performed in temporally separated pulses. In various embodiments, when the Mo-containing precursor is introduced to the process chamber, the second reactant flow is stopped, and when the second reactant is introduced to the process chamber, the Mo-containing precursor flow is stopped.

[0075] In some implementations, the ALD methods include plasma activation and may be referred to herein as PEALD. As described herein, the ALD methods and apparatuses described herein may be conformal film deposition (CFD) methods, which are described generally in U.S. Patent Application No.13 / 084,399 (now U.S. Patent No. 8,728,956), filed April 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” and in U.S. Patent Application No.13 / 084,305, filed April 11, 2011, and titled “SILICON NITRIDE FILMS AND METHODS,” which are herein incorporated by reference in their entireties.

[0076] In certain disclosed embodiments, Mo films may be deposited by PEALD and the plasma power used during PEALD may be modulated to tune film stress. In certain cases, Mo may be deposited using thermal ALD and process variables such as temperature and precursor dose can be used to tune film stress.

[0077] It is observed that when Mo is deposited by PEALD to a thickness of 0Å to about 80Å, Mo films tend to be more tensile, whereas Mo films deposited by thermal ALD to a thickness of up to about 100Å results in more compressive stress. While thickness and deposition technique affects the stress, other process conditions, such as temperature, dose conditions (such as dose time, or flow rate(s), etc.) may also affect the stress. In various embodiments, thermally deposited Mo and PEALD-deposited Mo are combined to modulate the overall stress of the deposited Mo material. The relative thickness of the ALD- and PEALD-deposited Mo layers and sequence of depositions can be varied to increase tunability of the film stress from highly tensile to highly compressive or a nearly zero stress film. Such embodiments may be used without a post- 10 LAMRP953WO_11461-1WOdeposition anneal process (which may be usually performed at a temperature of greater than about 450°C), which may be, in some embodiments, outside a thermal budget for logic applications. Some embodiments may also be used in conjunction with a post-deposition anneal. Some embodiments can be performed in process tools configured to perform multiple types of deposition (such as both thermal ALD and PEALD) in separate chambers, or in a tool that is configured to perform multiple processes in the same chamber, or without breaking vacuum.

[0078] Embodiments directed to usage of a dopant can also be used to modulate film stress. The dopants may have different atomic radii; examples include, but are not limited to, vanadium, titanium, tungsten, lanthanum, chromium, tantalum, manganese, silicon, niobium, iron, mercury, thallium, indium, gallium, germanium, tin, rhenium, nickel, boron, zirconium, and ruthenium. Other properties of the dopant, such as coefficient of thermal expansion (CTE), elastic modulus and microstructure, may also play a role in affecting the final stress of the doped Mo film.

[0079] Such dopants can be used to toggle varying stress in a Mo film, depending on the atomic size of the dopant, to thereby induce either compressive or tensile stress. A multi-step Mo deposition process can be used that incorporates dopant deposition, or a dopant precursor soak process, and the relative amount of Mo to dopant contribution, or thickness ratio, as well as sequence of deposition and other process conditions may be used to tune the film stress from highly tensile to highly compressive or to nearly zero stress. Using metal dopants also ensures that resistivity is maintained for the metal film, and in some cases the dopant may be deposited in the same platform as the Mo film such that both materials are deposited without breaking vacuum.

[0080] Figure 1 shows an example process flow diagram of operations that may be performed in accordance with certain disclosed embodiments. Figure 1 shows an example involving combining thermal ALD (TALD) and PEALD.

[0081] In Figure 1, in an operation 101, a substrate is provided to a process chamber. The substrate may be a silicon or other semiconductor wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi-conducting material deposited thereon. Certain disclosed methods may also be applied to form metallization stack structures on other substrates, such as glass, plastic, and the like. The substrate may also have a barrier layer or a metal-containing surface upon which Mo is to be deposited. Example materials on the surface of the semiconductor substrate include but are not limited to tungsten-containing materials such as tungsten metal or tungsten nitride, dielectric materials, and titanium-containing materials such as titanium nitride.

[0082] In an operation 102, Mo is deposited on the substrate by thermal ALD. 11 LAMRP953WO_11461-1WO

[0083] Figure 2 provides an example process flow diagram depicting operations that may be performed in thermal ALD. Operations 202-208 of Figure 2 may be performed to form a Mo layer directly at least a dielectric surface or other surface on a substrate. In some embodiments, the Mo layer is conformal.

[0084] In operation 202, the substrate is exposed to a reducing agent gas to form a reducing agent layer. In various embodiments, the reducing agent is a hydrogen-containing gas. In various embodiments, the reducing agent is hydrogen or hydrogen gas. In various embodiments, the reducing agent is diborane. In various embodiments, the reducing agent is hydrogen, a silane, a borane, or combinations thereof. In some embodiments, the reducing agent gas may be a silane, a borane, or a mixture of a silane and diborane. Examples of silanes including SiH4 and Si2H6 and examples of boranes include diborane (B2H6), as well as BnHn+4, BnHn+6, BnHn+8, BnHm, where n is an integer from 1 to 10, and m is a different integer than n. Other boron-containing compounds may also be used, e.g., alkyl boranes, alkyl boron, aminoboranes (CH3)2NB(CH2)2, carboranes such as C2BnHn+2.

[0085] Diborane may be used as a reducing agent to improve throughput. In some embodiments, throughput where diborane is used as the reducing agent, as compared to when hydrogen gas is used, may be at least about 20% greater.

[0086] In various embodiments, diborane may be used for favorable energetics of diborane reduction chemistry to assist in removing chlorine atoms from a molybdenum-containing precursor. The reaction Gibbs free energy of a reduction reaction where diborane reacts with a molybdenum-containing precursor may be lower than the reaction Gibbs free energy of a reduction reaction where hydrogen reacts with the molybdenum-containing precursor. The reaction involving diborane may be more energetically favorable. These energetics may improve molybdenum nucleation and chlorine scavenging. A mixture of diborane and hydrogen may also be used to mitigate formation of molybdenum boride, which might be undesirable.

[0087] Diborane may also be used to improve nucleation of molybdenum. In various embodiments, diborane is used as a co-reactant with hydrogen gas. In various embodiments, diborane is used as a co-reactant with hydrogen gas in some but not all deposition cycles. In some embodiments, diborane is used as a co-reactant with hydrogen gas for initial deposition cycles, such as at least the first deposition cycle, or at least the first few deposition cycles, up to the first 5 deposition cycles, or up to the first 10 deposition cycles. Where diborane is used in some but not all deposition cycles, hydrogen gas may be the only reducing agent flowed during the remaining deposition cycles where diborane is not used. In some embodiments, a different mixture 12 LAMRP953WO_11461-1WOof reducing agents may be used in this manner such that two or more reducing agents are flowed in at least the first or some number of initial deposition cycles, and in subsequent deposition cycles, one or more of the reducing agents are not used and only one or fewer than the initial two or more reducing agents are used in subsequent deposition cycles. The reducing agents selected may be different in each cycle. It will be understood that while the example above described an embodiment involving hydrogen and diborane as reducing agents for deposition using varied reducing agents in each deposition cycle, other reducing agents may be used in lieu of hydrogen or diborane or both, or other reducing agents may also be added to hydrogen or diborane or both.

[0088] In some embodiments, diborane may be used to soak between intermittent depositions of molybdenum material. For example, the substrate may be exposed to diborane for a soak period of about 1 second to about 10 seconds or about 2 seconds to about 7 seconds for every certain thickness of molybdenum deposited using hydrogen or a boron-free reducing agent as a reducing agent (such as every about 20 Å of molybdenum deposition).

[0089] Diborane may be used in various embodiments regardless of the technique used to deposition molybdenum. For example, diborane may be used as a reducing agent in ALD embodiments, CVD embodiments, PEALD embodiments, and / or pulsed CVD embodiments.

[0090] Diborane may be used as a pre-soak prior to deposition of Mo, or in between depositions of Mo, or after deposition of Mo. In some embodiments, purging may be performed immediately after flow of diborane using a purge gas. Purging is optional in various embodiments. In some embodiments, diborane may be used as a boron dopant precursor to form boron-doped Mo.

[0091] When diborane is used as at least one of the reducing agents, the deposition temperature may be about 100° to about 500°C or about 250°C to about 400°C. When diborane is used as at least one of the reducing agents, the chamber pressure may be less than about 500 Torr.

[0092] In some implementations, the reducing agent layer may include silicon or silicon- containing material, phosphorous or a phosphorous-containing material, germanium or a germanium-containing material, boron or boron-containing material that is capable of reducing a molybdenum precursor and combinations thereof. Further example reducing agent gases that can be used to form such layers include PH3, SiH2Cl2, and GeH4. According to various embodiments, hydrogen may or may not be run in the background. (While hydrogen can reduce molybdenum precursors, it does not function as a reducing agent in a gas mixture with a sufficient amount of stronger reducing agents such as silane and diborane.)

[0093] In some embodiments, the reducing agent gas is a mixture including a small amount of a boron-containing gas, such as diborane, with another reducing agent. The addition of a small 13 LAMRP953WO_11461-1WOamount of a boron-containing gas can greatly affect the decomposition and sticking coefficient of the other reducing agent. It should be noted that exposing the substrate sequentially to two reducing agents, e.g., silane and diborane may be performed. However, flowing a mixture of gases can facilitate the addition of very small amounts of a minority gas, e.g., at least a 100:1 ratio of silane to diborane. In some embodiments, a carrier gas may be flowed. In some embodiments, a carrier gas, such as nitrogen (N2), argon (Ar), helium (He), or other inert gases, may be flowed during operation 402.

[0094] In some embodiments, a reducing agent layer may include elemental silicon (Si), elemental boron (B), elemental germanium (Ge), or mixtures thereof. For example, as described below, a reducing agent layer may include Si and B. The amount of B may be tailored to achieve high deposition rate of the reducing agent layer but with low resistivity. In some embodiments, a reducing agent layer may have between 5% and 80% B for example, or between 5% and 50% B, between 5% and 30%, or between 5% and 20% B, with the balance consisting essentially of Si and in some cases, H. Hydrogen atoms be present, e.g., SiHx, BHy, GeHz, or mixtures thereof where x, y, and z may independently be between 0 and a number that is less than the stoichiometric equivalent of the corresponding reducing agent compound.

[0095] In some embodiments, the composition may be varied through the thickness of the reducing agent layer. For example, a reducing agent layer may be 20% B at the bottom of the reducing agent layer and 0% B the top of the layer. The total thickness of the reducing agent layer may be between 10Å and 50Å, and is some embodiments, between 15Å and 40Å, or 20Å and 30Å. The reducing agent layer may conformally lines the feature.

[0096] Substrate temperature during operation 202 may be maintained at a temperature T1 to achieve a conformal film. In various embodiments, the temperature may be about 200°C to about 700°C.

[0097] Operation 202 may be performed for any suitable duration. In some examples, Example durations include between about 0.25 seconds and about 30 seconds, about 0.25 seconds and about 20 seconds, about 0.25 seconds and about 5 seconds, or about 0.5 seconds and about 3 seconds.

[0098] In operation 204, the chamber is optionally purged to remove excess reducing agent that did not adsorb to the surface of the substrate. A purge may be conducted by flowing an inert gas at a fixed pressure thereby reducing the pressure of the chamber and re-pressurizing the chamber before initiating another gas exposure. Example inert gases include nitrogen (N2), argon (Ar), helium (He), and mixtures thereof. The purge may be performed for a duration between about 0.25 seconds and about 30 seconds, about 0.25 seconds and about 20 seconds, about 0.25 seconds 14 LAMRP953WO_11461-1WOand about 5 seconds, or about 0.5 seconds and about 3 seconds.

[0099] In operation 206, the substrate is exposed to a Mo-containing precursor at a substrate temperature T2. Examples of Mo-containing compounds are given elsewhere herein and include chlorides and oxychlorides. Use of oxygen-containing precursors can lead to impurity incorporation and higher resistivity. However, if oxygen is incorporated, a very thin, possibly discontinuous reducing agent layer may be used for an acceptable resistivity. In some embodiments, a carrier gas, such as nitrogen (N2), argon (Ar), helium (He), or other inert gases, may be flowed during operation 406. Examples of temperatures are 500oC to 700oC.

[0100] Operation 206 may be performed for any suitable duration. In some embodiments, it may involve a soak of the Mo-containing precursor and in some embodiments, a sequence of Mo- containing precursor pulses. According to various embodiments, operation 206 may or may not be performed in the presence of H2. If H2 is used, in some embodiments, it and the Mo-containing precursor may be applied in an ALD-type mode. For example: Pulse of H2 Argon purge Pulse of Mo-containing precursor with or without H2 in background Argon purge Repeat

[0101] The substrate temperature T2 is high enough that the Mo-containing precursor reacts with the reducing agent layer to form elemental Mo. The entire reducing agent layer is converted to Mo. In some embodiments, the temperature is at least 450oC, and may be at least 550oC to obtain conversion of at or near 100%. The resulting feature is now lined with a conformal film of Mo. It may be between 10Å and 50Å, and is some embodiments, between 15Å and 40Å, or 20Å and 30Å. In general, it will be about the same thickness as the reducing agent layer. In some embodiments, it may be may be up to 5% thicker than the reducing agent layer due to volumetric expansion during the conversion. In some embodiments, a CVD Mo layer may be deposited on the conformal Mo layer.

[0102] While the discussion above involves forming a reducing agent layer and converting the reducing agent layer to a Mo layer, it will be understood that operations 202 and 206 may be reversed. For example, in some embodiments, the substrate is exposed to the Mo precursor prior to exposing the substrate to the reducing agent. Additionally, operations 204 and 208 are optional. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce reducing agent, purge, introduce Mo precursor, purge. In some 15 LAMRP953WO_11461-1WOembodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce reducing agent, introduce Mo precursor, purge. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce reducing agent, purge, introduce Mo precursor. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce reducing agent, introduce Mo precursor, purge. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce reducing agent, introduce Mo precursor. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce Mo precursor, purge, introduce reducing agent, purge. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce Mo precursor, introduce reducing agent, purge. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce Mo precursor, purge, introduce reducing agent. In some embodiments, the following thermal ALD cycle may involve these operations in this order in one or more cycles: introduce Mo precursor, introduce reducing agent.

[0103] Returning to Figure 1, in operation 103, Mo is deposited by PEALD. PEALD may involve any of the above operations discussed with respect to Figure 2 except that a plasma may be used when either (1) exposing the substrate to the reducing agent or (2) exposing the substrate to the Mo-containing precursor or both. Like ALD, in some embodiments, the Mo precursor is introduced before exposing the substrate to a reducing agent plasma. In some embodiments, the reducing agent plasma is introduced before the Mo precursor. In some embodiments, the process chamber is purged.

[0104] Plasma may be generated remotely or in situ. In various embodiments, plasma is ignited during flow of the reducing agent, which may be hydrogen gas. The plasma power may be about 50 W to about 2000 W.

[0105] In operation 105, plasma power is optionally modulated during PEALD or during operation 103. Modulation may be performed by pulsing between an ON and OFF state, or between a LOW and HIGH plasma power.

[0106] During an ON state, the plasma power may be about 50 W to about 2000 W. During an OFF state, the plasma power is 0 W. For a LOW state, the plasma power may be about 0 W to about 100 W, or greater than 0 W and less than about 100 W. For a HIGH state, the plasma power may be about 50 W to about 2000 W. These example plasma powers may be for a tool for processing four wafers simultaneously. 16 LAMRP953WO_11461-1WO

[0107] In an operation 107, operations 102 and 103 are optionally repeated. In some embodiments, operation 105 is also repeated.

[0108] An example formula for a process flow that may be used in accordance with certain disclosed embodiments is as follows: ^^^^^^^^^^^^ ^^^^^^ → ^^^ℎ^^^^^^^^^^ ^^^^^^ ^^^^^^^^where A is the number of cycles of PEALD of Mo, B is the number of cycles of thermal ALD of Mo, and C is the number of overall cycles for performing both PEALD of Mo and thermal ALD of Mo. The number A affects the thickness of the film deposited by PEALD, and the number B affects the thickness of the film deposited by thermal ALD, and C, the number of times the overall cycle is repeated, affects the final stack thickness. A, B, and C may be any integer greater than or equal to 0.

[0109] Figures 3, 4, and 5 show example stacks of Mo deposited by various disclosed embodiments. In Figure 3, a thick thermally-deposited Mo 303 is deposited first using multiple cycles of a thermal ALD, then a thick plasma-deposited Mo 302 is deposited thereon using multiple cycles of PEALD. Example thicknesses for a “thick” thermally-deposited Mo include but are not limited to a thickness of about 10Å to about 500Å or about 5Å to about 250Å or about 20Å to about 250Å or about 1Å to about 20Å.

[0110] Figure 4 shows another example where a thick plasma-deposited Mo 412 is deposited thereon using multiple cycles of PEALD, followed by a thick thermally-deposited Mo 313 deposited using multiple cycles of thermal ALD. Example thicknesses for a “thick” plasma- deposited Mo include but are not limited to a thickness of about 10Å to about 500Å or about 20Å to about 250Å. While ALD embodiments are described herein, it will be understood that in some embodiments, chemical vapor deposition (CVD) may be used. For example, instead of thermal ALD, thermal CVD may be used. Instead of PEALD, PECVD may be used. In various embodiments, one or more of thermal ALD, PEALD, thermal CVD, and PECVD are used.

[0111] Figure 5 shows another example where a thin plasma-deposited Mo 522 is deposited using one or more cycles of PEALD, followed by a thin thermally-deposited Mo 523 deposited using one or more cycles of thermal ALD, followed by a thin plasma-deposited Mo 532 is deposited using one or more cycles of PEALD, followed by a thin thermally-deposited Mo 533 deposited using one or more cycles of thermal ALD, a thin plasma-deposited Mo 542 is deposited using one or more cycles of PEALD, followed by a thin thermally-deposited Mo 543 deposited using one or more cycles of thermal ALD. A “thin” Mo may have a thickness of about 1Å to about 20Å. While the example here shows that the plasma-deposited Mo is on the bottom of the 17 LAMRP953WO_11461-1WOstack, it will be understood that in some embodiments, a thermally-deposited Mo may be at the bottom of the stack. Likewise, while the example here shows that the thermally-deposited Mo is on the top of the stack, it will be understood that in some embodiments, a plasma-deposited Mo may be at the top of the stack. Additionally, both the top and bottom layers may both be plasma- deposited, or they may both be thermally-deposited. Fewer or more layers may also be deposited. Example thicknesses for a “thin” thermally-deposited Mo include but are not limited to a thickness of about 1Å to about 50Å. Example thicknesses for a “thin” plasma-deposited Mo include but are not limited to a thickness of about 1Å to about 50Å.

[0112] Figure 6 shows an example process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. Figure 6 begins with an operation 601, which involves providing a substrate to the process chamber. In various embodiments, this operation may involve the same operations and process conditions and techniques as operation 101 of Figure 1 as discussed above.

[0113] Returning to Figure 6, in an operation 603, Mo is deposited by PEALD. In various embodiments, this example process flow does not involve any thermal ALD. In various embodiments, the Mo deposited in operation 603 is deposited directly on the substrate without any thermally-deposited Mo present on the substrate surface. In various embodiments, the Mo deposited in operation 603 is deposited on a barrier layer or a metal-containing surface upon which Mo is to be deposited. Example materials on the surface of the semiconductor substrate prior to depositing the Mo in operation 603 include but are not limited to tungsten-containing materials such as tungsten metal or tungsten nitride, dielectric materials, and titanium-containing materials such as titanium nitride. Operation 603 may involve any of the operations, process conditions, and precursors that are described above with respect to operation 103 of Figure 1.

[0114] In an operation 605, plasma power is modulated during PEALD, or during operation 603, to change or tune the stress of the molybdenum film being deposited. For example, modulation may be performed by pulsing between an ON and OFF state, or between a LOW and HIGH plasma power.

[0115] During an ON state, the plasma power may be about 50 W to about 2000 W. For a LOW state, the plasma power may be about 0 W to about 100 W. For a HIGH state, the plasma power may be about 50 W to about 2000 W. These example plasma powers may be for a tool for processing four wafers simultaneously.

[0116] In one example, for a film of about 100Å in thickness, the stress may be tuned from about -100 MPa to about 400 MPa by using a variety of plasma powers ranging from about 350W 18 LAMRP953WO_11461-1WOto about 950W. In another example, for a film of about 200Å in thickness, the stress may be tuned from about -350 MPa to about 100 MPa using a variety of plasma powers ranging from about 350W to about 950W.

[0117] The stress depends on the thickness of the Mo film being deposited. In some embodiments, the Mo film is deposited to a thickness of about 20Å to about 500Å, or about 2 nm to about 50 nm. In some embodiments, the Mo film is used in gate or logic structures and is deposited to a thickness of about 3 nm to about 10 nm.

[0118] The temperature used during operation 605 may also affect the stress. In some embodiments, increasing the temperature may increase tensile stress. In certain disclosed embodiments, the temperature may be about 200°C to about 700°C to achieve a -2GPa to 5 GPa Mo film at a thickness of about 200Å.

[0119] Operation 605 may involve any of the process conditions described above with respect to operation 105 of Figure 1.

[0120] In an operation 607, operations 603 and 605 are optionally repeated. For example, multiple PEALD cycles may be performed. In one or several or all of the cycles, plasma power may be modulated.

[0121] In some embodiments, Mo may be deposited by thermal ALD with a dopant to modulate film stress. Figure 7 provides a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. In an operation 701, a substrate is provided to a process chamber. The substrate may have materials deposited thereon. Any of the substrate features described above with respect to operation 101 in Figure 1 may be applicable to operation 701.

[0122] In an operation 702, the substrate is exposed to a reducing agent gas. This may involve any of the operations, techniques, process conditions, and chemistries such as those described above with respect to operation 202 of Figure 2.

[0123] In an operation 703, the process chamber is optionally purged. This may involve any of the operations, techniques, process conditions, and chemistries such as those described above with respect to operation 204 of Figure 2.

[0124] In an operation 703, the substrate is exposed to a Mo-containing precursor. This may involve any of the operations, techniques, process conditions, and chemistries such as those described above with respect to operation 206 of Figure 2.

[0125] In an operation 705, the process chamber is optionally purged. This may involve any of the operations, techniques, process conditions, and chemistries such as those described above with 19 LAMRP953WO_11461-1WOrespect to operation 202 of Figure 2.

[0126] While Figure 7 shows a substrate exposed to a reducing agent gas prior to exposing the substrate to the Mo-containing precursor, it will be understood that in some embodiments, operations 702 and 704 may be reversed. Additionally in some embodiments neither operation 703 nor 705 may be performed, or only one of operations 703 or 705 are performed, or both of operations 703 and 705 are performed.

[0127] In an operation 706, the substrate is exposed to a dopant-containing precursor. The dopant used in the dopant-containing precursor may be any one or more of vanadium, titanium, tungsten, lanthanum or a variety of other metals. A metal with a smaller atom size may make the Mo film more tensile. A metal with a larger atom size may make the Mo film more compressive. The relative amount of dopant used and the dopant selected helps tailor the desired stress of the Mo film while maintaining the resistivity of the Mo film. An example range of dopant concentration in the Mo film is about 0.1% to about 25%. The amount of dopant concentration may be modulated by changing the dopant-containing precursor flow rate, changing the exposure time that the substrate is exposed to the dopant-containing precursor, changing temperature, changing pressure, or changing other process conditions. In various embodiments, operation 706 is performed without igniting a plasma. Operation 706 may be performed thermally. Operation 706 may involve forming a dopant-containing layer on the substrate in some embodiments. In some embodiments exposure incorporates the dopant into the Mo film. In various embodiments, operations 702 and 704 are performed thermally, or without a plasma.

[0128] In an operation 707, one or more operations from operations 702, 703, 704, 705, or 706 may be repeated in cycles. In one non-limiting example, one cycle that may be repeated may involve operation 702, 704, and 706 in that order. In some embodiments, operation 706 is only performed every certain thickness of Mo deposited by operations 702 and 704. For example, in some embodiments, operation 706 is performed every about 20Å of Mo deposited by operations 702 and 704. The thickness at which to perform operation 706 may depend on the dopant selected as well. For example, some atoms may have more difficulty incorporating itself into the Mo film, while other atoms may easily incorporate itself into the Mo film. It may also depend on the grain structure of the Mo film being grown on the surface of the substrate. Depending on the molecular structure of the Mo film, it may be challenging to incorporate certain dopant atoms at certain thicknesses.

[0129] In an operation 708, the substrate may be optionally annealed in a post-anneal process. A post-anneal process may be referred to as post-anneal when the anneal is performed after the 20 LAMRP953WO_11461-1WOMo film deposition is complete. In various embodiments, the post-anneal may be used to incorporate the dopant or to modulate the dopant concentration. In some embodiments, the anneal is performed thermally. Example anneal temperatures include about 300°C to about 750°C. In some embodiments, the anneal is performed by plasma. For a plasma anneal, the plasma power may be about 50W to about 2000W. The plasma anneal may be performed in situ or a plasma may be generated remotely and introduced into the process chamber. The plasma anneal may be performed by introducing an inert gas and igniting a plasma in the chamber. Example inert gases include but are not limited to helium, argon, nitrogen, hydrogen, and combinations thereof.

[0130] An example formula for a process flow that may be used in accordance with certain disclosed embodiments is as follows: ^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^ → ^^^^^^^^^^ → ^^^^ ^^^^^^^^^^^^^^^^^^ → ^^^^^^^^^^^^ → ^^^^^^^^^^^^^^^^^ → ^^^^^^^^^^^^^^where X is the number of cycles of ALD, Y is the duration or frequency of exposing the substrate to the dopant, and Z is the number of cycles for both (1) performing ALD and (2) exposing the substrate to the dopant in sequence. X, Y, and Z may be any integer greater than or equal to 1.

[0131] In various embodiments, Mo stress may also be modulated by changing the grain structure or grain orientation of the Mo film. The type of grain structure that is grown may depend on a seed layer deposited on the substrate prior to depositing Mo. For example, an Mo seed layer templates subsequent bulk Mo film and influences it to grow with a desired grain orientation, which can help achieve particular types of stress. Figure 8 shows an example timing schematic diagram 800 for an example process flow whereby a dopant-containing precursor is used in each cycle of ALD using reducing agent and Mo precursor exposures for two cycles. The diagram 800 includes two deposition cycles – deposition cycle 810A and deposition cycle 810B, but it will be understood that other numbers of deposition cycles may be used. The diagram 800 also shows that the deposition cycle 810A and deposition cycle 810B include the same exposure and purge phases in the same order; however, it will be understood that in some embodiments, exposures and purges may vary from deposition cycle to deposition cycle. Deposition cycle 810A includes reducing agent exposure phase 820A, purge phase 840A, Mo precursor exposure phase 850A, purge phase 860A, and dopant exposure phase 870A. In this diagram 800, argon is depicted as an example carrier gas as well as purge gas, but it will be understood that other gases may be used and that different gases may be used as carrier gases and as purge gases (e.g., the carrier gas and purge gas composition need not be the same). During reducing agent exposure phase 820A, argon flow is turned on, reducing agent flow is turned on, Mo precursor flow is turned off, and dopant precursor flow is turned off. During purge phase 840A, argon flow remains on, reducing agent 21 LAMRP953WO_11461-1WOflow is turned off, Mo precursor flow remains off, and dopant precursor flow remains off. During Mo precursor exposure phase 850A, argon flow remains on, reducing agent flow remains off, Mo precursor flow is turned on, and dopant precursor flow remains off. During purge phase 860A, argon flow remains on, reducing agent flow remains off, Mo precursor flow is turned off, and dopant precursor flow remains off. During dopant exposure phase 870A, argon flow remains on, reducing agent flow remains off, Mo precursor flow remains off, and dopant precursor flow is turned on. Following deposition cycle 810A, a second deposition cycle 810B is performed. Deposition cycle 810B includes reducing agent exposure phase 820B, purge phase 840B, Mo exposure precursor phase 850B, purge phase 860B, and dopant exposure phase 870B. During reducing agent exposure phase 820B, argon flow remains on, reducing agent flow is turned on, Mo precursor flow remains off, and dopant precursor flow is turned off. During purge phase 840B, argon flow remains on, reducing agent flow is turned off, Mo precursor flow remains off, and dopant precursor flow remains off. During Mo precursor exposure phase 850B, argon flow remains on, reducing agent flow remains off, Mo precursor flow is turned on , and dopant precursor flow remains off. During purge phase 860B, argon flow remains on, reducing agent flow remains off, Mo precursor flow is turned off, and dopant precursor flow remains off. During dopant exposure phase 870B, argon flow remains on, reducing agent flow remains off, Mo precursor flow remains off, and dopant precursor flow is turned on.

[0132] Certain disclosed embodiments are particularly suitable for PMOS and NMOS devices, as gate Mo film stress can then be modulated to control carrier mobility and transistor characteristics of the underlying channel. Certain disclosed embodiments are also particularly suitable for NAND applications for formation of the wordline to modulate stress of Mo films used. PRECURSORS

[0133] Generally, molybdenum precursors that may be used in certain disclosed embodiments may have from two (MoL2) to six (MoL6) ligands and can include molybdenum in a wide range of oxidation states ranging from 0 to +6. Molybdenum precursors may also be dimolybdenum compounds having 1) two molybdenum atoms singly or multiply bonded to one another; or 2) two molybdenum atoms connected by a linking group such as a bidentate ligand.

[0134] Low valent molybdenum complexes or compounds are those having molybdenum in low oxidation states 0, +1, +2 or +3. In certain embodiments, the low valent molybdenum complexes may be efficacious precursors as it is easier to reduce Mo(I) to Mo (0) or Mo(II) / (III) to Mo(0) than it is to reduce the more commonly utilized Mo(IV) / (V) halide precursors. 22 LAMRP953WO_11461-1WO

[0135] Low valent molybdenum precursors may offer a less circuitous surface redox process to obtain fully reduced molybdenum metal films with minimal impurities. Without wishing to be bound by a particular theory, this is likely the result of the ease of reduction of low valent molybdenum precursors.

[0136] In some embodiments, the molybdenum precursor is molybdenum oxychloride. In some embodiments, the molybdenum precursor is molybdenum pentachloride. MOLYBDENUM ZERO COMPLEXES

[0137] Mo (0) precursors are advantageous because do not require any reduction steps, and are energetically facile, as their use provides a lower energy barrier to Mo film formation upon exposure to a reducing agent. They are especially amenable in multi-step ALD processes where surface-ligand exchange and conversion (reduction) occurs. Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex existing in the oxidation state of zero.

[0138] A general structure for low valent molybdenum precursors having one molybdenum is MoLn(Formula I), and general structures for low valent molybdenum precursors with two molybdenum atoms are Mo2Ln (Formula II) or LnMo(L’)mMoLn (Formula III). For any of Formulas I-III, each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand and n is an integer of 2 to 6. For Formula III, L’ is a linking moiety such as a bidentate ligand; and m is an integer of 1 to 3. MONODENTATE LIGANDS

[0139] Suitable ligands for the low valent molybdenum complexes include monodentate ligands, also referred to as unidentate ligands. A monodentate ligand is one which binds or coordinates to a metal center via one coordination site of the metal only, or via one site of the ligand only. They may include a wide variety of substituents such as hydrogen, halo, hydroxy, alkyl silyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, di(C1- C3alkyl)amino, -C(O)O-(C1-C3alkyl), -C(O)NH-(C1-C3alkyl), -CH=NOH, -P(C1-C3alkyl)3, - PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, =O, =S, N, CR, =CR2,-NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyano or cyclyl groups where each R is 23 LAMRP953WO_11461-1WOindependently an aliphatic such as haloalkyl or aryl such as a haloaryl group.

[0140] In some embodiments, the low valent molybdenum precursors include at least one OR, P(R)3, CNR, allyl or aryl group, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group.

[0141] In some embodiments, the monodentate ligand can include an oxygen atom. In particular embodiments, one or more ligands can be optionally substituted alkoxy. Non-limiting ligands include, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)- CH=C(CH3)-O- (acac). Non-limiting molybdenum-containing precursors include, e.g., Mo(CH2F)(t-BuO)3, Mo(CF3)(t-BuO)3, Mo(CH2I)(t-BuO)3, Mo(CI3)(t-BuO)3, Mo(CH2CH2F)(t- BuO)3, Mo(CH2CH2I)(t-BuO)3, Mo(CH2F)2(t-BuO)2, Mo(CF3)2(t-BuO)2, Mo(CH2I)2(t-BuO)2, Mo(CI3)2(t-BuO)2, Mo(CH2CH2F)2(t-BuO)2, Mo(CH2CH2I)2(t-BuO)2, Mo(t-BuO)2, Mo(CH3)(t- BuO)3, Mo(CH2CH3)(t-BuO)3, Mo(CH=CH2)(t-BuO)3, Mo(CH=CHCH3)(t-BuO)3, Mo(CH2- CH=CH2)(t-BuO)3, Mo(C≡CH)(t-BuO)3, Mo(C≡CCH3)(t-BuO)3, Mo(CH2C≡CH)(t-BuO)3, or Mo(acac)2.

[0142] In certain embodiments, the oxygen-containing monodentate ligand maybe -OC(CH3)(CF3)2, -OC(CH3)2(CF3), -OC(CH3)3, -OSiR3 (such as -OSiPh3), C O (carbonylligand) or -OAr (where Ar groups include but are not limited to phenyl, mesitylenyl, 2,6-iPr2C6H3, hexa-iso-propyl-ter-phenyl, and 2,3,5,6-Ph4C6H). In certain embodiments, the oxygen-containing ligand is an ether, epoxide, or ketone. In some cases, the oxygen-containing ligand may be a silyloxy group.

[0143] In certain embodiments, the ligand is a phosphorous-containing ligand. Suitable complexes may be of the formula R3P where R is a halo, aliphatic or aryl group. Examples include secondary or tertiary organophosphines such as P(t-Bu)3, PMe3, PPh3, P(OMe)3, P(OEt)3, PCl3or PF3. In some embodiments, the phosphorus containing ligand is phosphanetriyltris(benzene sulfonic acid). Other phosphorus containing ligands include -CH2P(CH3)3, -P(O)OH, - P(O)(OCH3)2, -P(O)(OCH2CH3)2, and -CH(Si(CH3)3)(P(CH3)3).

[0144] In some embodiments, the ligand is an isocyano functional group, including isonitrilesof the formula -C NR, such as isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl.In some embodiments, R is an aliphatic group such as a haloalkyl, or an aryl group such as haloaryl. In certain embodiments, R may be -CH2CF3, -C(F)=CF2, -C(F)=C(F)CF3, - CF2C(F)=CF2, -CH(CF3)2, -CH(CH3)(CF3), or -C(CH3)2(CF3). In certain embodiments, R is a perfluoroalkyl substituent of one to ten carbon atoms such as perfluorinated methyl, ethyl, i- propyl, n-propyl, t-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl or n-hexyl group. 24 LAMRP953WO_11461-1WO

[0145] In some embodiments, the monodentate ligand is one with sp2hybridized character such as an allyl, allenyl, ethenyl, indenyl or cyclopentadienyl group. Two of the same such substituents or two different such substituents may be utilized to form precursors with a sandwich structure. In some embodiments, one such substituent is utilized to form a half-sandwich complex. In certain embodiments, the ligand may be mesitylenyl, tolyl, xylyl, benzyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, or pyrimidinyl.

[0146] In some embodiments, the ligand is an atom which is connected directly to molybdenum via a multiple bond such as a double or triple bond. Examples include =O, =NR, =S, N, =CR2 or CR, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group.

[0147] In some embodiments, the molybdenum-containing precursor has at least one optionally substituted haloalkyl group. Non-limiting haloaliphatic group ligands include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; or -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I). Yet other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (- CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (- CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (- CH2CHFI), and the like. In particular embodiments, the C1-2 haloalkyl includes β-halo-substituted ethyl. Yet other haloaliphatic groups include C1-4haloalkyl, C2-4haloalkenyl, and C2-4haloalkynyl.

[0148] In other embodiments, the ligand is an optionally substituted alkyl group, optionally substituted alkenyl, or optionally substituted alkynyl. Non-limiting groups include -CnH2n+1, in which n is 1 or 2; -CnH2n-1, in which n is 2, 3, or 4; or -CnH2n-3, in which n is 2, 3, or 4. Yet other non-limiting groups include methyl (-CH3), ethyl (-CH2CH3), vinyl or ethenyl (-CH=CH2), 1- propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2- butenyl (-CH2CH=CHCH3), 3-butenyl (e.g. -CH2CH2CH=CH2), ethynyl (-C≡CH), 1-propynyl (- C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl 25 LAMRP953WO_11461-1WO(-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), 2-methyl-1-propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2, 1-methylallyl (CH(CH3)CH=CH2and the like.

[0149] In some embodiments, the monodentate ligand may be -CH2P(CH3)3, -CH(Si(CH3)3)(P(CH3)3), -C(O)C3F7, or -CHCHSO2C6H5.

[0150] In some embodiments, the monodentate ligand includes a sulfur atom. In particular embodiments, one or more monodentate ligands can be -SO2CF3, -SO2C3N2H3, -CHCHSO2C6H5, -SO2OCH3, or -SO2C6H4CH3.

[0151] In some embodiments, the monodentate ligand includes a nitrogen atom. In particular embodiments, one or more monodentate ligands can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino. Non-limiting ligands can include, e.g., -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0152] In some embodiments, the optionally substituted amino is -NR1R2, in which each R1and R2is, independently, H or alkyl; or in which R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is -N(SiR1R2R3)2, in which each R1, R2, and R3is, independently, alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is -SiR1R2R3, in which each R1, R2, and R3is, independently, alkyl.

[0153] In other embodiments, the low valent molybdenum precursor includes a first ligand that is -NR1R2and a second ligand that is -NR1R2, in which each R1and R2is, independently, H or alkyl. In yet other embodiments, the formula includes a first ligand that is -OR1and a second ligand that is -OR1, in which each R1is, independently, H or alkyl.

[0154] In some embodiments, the monodentate ligand is optionally substituted alkyl. Non- limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, the ligand has at least one beta-hydrogen or beta-halogen.

[0155] In some embodiments, at least one monodentate ligand is optionally substituted haloalkyl. Non-limiting haloalkyl groups include, e.g., CnH2n+1-zXz, wherein n is 1, 2, 3, or greater; wherein z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7); and wherein each X is, independently, halo (F, Cl, Br, or I).

[0156] In some embodiments, at least one monodentate ligand is optionally substituted alkenyl or optionally substituted alkynyl. Non-limiting alkenyl groups include, e.g., CnH2n-1, where n is 2, 3, 4, or greater, such as ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl. Non-limiting alkynyl groups include, e.g., CnH2n-3, where n is 2, 3, 4, or greater, such as ethynyl, 26 LAMRP953WO_11461-1WO1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0157] Alkynyl groups are also suitable monodentate ligands in certain embodiments. In some embodiments, the carbon-carbon triple bond is not bound directly to the molybdenum, for example in a formula R1CCCH2MoL3where R1is a C1-C2linear or branched alkane such as methyl or ethyl; and L is an amino (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminiocyclopentane, aminocyclohexane) or alkoxy group (methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy).

[0158] Alkyne compounds which have a carbon-carbon triple bond directly bonded to the molybdenum atom will hydrolyze in the presence of water similar to, although much slower than, amino and alkoxy groups. Therefore, compounds such as (R1C≡C)3MoR2and (R1C≡C)4Mo where R1is a simple alkane such as methyl or ethyl, and R2is a C1-C2hydrocarbon are precursors having monodentate ligands in accordance with certain embodiments. In compound (R1C≡C)3MoR2the molybdenum center has three alkynes with the carbon-carbon triple bond bonded to the molybdenum center. Tetra-alkynes such as those shown for (R1C≡C)4Mo.

[0159] In some embodiments, the monodentate ligand is halo. In particular, the metal- containing precursor can be a metal halide or organometal halide. Non-limiting metal halides and organometal halides include FCH2MoX3, CF3MoX3, ICH2MoX3, CI3MoX3, CH2FCH2MoX3, CH2ICH2MoX3, MoX2, or MoX4, in which each X is, independently, halo. In other embodiments, the metal-containing precursor is RMoX3, in which R is C1-4haloalkyl, C2-4haloalkenyl, or C2-4haloalkynyl; and in which each X is, independently, halo. In yet other embodiments, the metal- containing precursor is RMoX3, in which R is C1-2alkyl, C2-4alkenyl, or C2-4alkynyl; and in which each X is, independently, halo.

[0160] In other embodiments, the monodentate ligand is C1- C3aliphatic (wherein the C1-C3aliphatic may be optionally substituted with a ketone, an alkoxy group, an epoxy group) or a - C(O)C1-C3alkyl group. Ethers, ketones or epoxide-containing ligands on the low valent molybdenum-containing precursors may be advantageous to assist in crosslinking.

[0161] In some embodiments, the monodentate ligand can include a silicon atom. In some embodiments, the monodentate ligand may be -Si(CH3)3, -Si(C2H5)3, -CH2Si(CH3)3, - CH(Si(CH3)3)2 or -C(Si(CH3)3)3. In particular embodiments, one or more ligands can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting ligands can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0162] For any formula herein, each monodentate ligand may independently be hydrogen, halo, azido, cyano, akylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally 27 LAMRP953WO_11461-1WOsubstituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1can be alkyl).

[0163] The present disclosure also encompasses hydrogen as a monodentate ligand. An example of a complex having a hydrogen monodentate ligand is a molybdenum hydride precursor such as Mo(Cp)2H2, where Cp is cyclopentadienyl.

[0164] The monodentate ligand may be an ambidentate ligand, which has two potential donor atoms, but only attaches to a metal via one of the two. In certain embodiments, the ambidentate ligand is NO2-, which may bond to a metal through either the nitrogen atom or the oxygen atom. BIDENTATE LIGANDS

[0165] Suitable ligands for the low valent molybdenum complexes include bidentate ligands. A bidentate ligand (also referred to as a chelating ligand) is one which binds or coordinates to a metal center via two coordination sites of the metal, or via two sites of the ligand. Bidentate ligands are Lewis bases that donate two pairs of electrons to a metal atom. The bidentate ligands may be neutral or anionic. Furthermore, the bidentate ligands may have the same two coordination atoms, or may be unsymmetrical bidentate ligands, where the two coordination atoms are not the same. In some embodiments, the bidentate ligands may be ethylenediamine (en), bipyridyl (bpy), 1,2- bis(dimethylphosphino)ethane (dmpe), phenanthroline (phen), 1,2-bis(diphenylphosphino)ethane (dppe), acetate (OAc), oxalate (ox), or acetylacetonate (acac).

[0166] Example structures containing the bidentate ligand include, but are not limited to .L’ of the structure –(E)e- where each E independently includes NR, C(R)n, Si(R)n, S, O or P(R)n; each R independently includes hydrogen, aryl, amino or aliphatic; n is 0, 1 or 2 and e is 1, 2, 3, 4 or 5.

[0168] Suitable low valent molybdenum precursors may contain one, two or three bidentate ligands each of which may be the same or different.

[0169] The bidentate ligand may be an amidinate, an amidate, an iminopyrrolidinate, a 28 LAMRP953WO_11461-1WOdiazabutadiene, a beta-imino amide, an alpha-imino alkoxide, a beta-diketiminate, a beta- ketoiminate, a beta-diketonate, a pyrazolate, a beta-amino alkoxide, a guanidinidate, a dithiolene, an alpha-iminothiolene, an alpha-dithiolate, or a beta-dithiolate. Other examples of suitable materials include the bidentate ligands described in US 2022 / 0170155 and WO 2021 / 035236, which are incorporated herein by reference in their entireties. TRIDENTATE LIGANDS

[0170] A tridentate ligand is one with three atoms that can function as acceptors in a coordination complex. In certain embodiments, the tridentate ligand three nitrogen, three sulfur, three phosphorus or three oxygen atoms available for chelation. Tridentate ligands include cis,cis- 1,3,5-triaminocyclohexane, 1,4,7-triazacyclononane, 1,4,7,-trimethyl-1,4,7-triazacyclononane, 1,4,7-trithiacyclononane, bis(diphenylphosphinoethyl)phenylphosphine, N,N,N’,N”N”- pentamethyldiethylenetriamine, tris(4S-isopropyl-2-oxazolinyl)phenylborate, tris(4,4-dimethyl- 2-oxazolinyl)phenyl borate, trispyrazolylborate, 1,4,7-trioxonane, diethylenetriamine, or an iminodiacetate anion. Suitable low valent molybdenum precursors may contain one, two or more tridentate ligands which may be the same or different.

[0171] The low valent molybdenum precursors may have two to six ligands. Each occurrence of L may independently be a monodentate, ambidentate, bidentate or tridentate ligand as described above. Low valent molybdenum precursors having two ligands may be of the formula MoL2.FIG. 1 illustrates example structures for molybdenum precursors having three ligands (Formula XIV), four ligands (Formula V and Formula VI) or five ligands (Formula IX and Formula X) in certain embodiments. For Formulas XIV, VI, IX and X, R4, R6, R7and R15are each independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -CF3, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3or - CH2Si(CH3)3. -CH(Si(CH3)3)2, -C(Si(CH3)3)3, -P(CH3)3, -CH2P(CH3)3, -P(O)OH, -P(O)(OCH3)2, -P(O)(OCH2CH3)2, -CH(Si(CH3)3)(P(CH3)3), -SO2CF3, -SO2C3N2H3, -C(O)C3F7, -CHCHSO2C6H5, -SO2OCH3, or -SO2C6H4CH3. For Formula IX, G may be =O, =NR, =S or =CR2, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. For Formula X, each R8is independently any of the monodentate, ambidentate or bidentate ligands described above. For Formula V, R1may be aliphatic, R2may be any of the monodentate, ambidentate, bidentate or tridentate ligands described above, and n may be 1, 2, 3, 4 or 5.

[0172] Low valent molybdenum precursors may also have six ligands. Such precursors may have the general formula Mo(X)p(R10)q (XII) where each X independently includes chloro, fluoro, 29 LAMRP953WO_11461-1WObromo or iodo; each R10independently includes allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, - P(CH2CH3)3or -CNR11, where R11includes aliphatic, aryl or heterocyclyl; p is 1 to 4; q is 2 to 5; and p + q = 6.

[0173] Low valent molybdenum precursors having six ligands may also be of the formula the Formula (XIII): Mo(R12)r(R13)s (XIII) where each R12independently includes allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N- dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR14, where R14includes aliphatic, aryl or heterocyclyl; each R13independently includes trimethylphosphine, triethylphosphine, tri-i-propyl phosphine, triphenylphosphine, tris(trimethylsilyl)phosphine, tris(2-carboxyethyl)phosphine, tris(dimethylamino)phosphine, tris(o-tolyl)phosphine, tris(4- methoxyphenyl)phosphine or tris(2-furyl)phosphine; r is 1 to 6; s is 0 to 5; and r + s = 6. APPARATUS

[0174] The deposition methods described herein can be carried out in a variety of apparatuses. A suitable apparatus includes a processing chamber having one or more inlets for introduction of reactants, a substrate holder in the process chamber configured to hold the substrate in place during deposition, and, optionally, a plasma generating mechanism configured for generating a plasma in a process gas. The apparatus may include a controller having program instructions for causing any of the method steps described herein. The deposition methods described herein may be carried out in corresponding ALD and CVD apparatuses.

[0175] For example, in some embodiments the apparatus includes a controller having program instructions that include instructions for: causing an introduction of a molybdenum precursor to the processing chamber, wherein the precursor is any of the precursors described herein; and causing a reaction between the molybdenum precursor and a second reactant to form a layer of molybdenum-containing material on a substrate. The controller may include program instructions for causing any of the methods described herein.

[0176] An example of a deposition apparatus suitable for depositing molybdenum-containing films using provided methods is shown in Figure 9 which schematically illustrates an embodiment of a process station 900 that may be used to deposit material using atomic layer deposition (ALD) 30 LAMRP953WO_11461-1WOand / or chemical vapor deposition (CVD), either of which may be plasma enhanced. For simplicity, the process station 900 is depicted as a standalone process station having a process chamber body 902 for maintaining a low-pressure environment. However, it will be appreciated that a plurality of process stations 900 may be included in a common process tool environment. Further, it will be appreciated that, in some embodiments, one or more hardware parameters of process station 900, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers.

[0177] Process station 900 fluidly communicates with reactant delivery system 901 for delivering process gases to a distribution showerhead 906. Reactant delivery system 901 includes a mixing vessel 904 for blending and / or conditioning process gases for delivery to showerhead 906. One or more mixing vessel inlet valves 920 may control introduction of process gases to mixing vessel 904. Similarly, a showerhead inlet valve 905 may control introduction of process gasses to the showerhead 906.

[0178] Some molybdenum-containing precursors may be stored in solid or liquid form prior to vaporization and subsequent delivery to the process station. For example, the embodiment of Figure 9 includes a vaporization point 903 for vaporizing solid reactant to be supplied to mixing vessel 904. In some embodiments, vaporization point 903 may be a heated vaporizer. In some embodiments a flow of an inert gas is passed over the heated solid molybdenum precursor, or bubbled through the heated liquid molybdenum precursor, under subatmospheric pressure, and carries the precursor vapor to the process chamber. The precursor vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve sweeping and / or evacuating the delivery piping to remove residual reactant. However, sweeping the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of vaporization point 903 may be heat traced. In some examples, mixing vessel 904 may also be heat traced. In one non-limiting example, piping downstream of vaporization point 903 has an increasing temperature profile extending from approximately 100°C to approximately 200°C at mixing vessel 904.

[0179] Showerhead 906 distributes process gases toward substrate 912. In the embodiment shown in Figure 9, substrate 912 is located beneath showerhead 906, and is shown resting on a pedestal 908. It will be appreciated that showerhead 906 may have any suitable shape and may have any suitable number and arrangement of ports for distributing processes gases to substrate 31 LAMRP953WO_11461-1WO912. While not explicitly shown, in some embodiments the showerhead 906 is a dual plenum showerhead that includes at least two types of conduits, where the first type of conduit is dedicated to delivery of molybdenum-containing precursor vapor, and the second type of conduit is dedicated to delivery of the second (or other) reactant. In these embodiments the molybdenum- containing precursor and the reactant are not allowed to mix in the conduits prior to entry to the process chamber, and do not share the conduits if delivered to the chamber consecutively.

[0180] In some embodiments, a microvolume 907 is located beneath showerhead 906. Performing an ALD and / or CVD process in a microvolume rather than in the entire volume of a process station may reduce reactant exposure and sweep times, may reduce times for altering process conditions (e.g., pressure, temperature, etc.), may limit an exposure of process station robotics to process gases, etc. Example microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. This microvolume also impacts productivity throughput. While deposition rate per cycle drops, the cycle time also simultaneously reduces. In certain cases, the effect of the latter is dramatic enough to improve overall throughput of the module for a given target thickness of film.

[0181] In some embodiments, pedestal 908 may be raised or lowered to expose substrate 912 to microvolume 907 and / or to vary a volume of microvolume 907. For example, in a substrate transfer phase, pedestal 908 may be lowered to allow substrate 912 to be loaded onto pedestal 908. During a deposition process phase, pedestal 908 may be raised to position substrate 912 within microvolume 907. In some embodiments, microvolume 907 may completely enclose substrate 912 as well as a portion of pedestal 908 to create a region of high flow impedance during a deposition process.

[0182] Optionally, pedestal 908 may be lowered and / or raised during portions the deposition process to modulate process pressure, reactant concentration, etc., within microvolume 907. In one scenario where process chamber body 902 remains at a base pressure during the deposition process, lowering pedestal 908 may allow microvolume 907 to be evacuated. Example ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller.

[0183] While the example microvolume variations described herein refer to a height-adjustable pedestal, it will be appreciated that, in some embodiments, a position of showerhead 906 may be adjusted relative to pedestal 908 to vary a volume of microvolume 907. Further, it will be appreciated that a vertical position of pedestal 908 and / or showerhead 906 may be varied by any 32 LAMRP953WO_11461-1WOsuitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 908 may include a rotational axis for rotating an orientation of substrate 912. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers.

[0184] Returning to the embodiment shown in Figure 9, showerhead 906 and pedestal 908 electrically communicate with RF power supply 914 and matching network 916 for powering a plasma. In other embodiments apparatuses without a plasma generator are used for depositing molybdenum-containing films using provided methods. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, a radio frequency (RF) source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 914 and matching network 916 may be operated at any suitable power to form a plasma having a desired composition of radical species. Likewise, RF power supply 914 may provide RF power of any suitable frequency. In some embodiments, RF power supply 914 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 700 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasmas.

[0185] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0186] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. In one example, the instructions for setting plasma conditions for a 33 LAMRP953WO_11461-1WOplasma process phase may be included in a corresponding plasma activation recipe phase of a deposition process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a deposition process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe phase preceding a plasma process phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for enabling the plasma generator and time delay instructions for the second recipe phase. A third recipe phase may include instructions for disabling the plasma generator and time delay instructions for the third recipe phase. It will be appreciated that these recipe phases may be further subdivided and / or iterated in any suitable way within the scope of the present disclosure.

[0187] In some embodiments, pedestal 908 may be temperature controlled via heater 910. Further, in some embodiments, pressure control for deposition process station 900 may be provided by butterfly valve 918. As shown in the embodiment of Figure 9, butterfly valve 918 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 900 may also be adjusted by varying a flow rate of one or more gases introduced to process station 900.

[0188] Figure 10 shows a schematic view of an embodiment of a multi-station processing tool 1000 with an inbound load lock 1002 and an outbound load lock 1004, either or both of which may comprise a remote plasma source. Such tool may be used for processing the substrates using the methods provided herein. A robot 1006, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 1008 into inbound load lock 1002 via an atmospheric port 1010. A wafer is placed by the robot 1006 on a pedestal 1012 in the inbound load lock 1002, the atmospheric port 1010 is closed, and the load lock is pumped down. Where the inbound load lock 1002 comprises a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 1014. Further, the wafer also may be heated in the inbound load lock 1002 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 1016 to processing chamber 1014 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in Figure 10 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided. 34 LAMRP953WO_11461-1WO

[0189] The depicted processing chamber 1014 comprises four process stations, numbered from 1 to 4 in the embodiment shown in Figure 10. Each station has a heated pedestal (shown at 1018 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. While the depicted processing chamber 1014 comprises four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.

[0190] Figure 10 also depicts an embodiment of a wafer handling system 1090 for transferring wafers within processing chamber 1014. In some embodiments, wafer handling system 1090 may transfer wafers between various process stations and / or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. Figure 10 also depicts an embodiment of a system controller 1050 employed to control process conditions and hardware states of process tool 1000. System controller 1050 may include one or more memory devices 1056, one or more mass storage devices 1054, and one or more processors 1052. Processor 1052 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0191] In some embodiments, system controller 1050 controls all of the activities of process tool 1000. System controller 1050 executes system control software 1058 stored in mass storage device 1054, loaded into memory device 1056, and executed on processor 1052. System control software 1058 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by process tool 1000. System control software 1058 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes in accordance with the disclosed methods. System control software 1058 may be coded in any suitable computer readable programming language.

[0192] In some embodiments, system control software 1058 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of an ALD process may include one or more instructions for execution by system controller 1050. The instructions for setting process conditions for an ALD process phase 35 LAMRP953WO_11461-1WOmay be included in a corresponding ALD recipe phase. In some embodiments, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase.

[0193] Other computer software and / or programs stored on mass storage device 1054 and / or memory device 1056 associated with system controller 1050 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0194] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 1018 and to control the spacing between the substrate and other parts of process tool 1000.

[0195] A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rates within any of the disclosed ranges. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any of the disclosed pressure ranges.

[0196] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions to maintain the temperature of the substrate within any of the disclosed ranges.

[0197] A plasma control program may include code for setting RF power levels and frequencies applied to the process electrodes in one or more process stations, for example using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0198] In some embodiments, there may be a user interface associated with system controller 1050. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0199] In some embodiments, parameters adjusted by system controller 1050 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, 36 LAMRP953WO_11461-1WOtemperature, pressure, plasma conditions (such as RF power levels, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0200] Signals for monitoring the process may be provided by analog and / or digital input connections of system controller 1050 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 1000. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0201] Any suitable chamber may be used to implement the disclosed embodiments. Two or more of the stations may perform the same functions. Similarly, two or more stations may perform different functions. Each station can be designed / configured to perform a particular function / method as desired.

[0202] Figure 11 is a block diagram of a processing system suitable for conducting thin film deposition processes in accordance with certain embodiments. The system 1100 includes a transfer module 1103. The transfer module 1103 provides a clean, pressurized environment to minimize risk of contamination of substrates being processed as they are moved between various reactor modules. Mounted on the transfer module 1103 are two multi-station reactors 1109 and 1110, each capable of performing atomic layer deposition (ALD) and / or chemical vapor deposition (CVD) according to certain embodiments. Reactors 1109 and 1110 may include multiple stations 1111, 1113, 1115, and 1117 that may sequentially or non-sequentially perform operations in accordance with disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate.

[0203] Also mounted on the transfer module 1103 may be one or more single or multi-station modules 1107 capable of performing plasma or chemical (non-plasma) pre-cleans, or any other processes described in relation to the disclosed methods. The module 1107 may in some cases be used for various treatments to, for example, prepare a substrate for a deposition process. The module 1107 may also be designed / configured to perform various other processes such as etching or polishing. The system 1100 also includes one or more wafer source modules 1101, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 1119 may first remove wafers from the source modules 1101 to loadlocks 1121. A wafer transfer device (generally a robot arm unit) in the transfer module 1103 37 LAMRP953WO_11461-1WOmoves the wafers from loadlocks 1121 to and among the modules mounted on the transfer module 1103.

[0204] In various embodiments, a system controller 1129 is employed to control process conditions during deposition. The controller 1129 will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0205] The controller 1129 may control all of the activities of the deposition apparatus. The system controller 1129 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 1129 may be employed in some embodiments.

[0206] Typically, a user interface will be associated with the controller 1129. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0207] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application-specific integrated circuits, and other devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. System control software may be coded in any suitable computer readable programming language.

[0208] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flow, and tungsten-containing precursor pulses, and other processes in a process sequence can be written in any conventional computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded.

[0209] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe 38 LAMRP953WO_11461-1WOand may be entered utilizing the user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 1129. The signals for controlling the process are output on the analog and digital output connections of the deposition apparatus 1100.

[0210] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control operation of the chamber components necessary to carry out the deposition processes (and other processes, in some cases) in accordance with the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0211] In some implementations, a controller 1129 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller 1129, depending on the processing requirements and / or the type of system, may be control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0212] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some 39 LAMRP953WO_11461-1WOembodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0213] The controller, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated to the system from the remote computer.

[0214] In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0215] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and / or manufacturing of semiconductor wafers.

[0216] As noted above, depending on the process step or steps to be performed by the tool, the 40 LAMRP953WO_11461-1WOcontroller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0217] The apparatus and processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such apparatus and processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically comprises some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a work piece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or work piece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper. EXPERIMENTAL EXPERIMENT 1

[0218] Molybdenum was deposited by thermal atomic layer deposition to a thickness of about 100 Å on a substrate having titanium nitride deposited thereon by physical vapor deposition. The stress was 1250 MPa and the film had tensile stress.

[0219] Molybdenum was deposited by thermal atomic layer deposition to a thickness of about 100 Å on a substrate having tungsten deposited thereon by physical vapor deposition. The stress was 2830 MPa and the film had tensile stress.

[0220] These results suggest that the film stress may be substrate dependent. EXPERIMENT 2

[0221] Molybdenum was deposited by thermal atomic layer deposition (TALD) to various thicknesses at a temperature of about 450°C using molybdenum pentachloride (MoCl5) as a molybdenum precursor. Molybdenum was deposited by plasma-enhanced atomic layer deposition (PEALD) at a temperature of about 300°C to various thicknesses MoO2Cl2 as a molybdenum 41 LAMRP953WO_11461-1WOprecursor. These films were deposited on a substrate having titanium nitride deposited thereon by physical vapor deposition The stress was evaluated for the films. Figure 12 shows the results.

[0222] These results suggest plasma-deposited Mo films may have significantly lower stress than thermally-deposited Mo films. EXPERIMENT 3

[0223] Molybdenum was deposited by PEALD at a temperature of about 300°C to various thicknesses using various plasma powers. The stress was evaluated for the films. Figure 13 shows the results. The line and data shown on the left side is for a Mo film deposited to about 100 Å. The line and data shown on the right side is for a Mo film deposited to about 200 Å. These results suggest modulating plasma power in plasma-deposited Mo films affects the stress of the Mo film.

[0224] Molybdenum was deposited by PEALD at a temperature of about 300°C to various thicknesses using various plasma powers. The bow change was evaluated for the films. Figure 14 shows the results. The line and data shown on the left side is for a Mo film deposited to about 100 Å. The line and data shown on the right side is for a Mo film deposited to about 200 Å. These results suggest modulating plasma power plasma-deposited Mo films affects the bowing of the Mo film. EXPERIMENT 4

[0225] A Mo film was deposited at 300°C by PEALD and a Mo film was deposited at 475°C by thermal ALD on thermal oxide substrates. In both cases, MoO2Cl2 was used as the precursor for Mo deposition.

[0226] Figure 15 shows the stress and average thickness of the film. These results suggest that hybrid stacks may be used by mixing and matching these two types of depositions to create a Mo film of custom stress type / magnitude. EXPERIMENT 5

[0227] A Mo film was deposited using hydrogen gas as a reducing agent. A Mo film was deposited using intermittent diborane soak between Mo layers grown up to a particular thickness.

[0228] Figure 16 shows the thickness of the film per deposition cycle for each film. These results suggest that using diborane increased the throughput by 23%. EXPERIMENT 6

[0229] A Mo film was deposited using hydrogen gas as a reducing agent. A Mo film was 42 LAMRP953WO_11461-1WOdeposited using intermittent diborane soak between Mo layers grown up to a particular thickness.

[0230] Figure 17 shows the roughness for each Mo film. These results suggest that using diborane reduced roughness. DEFINITIONS

[0231] “Molybdenum metal” or “metallic molybdenum” as used herein, refers to material that consists essentially of molybdenum (Mo). Other elements (e.g., C, N, or O) can be present in molybdenum metal in small quantities (e.g., with a total content of less than about 15 atomic %, or less than about 10%, where hydrogen is not included in the calculation). “High purity molybdenum metal” as used herein refers to molybdenum metal that includes less than about 5% of other elements, such as less than about 1% of other elements, where hydrogen is not included in the calculation.

[0232] Molybdenum nitride (MoNx), molybdenum carbide (MoCx), molybdenum boride (MoBx), molybdenum silicide (MoSix), molybdenum boride carbide (MoBxCy), and molybdenum carbonitride (MoCxNy), refer to materials that consist essentially of molybdenum and nitrogen (MoNx), molybdenum and carbon (MoCx), molybdenum and boron (MoBx), molybdenum and silicon (MoSix), molybdenum, boron and carbon (MoBxCy), and molybdenum, carbon and nitrogen (MoCxNy), where x and y indicate that the stoichiometry of these compounds may vary. Other elements may be present in these compounds in small quantities, e.g., in an amount of less than about 10% atomic, where hydrogen is excluded from the calculation.

[0233] The term “semiconductor substrate” as used herein refers to a substrate at any stage of semiconductor device fabrication containing a semiconductor material anywhere within its structure. It is understood that the semiconductor material in the semiconductor substrate does not need to be exposed. Semiconductor wafers having a plurality of layers of other materials (e.g., dielectrics) covering the semiconductor material, are examples of semiconductor substrates. The following detailed description assumes the disclosed implementations are implemented on a semiconductor wafer, such as on a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed implementations are not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of the disclosed implementations include various articles such as printed circuit boards and the like.

[0234] By “aliphatic” is meant a hydrocarbon moiety having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), and which includes saturated groups such as alkanes (or alkyl) and unsaturated groups such as 43 LAMRP953WO_11461-1WOalkenes (or alkenyl), alkynes (or alkynyl), and also includes cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. Such a hydrocarbon can be unsubstituted or substituted with one or more groups, such as halogens or groups described herein for an alkyl group.

[0235] By “alkenyl” is meant an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be cyclic (e.g., C3-24cycloalkenyl) or acyclic. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include C2-8 alkenyl, C2-6 alkenyl, C2-5 alkenyl, C2-4 alkenyl, or C2-3 alkenyl. Exemplary, non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g. -CH2CH2CH=CH2), 2-butenylidene (e.g., =CH-CH=CHCH3), and the like.

[0236] By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C2-24alkyl group having one or more double bonds. The alkenylene group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0237] By “alkoxy” is meant -OR, where R is an optionally substituted alkyl group, as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkoxy groups.

[0238] By “alkyl” and the prefix “alk” is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t- butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic (e.g., C3-24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The 44 LAMRP953WO_11461-1WOalkyl group can also be substituted or unsubstituted. For example, the alkyl group can include haloalkyl, in which the alkyl group is substituted by one or more halo groups, as described herein. In another example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-Ak, wherein Ak is optionally substituted C1-6 alkyl); (2) amino (e.g., -NRN1RN2, where each of RN1and RN2is, independently, H or optionally substituted alkyl, or RN1and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (5) aryloyl (e.g., -C(O)-Ar, wherein Ar is optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxyaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -CO2H); (9) C3-8cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C3-8 hydrocarbon group); (10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorous, sulfur, or halo); (12) heterocyclyloxy (e.g., -O-Het, wherein Het is heterocyclyl, as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, wherein Het is heterocyclyl, as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO2); (17) oxo (e.g., =O); (18) -CO2RA, where RAis selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) (C4-18 aryl) C1-6alkyl (e.g., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl); (19) -C(O)NRBRC, where each of RBand RCis, independently, selected from the group consisting of (a) hydrogen, (b) C1-6alkyl, (c) C4-18aryl, and (d) (C4-18aryl) C1-6 alkyl (e.g., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl); and (20) -NRGRH, where each of RGand RHis, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6alkenyl (e.g., optionally substituted alkyl having one or more double bonds), (e) C2-6alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C4-18 aryl, (g) (C4-18 aryl) C1-6alkyl (e.g., Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl), (h) C3-8 cycloalkyl, and (i) (C3-8 cycloalkyl) C1-6 alkyl (e.g., -Lk-Cy, wherein Lk is a bivalent form of optionally substituted alkyl group and Cy is optionally substituted cycloalkyl, as described herein), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-2, C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2- 45 LAMRP953WO_11461-1WO3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkyl group.

[0239] By “alkylene” is meant a multivalent (e.g., bivalent) form of an alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0240] By “alkylcarbonyl” is meant an alkyl group as previously defined appended to the parent molecular moiety through a carbonyl group. Exemplary, non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl among others.

[0241] The term “alkylsilyl”, as used herein, refers to SiR3group, wherein at least one R is an alkyl, and each R is independently selected from H and an alkyl. Alkylsilyls include mono, bis, and tris alkylsilyls. Examples of alkylsilyls include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, and ethylsilyl.

[0242] By “alkynyl” is meant an optionally substituted C2-24alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non- limiting unsubstituted alkynyl groups include C2-8alkynyl, C2-6alkynyl, C2-5alkynyl, C2-4alkynyl, or C2-3 alkynyl. Exemplary, non-limiting alkynyl groups include ethynyl (-C≡CH), 1-propynyl (- C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), and the like.

[0243] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0244] By “amido” is meant -N(RN1)C(O)-, where RN1is H, optionally substituted alkyl, or optionally substituted aryl.

[0245] By “amino” is meant -NRN1RN2, where each of RN1and RN2is, independently, H, optionally substituted alkyl, or optionally substituted aryl, or RN1and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. 46 LAMRP953WO_11461-1WO

[0246] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0247] By “aminoaryl” is meant an aryl group, as defined herein, substituted by an amino group, as defined herein.

[0248] By “aryl” is meant a group that contains any carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C4-8cycloalkyl radicals (e.g., as defined herein) such as, for instance, indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents, such as any described herein for alkyl.

[0249] By “azido” is meant -N3.

[0250] By “branched alkenyl” is meant an isomer of a straight chain alkenyl compound; one having alkyl groups bonded to the main carbon chain.

[0251] By “cyano” is meant -CN.

[0252] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0253] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl.

[0254] By “deposition” or “vapor deposition” is meant a process in which a metal layer is formed on one or more surfaces of a substrate from vaporized precursor composition(s) including one or more metal containing compounds. The metal-containing compounds are vaporized and directed to and / or contacted with one or more surfaces of a substrate (i.e., semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal containing compounds form a non-volatile, thin, uniform metal-containing layer on 47 LAMRP953WO_11461-1WOthe surface(s) of the substrate. One operation of the method is one cycle, and the process can be repeated for as many cycles necessary to obtain the desired metal thickness.

[0255] By “dicarbonyl” is meant any moiety or compound including two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., RC1-C(O)- C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group); 1,3-dicarbonyl (e.g., RC1-C(O)- C(R1aR2a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1aand R2ais, independently, H or an optional substituent provided for alkyl, as defined herein); and 1,4- dicarbonyl (e.g., RC1-C(O)-C(R1aR2a)-C(R3aR4a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1a, R2a, R3a, and R4ais, independently, H or an optional substituent provided for alkyl, as defined herein).

[0256] The term “fluoroalkyl”, as used herein, refers alkyl groups containing one or more fluorine substituents. In some implementations fluoroalkyls contain exclusively fluorine substituents, such as in CF3, C2F5, C3F7. Fluoroalkyls may be linear, branched and cyclic.

[0257] By “halo” is meant F, Cl, Br, or I.

[0258] By “halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group.

[0259] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.

[0260] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0261] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0262] By “haloalkyl” is meant an alkyl group, as defined herein, substituted with one or more halogen. Non-limiting unsubstituted haloalkyl groups include C1-2haloalkyl, C1-3haloalkyl, C1-4haloalkyl, C1-5 haloalkyl, C1-6 haloalkyl, C2-3 haloalkyl, C2-4 haloalkyl, C2-5 haloalkyl, C2-6 haloalkyl, or C3-6 haloalkyl. Other non-limiting haloalkyl groups include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXz1H2-z1CXz2H2-z2CXyH3-y, wherein each of z1 and 48 LAMRP953WO_11461-1WOz2 is, independently, 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z1, z2, or y is not 0; and -CXzH1-z[CXy1H3-y1][CXy2H3-y2], wherein z is 0 or 1, wherein each of y1 and y2 is, independently, 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z, y1, or y2 is not 0.

[0263] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo.

[0264] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). The 3- membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, 49 LAMRP953WO_11461-1WOdibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, 50 LAMRP953WO_11461-1WOxanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and / or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for aryl.

[0265] By “hydroxyl” is meant -OH.

[0266] By “imino” is meant -NR-, in which R can be H or optionally substituted alkyl.

[0267] By “isocyanato” is meant -NCO.

[0268] By “isocyano” is meant -N ≡ C -, and includes nitriles of the formula RN≡C-, whereinR is an aliphatic, aryl or heteroaryl group.

[0269] By “isothiocyanato” is meant -N=C=S.

[0270] By “low valent” is meant the lower oxidation states when a metal has multiple oxidation states.

[0271] By “oxo” is meant an =O group.

[0272] By “oxy” is meant -O-.

[0273] By “silyl” is meant a -SiR1R2R3or -SiR1R2- group. In some embodiments, each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0274] By “silyloxy” is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR1R2R3, in which each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally 51 LAMRP953WO_11461-1WOsubstituted amino. In other embodiments, the silyloxy group is -O-Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl- alkyl.

[0275] Use of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohols, ethers, esters, amides, sulfones, sulfides, hydroxyl, nitro, cyano, carboxy, amines, heteroatoms, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogens, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl and aralkyaminocarbonyl, or any of the substituents of the preceding paragraphs or any of those substituents either directly attached or by suitable linkers. The linkers are typically short chains of 1-3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or -S(O)O- . Rings may be substituted multiple times.

[0276] The term “lower” modifying “alkyl”, “alkenyl”, “alkynyl”, “alkoxy” or “alkoxycarbonyl” refers to a C1-C6 unit for a particular functionality. For example, “lower alkyl” means C1-C6alkyl.

[0277] By “substituted” is meant having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcaronyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether, ester, silicon-containing moieties, thioester or a combination thereof. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0278] By “thiocyanato” is meant -SCN.

[0279] By “thioether” is meant to include to include both unidentate and multidentate (e.g. bidentate ot tridentate) thioethers, as well as ligands that contain both thioether and thiolate (or 52 LAMRP953WO_11461-1WOother) moieties.

[0280] By “unsubstituted” is meant any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified, then it is hydrogen.

[0281] As used herein, the term “about” is understood to account for minor increases and / or decreases beyond a recited value, which changes do not significantly impact the desired function of the parameter beyond the recited value(s). In some cases, “about” encompasses + / -10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges.

[0282] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus.

[0283] The implementations disclosed below describe deposition of a material on a substrate such as a wafer, substrate, or other work piece. The work piece may be of various shapes, sizes, and materials. In this application, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the processing details recited herein (e.g., flow rates, power levels, etc.) are relevant for processing 300 mm diameter substrates, or for treating chambers that are configured to process 300 mm diameter substrates and can be scaled as appropriate for substrates or chambers of other sizes. In addition to semiconductor wafers, other work pieces that may be used implementations disclosed herein include various articles such as printed circuit boards and the like. The processes and apparatuses can be used in the fabrication of semiconductor devices, displays, LEDs, photovoltaic panels and the like.

[0284] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds.

[0285] By “unsaturated substituent” is meant a double or triple bond containing aliphatic chain, cyclic, aryl or heteroaryl group.

[0286] The term “independently selected”, when referring to R substituent selection in a molecule containing multiple R groups, means that the selection of R substituents at different atoms of a molecule is independent and that the selection of R substituents at one atom having multiple R substituents is also independent. 53 LAMRP953WO_11461-1WOCONCLUSION

[0287] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein. 54 LAMRP953WO_11461-1WO

Claims

CLAIMS What is claimed is:

1. A method for processing substrates, the method comprising: depositing a molybdenum film by one or more plasma-enhanced atomic layer deposition cycles, a plasma-enhanced atomic layer deposition cycle comprising: exposing a semiconductor substrate to a molybdenum-containing precursor, and exposing the semiconductor substrate to a reducing agent in a plasma environment, the plasma environment generated by igniting a plasma at a plasma power; and pulsing the plasma between either (1) an ON state and OFF state, or (2) a LOW state or HIGH state to modulate stress of the molybdenum film, wherein the exposing of the semiconductor substrate to the molybdenum-containing precursor and exposing the semiconductor substrate to the reducing agent in the plasma environment are performed in temporally separated pulses.

2. The method of claim 1, further comprising selecting different plasma powers for at least two of the one or more plasma-enhanced atomic layer deposition cycles to modulate stress of the molybdenum film.

3. A method for depositing a molybdenum film comprising a first molybdenum layer and a second molybdenum layer, the method comprising: depositing the first molybdenum layer to a first thickness at a first deposition temperature by: exposing a semiconductor substrate to a first molybdenum-containing precursor, and exposing the semiconductor substrate to a first reducing agent in a plasma environment; and depositing the second molybdenum layer to a second thickness at a second deposition temperature by: exposing a semiconductor substrate to a second molybdenum-containing precursor, and exposing the semiconductor substrate to a second reducing agent in a thermal environment. 55 LAMRP953WO_11461-1WO4. The method of claim 3, further comprising adjusting at least one of the following process conditions to modulate stress of the molybdenum film: plasma power during exposing of the semiconductor substrate in the plasma environment, the first deposition temperature, a duration of the exposing of the semiconductor substrate to the first molybdenum- containing precursor, a duration of the exposing of the semiconductor substrate to the first reducing agent, the second deposition temperature, a duration of the exposing of the semiconductor substrate to the second molybdenum- containing precursor, and a duration of the exposing of the semiconductor substrate to the second reducing agent.

5. A method for processing substrates, the method comprising: exposing a semiconductor substrate to a molybdenum-containing precursor, exposing the semiconductor substrate to a reducing agent to form at least a molybdenum- containing film; and exposing the semiconductor substrate to a dopant-containing precursor to modulate stress of the molybdenum-containing film.

6. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising a chuck; a plasma generator; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a molybdenum-containing precursor to the one or more process 56 LAMRP953WO_11461-1WOchambers, cause generation of a plasma, cause introduction of a reducing agent to the one or more process chambers, cause pulsing of the plasma between either (1) an ON state and OFF state, or (2) a LOW state or HIGH state.

7. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising a chuck; a plasma generator; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a first molybdenum-containing precursor to the one or more process chambers, cause introduction of a first reducing agent to the one or more process chambers, cause generation of a plasma during the at least one of the introduction of the first reducing agent or the introduction of the first molybdenum-containing precursor to form a first molybdenum layer to a first thickness, cause introduction of a second molybdenum-containing precursor to the one or more process chambers, and cause introduction of a second reducing agent without generating a plasma to form a second molybdenum layer to a second thickness.

8. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and 57 LAMRP953WO_11461-1WOa controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a molybdenum-containing precursor to the one or more process chambers, cause introduction of a reducing agent, and cause introduction of a dopant-containing precursor to the one or more process chambers.

9. A device comprising: two or more alternating layers of: a tensile molybdenum layer having a thickness of about 5Å to about 250Å, and a compressive molybdenum layer having a thickness of about 5Å to about 250Å.

10. A device comprising: a molybdenum layer doped with a dopant selected from the group consisting of vanadium, lithium, titanium, tungsten, chromium, tantalum, manganese, silicon, niobium, iron, mercury, thallium, indium, gallium, germanium, tin, rhenium, nickel, boron, zirconium, hafnium, carbon, and ruthenium, wherein dopant concentration of the dopant is selected to modulate stress without substantially affecting resistivity of the molybdenum layer. 58 LAMRP953WO_11461-1WO

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