Isonitrile inhibitors in ald

Abstract

Methods and apparatuses for using molecules having a carbon-nitrogen triple bond as inhibitors on metal-containing surfaces to selectively deposit dielectric material on a dielectric surface on a substrate surface having a metal-containing surface and a dielectric surface are provided. A method for processing substrates comprises providing a substrate having a first material and a second material thereon to a process chamber, exposing the substrate to an isonitrile inhibitor to adsorb onto the first material to inhibit deposition on the first material, and depositing a dielectric film on the second material.

Description

Attorney Docket No. LAM1P033WO-11869JD-1WO ISONITRILE INHIBITORS IN ALD RELATED APPLICATION(S)

[0000] 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 its entirety and for all purposes. BACKGROUND

[0001] Inhibitor molecules may be used to block certain surfaces on a semiconductor substrate to allow deposition on unblocked surfaces of a semiconductor substrate. However, some inhibitor molecules have limitations as devices shrink and it may be difficult to achieve selective deposition on one material versus another.

[0002] 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

[0003] One aspect involves a method for processing substrates, the method including: providing a substrate having a first material and a second material thereon to a process chamber; exposing the substrate to an isonitrile inhibitor to adsorb onto the first material to inhibit deposition on the first material; and depositing a dielectric film on the second material.

[0004] In various embodiments, isonitrile inhibitor is a metal-containing isonitrile precursor.

[0005] In various embodiments, the isonitrile inhibitor is a polyfluorinated isonitrile precursor.

[0006] In various embodiments, the isonitrile inhibitor is a molybdenum-containing isonitrile precursor.

[0007] In various embodiments, the isonitrile inhibitor is 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8- septadecafluoro-9-isocyanononane.

[0008] In various embodiments, the second material includes a metal capable of forming carbonyl bonds.

[0009] In various embodiments, exposing the substrate to the isonitrile inhibitor is performed at a temperature of about 0°C to about 150°C.

[0010] In various embodiments, exposing the substrate to the isonitrile inhibitor is performed thermally.

[0011] In various embodiments, exposing the substrate to the isonitrile inhibitor is performed using a plasma. In some embodiments, the method also includes repeating exposing the substrateAttorney Docket No. LAM1P033WO-11869JD-1WO to the isonitrile inhibitor and depositing the dielectric film in cycles.

[0012] In various embodiments, the isonitrile inhibitor includes a mixture of two or more isonitrile inhibitors.

[0013] Another aspect involves a method for processing substrates, the method including: providing a substrate having a first material and a second material thereon to a process chamber; exposing the substrate to an isocyanide precursor to adsorb onto the first material to inhibit deposition on the first material; and depositing a dielectric film on the second material.

[0014] In various embodiments, the above methods also include depositing a metal-containing material on the first material while depositing the dielectric film on the second material. In some embodiments, depositing the metal-containing material includes exposing the substrate to a reducing agent. In some embodiments, the substrate is exposed to the reducing agent in a plasma.

[0015] In various embodiments, the first material includes a metal.

[0016] In various embodiments, the method also includes annealing the substrate.

[0017] In various embodiments, depositing the dielectric film is performed by atomic layer deposition.

[0018] In various embodiments, depositing the dielectric film is performed by chemical vapor deposition.

[0019] In various embodiments, the substrate includes a recessed feature. In some embodiments, the recessed feature includes dielectric sidewalls and a metal-containing bottom surface.

[0020] Another aspect involves a method for processing substrates, the method including: providing a substrate having a metal surface including a first metal and a dielectric surface thereon to a process chamber; exposing the substrate to a metal-containing isocyanide precursor including a second metal to adsorb onto the metal surface to form an adsorbed layer; exposing the adsorbed layer to a reducing agent to form a surface including a complex including the second metal; and exposing the complex to a halogen-containing precursor.

[0021] In various embodiments, the halogen-containing precursor includes molybdenum pentachloride, molybdenum hexachloride, or molybdenum tetrachloride.

[0022] In various embodiments, the halogen-containing precursor includes molybdenum oxychloride.

[0023] In various embodiments, the method also includes annealing the substrate.

[0024] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a process flow diagram depicting operations of a method that may be performed in accordance with certain disclosed embodiments.

[0026] Figures 2A-2C are schematic illustrations of example substrates undergoing operationsAttorney Docket No. LAM1P033WO-11869JD-1WO that may be performed in accordance with certain disclosed embodiments.

[0027] Figures 3, 4, and 5 are process flow diagrams depicting operations of methods that may be performed in accordance with certain disclosed embodiments.

[0028] Figure 6 is a schematic illustration of a chamber that may be used to perform certain disclosed embodiments.

[0029] Figures 7A and 7B are schematic illustrations of tools that may be used to perform certain disclosed embodiments.

[0030] Figure 8 provides examples of general structures for molybdenum precursors in accordance with certain disclosed embodiments.

[0031] Figure 9 provides examples of low valent molybdenum precursors of the formula Mo(L)6 in accordance with certain disclosed embodiments.

[0032] Figure 10 provides examples of low valent dimolybdenum precursors in accordance with certain disclosed embodiments. DETAILED DESCRIPTION

[0033] 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.

[0034] Area selective atomic layer deposition (AS-ALD) presents a means to achieve the ever- increasing architectural density and decrementing feature sizes demanded by Moore’s law beyond what is possible when patterning by photolithography alone. With inherently selective ALD processes being rare, the use of surfactants to promote or inhibit growth of films has gained traction. Further description about surfactants is described in Parsons, G. N.; Clark, R. D. Area- Selective Deposition: Fundamentals, Applications, and Future Outlook. Chem. Mater. 2020, 32 (12), 4920–4953. https: / / doi.org / 10.1021 / acs.chemmater.0c00722 which is incorporated by reference herein in its entirety. In particular, small molecule inhibitors (SMIs) are preferable to self-assembled monolayers (SAMs) for modification of growth behavior owing to their smaller size, improved thermal characteristics, vapor phase adsorption, and (when compared to the most common SAMs) lack of heavy heteroatoms, in particular sulfur, preventing film contamination. Further description of SMIs are described in Yasmeen, S.; Ryu, S. W.; Lee, S.-H.; Lee, H.-B.-R. Atomic Layer Deposition Beyond Thin Film Deposition Technology. Advanced Materials Technologies 2023, 8 (20), 2200876. https: / / doi.org / 10.1002 / admt.202200876 which is incorporated by reference herein in its entirety.Attorney Docket No. LAM1P033WO-11869JD-1WO

[0035] Provided herein are methods of using molecules having a carbon-nitrogen triple bond as selective inhibitors to inhibit deposition on metal-containing surfaces while allowing deposition on non-metal-containing surfaces, such as dielectric surfaces. A molecule having a carbon- nitrogen triple bond is defined as a molecule having at least one carbon atom triple-bonded to a nitrogen atom, where the carbon atom triple-bonded to the nitrogen atom is a termination group on the molecule. Examples include isonitrile molecule and isocyanide. An inhibitor in accordance with certain disclosed embodiments may have any organic groups thereon or a carbon chain of any kind bonded to a N≡C terminated group or a C≡N terminated group. For example, R-N≡C or R- C≡N may be general formulas for an inhibitor molecule, where R is any organic group, including but not limited to alkyls, alkenes, and alkynes. R may be 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-C3 alkyl)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, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl or cyclyl.

[0036] Inhibitor molecules in certain disclosed embodiments strongly prefer binding to metal- containing surfaces, such as transition metal-containing surfaces, relative to dielectric surfaces compared to other inhibitor molecules, such as thiols, phosphates, silanes, and amines. In contrast to inhibitor molecules having a carbon-nitrogen triple bond, other inhibitors like CFxinhibitors are more resilient to harsh conditions like high temperature and plasma, but oxidizing conditions would break C-H bonds. In many embodiments herein, the inhibitor molecule having a carbon- nitrogen triple bond is used on metal-containing surface, or a metal surface, to block deposition on the metal-containing surface, or metal surface. Example transition metals include any transition metals capable of forming a carbonyl. Specific examples include but are not limited to molybdenum, tungsten, cobalt, copper, niobium, and ruthenium.

[0037] Certain disclosed embodiments use inhibitor molecules having a carbon-nitrogen triple bond that maximize packing density on a surface. For example, there are competing factors when maximizing packing density – a shadowing effect (a large, bulkier molecule can shadow reactive sites) whilst smaller inhibitors which can most effectively access more reactive sites. In some embodiments, multiple inhibitors of different structures and sizes may be used to strike a balanceAttorney Docket No. LAM1P033WO-11869JD-1WO between covering more reactive sites and maximizing packing density on the surface. In some embodiments, two or more inhibitor molecules having a carbon-nitrogen triple bond are used. In some embodiments, one or more inhibitor molecules having a carbon-nitrogen triple bond are mixed with one or more other types of inhibitors, such as thiols, phosphates, silanes, amines, and CFx inhibitors. For metal surfaces, it may be valuable to multiple inhibitor molecules having a carbon-nitrogen triple bond as inhibitors in particular. Certain disclosed embodiments also involve removing inhibitors after selective deposition is performed on the non-blocked or non-inhibited surface. Removing inhibitor molecules having a carbon-nitrogen triple bond can be performed even if a mix of inhibitor molecules having a carbon-nitrogen triple bond is used, so long as the terminating groups are similar in nature. For example, an ethyl isonitrile and a dodecyl isonitrile may be removed together or simultaneously or using the same technique. Removal may be performed using a reducing agent, such as hydrogen plasma. The conditions for the reducing agent exposure may be tuned to reduce or mitigate damage to the dielectric surface.

[0038] Certain disclosed embodiments involve using and synthesizing a family of novel polyfluorinated isonitriles with different chain lengths for use as a SMI in AS-ALD. As an example, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-septadecafluoro-9-isocyanononane (hereinafter “C9”) may be used as an inhibitor that is capable of selectively binding to a metal-containing surface. C9 is readily synthesized in two steps from the amine and is volatile, with a 1 Torr vapor pressure at 33°C. This compound shows promising selectivity for adsorption to metals over oxides as measured via quartz crystal microbalance (QCM), saturating gold with a surface density of 62 ng / cm2(0.81 molecules / nm2) with concurrently negligible adsorption on alumina. The synthesis and thermal characterization of several fluorinated isonitriles will be discussed. Their selectivity for metal surfaces by QCM, as well as ToF-SIMS mapping on metal / SiO2 patterned substrates demonstrate selectivity, with excellent resolution provided by the high fluorine content of the molecule. Selective inhibition of zinc oxide ALD may also be performed and selectivity values will be reported.

[0039] There is a need for inhibition methodology for area-selective deposition of dielectric films on dielectrics (such as metal oxide on metal oxide selective dep) within inherently selective recessed features (i.e. a trench or via structure with metal plug at the bottom).

[0040] Provided herein are Mo ALD / CVD metals with a precursor family for Mo (or MoC liner) deposition as well as an inhibitor for selective Mo ALD processes (e.g. MoCl5).

[0041] Various embodiments involve using isonitriles and / or isocyanides for dielectric-on- dielectric growth.

[0042] Certain disclosed embodiments are directed to using a 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8- septadecafluoro-9-isocyanononane (C9) ligand for area-selective growth:Attorney Docket No. LAM1P033WO-11869JD-1WO in two steps from the amine and is volatile, with a 1 Torr vapor pressure

[0044] Certain disclosed embodiments involve using Mo-C9-based precursors (but not limited to Mo metal). INHIBITION OF DIELECTRIC-ON-DIELECTRIC DEPOSITION FOR SELECTIVE AREA ALD USING “C9”

[0045] While certain methods can be used for silicon-based inhibitor for fully aligned via (FAV) applications, silicon-based impurities arise from various plasma-enhanced ALD / CVD (PEALD / PECVD) precursors.

[0046] Provided herein includes a method to (1) selectively deposit a dielectric film on a dielectric surface with minimal overhang / mushrooming & (2) a method to simultaneously deposit a dielectric film on a dielectric surface and a metal film on a metal surface.

[0047] Some selective deposition processes of dielectric-on-dielectric surface (for example for the FAV SiO2, AlOx, TaN on a dielectric (low-k or SiO2) and not on conductor (Co / Cu / W / Mo) use silicon-based inhibitors (silanes such as CxHy-SiH3 or amides such as (CH3)3Si(N(CH3)2) to block deposition on the metal surfaces to block dielectric deposition on the metal surface and allow deposition to occur on the dielectric surface. However, overhang of the film onto the inhibited metal surface is a strong risk as the thickness increases (precursor mass loading in features is also a concern). USE OF Mo-C9 (MO ISONITRILE PRECURSORS AND SIMILAR) AS INHIBITORS FOR SELECTIVE Mo ALD USING OTHER PRECURSORS (MoCl5, MoO2Cl2)

[0048] Some Mo precursors include MoO2Cl2, MoCl5, MoOCl4, and many other halogenated precursors thereof. Many of these, such as MoO2Cl2, are non-selective which means they deposit indiscriminately on dielectric and metal surfaces or incoming logic customer device features. Other more selective choices such as MoCl5(MoF6, etc.) have a self-etch mechanism which makes them less amenable to many applications, especially on the back end (BEOL) due to Cu (or Co-cladded Cu) damage, migration of the Cu into the Mo bulk and even the surface of Mo film, as well as Cl incorporation (damage) to the surround low k dielectric.

[0049] Certain disclosed embodiments use isonitrile-based molecular inhibitors and Mo- isonitrile molecules as dual-purpose inhibitor / precursors.

[0050] Figure 1 shows a process flow diagram depicting operations that may be performed inAttorney Docket No. LAM1P033WO-11869JD-1WO accordance with certain disclosed embodiments. In operation 102, an inhibitor molecule having a carbon-nitrogen triple bond such as an isonitrile inhibitor (or multiple isonitrile inhibitors, or isonitrile inhibitors mixed with non-isonitrile inhibitors) may be introduced to a semiconductor substrate having a non-metal and a metal-containing surface thereon, causing binding of the inhibitor to the metal-containing surface. This may be performed in a thermal process, or in a plasma-free process. It may be performed at lower temperatures. An example range of temperatures includes but is not limited to room temperature to about 500°C, or about 50°C to about 200°C, or about 50°C to about 150°C, or about 0°C to about 150°C. Each of the one or more inhibitors may be flowed at a flow rate of about 80 sccm to about 100 sccm for a 4-station chamber. The inhibitor may be introduced using a carrier gas or an inert gas, such as helium, argon, or neon.

[0051] In operation 104, a deposition process is performed to deposit material selectively on the non-metal, non-blocked, and / or non-inhibited surface. In various embodiments, deposition is performed to deposit dielectric material on the non-metal surface. The non-metal surface may be a dielectric material as well. Deposition may be performed using atomic layer deposition (ALD). Deposition may be performed thermally. Operations 104 and 102 may be performed in the same chamber on different stations or in different chambers or different tools. Example materials that may be deposited include silicon oxide, silicon nitride, silicon, polysilicon, titanium oxide, or any other metal oxides.

[0052] In operation 106, operations 102 and 104 may be optionally repeated. This may be performed in cycles. In some embodiments, cycles are performed to replenish the inhibitor onto the metal-containing or metal surface. In some embodiments, cycles may be performed if the deposition process in operation 104 involves a plasma.

[0053] In operation 108, the inhibitor is optionally removed from the surface. In some embodiments, removal is optional if the inhibitor gets consumed during deposition. In some embodiments, removal is performed using a reducing agent plasma under mild conditions. Example plasmas include helium plasma and hydrogen plasma. The plasma may be generated by a single frequency plasma or a dual frequency plasma. Plasma may be generated remotely or in situ. The plasma frequency depends on the type of plasma used.

[0054] In operation 110, an optional annealing operation may be performed to remove the last of the inhibitor from the surface. Annealing may be performed at temperatures of about 350°C to about 400°C or higher depending on the substrate limitations. For example, for back end of line (BEOL), temperature may be about 400°C, whereas for front end of line (FEOL), higher temperatures may be tolerable.

[0055] Figures 2A-2C show a schematic illustration of the selective nature of certain disclosedAttorney Docket No. LAM1P033WO-11869JD-1WO embodiments. In Figure 2A, a substrate having a metal material 201 and dielectric material 203 is provided. In Figure 2B, the substrate is exposed to an isonitrile inhibitor which forms a blocking layer 205 onto the metal material 201. This blocking layer may compose of one or more isonitrile inhibitors, or isonitrile inhibitors in combination with non-isonitrile inhibitors. They may be bound to the metal with tail groups exposed on the surface (not shown). In Figure 2C, selective deposition is achieved whereby material 207 is deposited selectively on the dielectric material 203 and not on the blocking layer 205. In some embodiments, material 207 is a dielectric material as well.

[0056] Figure 3 shows a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. In operation 302, the “C9” inhibitor may be introduced to the metal-dielectric surface or recessed feature, selectively binding to the metal surface. in operation 304, dielectric ALD (PEALD / PECVD) process may be performed to selectively deposit on exposed dielectric portion of the surface or feature. Optionally selective area ALD can be cycled in operation 305. In operation 306, operations 302 and 304 may be optionally repeated. This may be the same as operation 305. In operation 308, the C9-inhibited surface can be optionally exposed to a reducing agent or reducing agent plasma which may be used to remove the inhibitor. Optionally, in operation 310, thermal or flash-enhanced atomic layer annealing may be performed which may combust any residues from the C9 inhibitor.

[0057] Figure 4 shows a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. Operations include in operation 404, introducing Mo-C9 precursor / inhibitor to the metal-dielectric surface or recessed feature, in operation 404, selectively binding to the metal surface; performing dielectric ALD (PEALD / PECVD) process selectively on exposed dielectric portion of the surface or feature; optionally purging in operation 406; in operation 408, exposure of the Mo-C9-inhibited surface or structure to reducing agent to remove C9 and leave Mo (or metal) film behind; an optional purge in operation 409; and in operation 411, optional thermal or flash-enhanced atomic layer annealing step to combust any residues from C9 inhibitor. Purge operations may be performed before or after or between any operations described herein and use of inhibitor and ALD can be cycled.

[0058] In some embodiments, the precursor is a different metal precursor, such as a W precursor, or a Co precursors. Various isocyanide ligands may be attached, including but not limited to L = C9NC and C8NC ligand.

[0059] Figure 5 includes a process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. Operations include in operation 502, introduction of Mo-C9 precursor / inhibitor* to the metal-dielectric surface or recessed BEOL feature (e.g. Cu at the bottom with dielectric field / sidewall), selectively binding to the metal surface; in operation 504, reduction of the Mo-C9 to Mo / MoCxNy; optionally purging in operationAttorney Docket No. LAM1P033WO-11869JD-1WO 506; exposure of the Mo / MoCxNy-protected metal (e.g. Cu) to MoCl5 or MoO2Cl2 (all MoOzXy relevant here; X=halogen such as F, Cl, Br, or I); optionally purging in operation 509; and in operation 511, optional thermal or flash-enhanced atomic layer annealing / post-processing step to combust any residues from C9 inhibitor and remove Cl. Purge operations may be performed before or after or between any operations described herein and use of inhibitor and ALD can be cycled. Additional ligands are described in the definitions section.

[0060] Precursors may include other perfluoro ethyl, propyl, and butyl isocyanide complexes, and other ligands. Example ligands are described in the Definitions section. Precursors may be synthesized using various techniques. APPARATUS

[0061] Figure 6 depicts a schematic illustration of an embodiment of an ALD process station 600 having a process chamber 602 for maintaining a low-pressure environment. In some embodiments, a plurality of ALD process stations may be included in a common low-pressure process tool environment. For example, Figures 7A and 7B depict embodiments of a multi-station processing tool 700. In some embodiments, one or more hardware parameters of ALD process station 600, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers 750. In some other embodiments, a process chamber may be a single station chamber.

[0062] ALD process station 600 fluidly communicates with reactant delivery system 601a for delivering process gases to a distribution showerhead 606. Reactant delivery system 601a includes a mixing vessel 604 for blending and / or conditioning process gases, such as a Mo precursor-containing gas, a hydrogen-containing gas, an argon or other carrier gas, or other reactant-containing gas, for delivery to showerhead 606. One or more mixing vessel inlet valves 620 may control introduction of process gases to mixing vessel 604. In various embodiments, introduction of the isonitrile inhibitor is performed in process station 600 and in some embodiments, other operations such as deposition of dielectric material may be performed in the same or another station of the multi-station processing tool 700 as further described below with respect to Figure 7A.

[0063] As an example, the embodiment of Figure 6 includes a vaporization point 603 for vaporizing liquid reactant to be supplied to the mixing vessel 604. In some embodiments, vaporization point 603 may be a heated vaporizer. In some embodiments, a liquid precursor or liquid reactant may be vaporized at a liquid injector (not shown). For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel 604. In one embodiment, a liquid injector may vaporize the reactant by flashing the liquid from a higherAttorney Docket No. LAM1P033WO-11869JD-1WO pressure to a lower pressure. In another example, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 603. In one scenario, a liquid injector may be mounted directly to mixing vessel 604. In another scenario, a liquid injector may be mounted directly to showerhead 606.

[0064] In some embodiments, a liquid flow controller (LFC) upstream of vaporization point 603 may be provided for controlling a mass flow of liquid for vaporization and delivery to process chamber 602. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend the time for dosing a liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by disabling a sense tube of the LFC and the PID controller.

[0065] Showerhead 606 distributes process gases toward substrate 612. In the embodiment shown in Figure 6, the substrate 612 is located beneath showerhead 606 and is shown resting on a pedestal 608. Showerhead 606 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to substrate 612.

[0066] In some embodiments, pedestal 608 may be raised or lowered to expose substrate 612 to a volume between the substrate 612 and the showerhead 606. In some embodiments, pedestal 608 may be temperature controlled via heater 610. Pedestal 608 may be set to any suitable temperature, such as between about 0°C and about 500°C or 0°C to about 150°C during operations for performing various disclosed embodiments. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller 850. At the conclusion of a process phase, pedestal 608 may be lowered during another substrate transfer phase to allow removal of substrate 612 from pedestal 608.

[0067] In some embodiments, a position of showerhead 606 may be adjusted relative to pedestal 608 to vary a volume between the substrate 612 and the showerhead 606. Further, it will be appreciated that a vertical position of pedestal 608 and / or showerhead 606 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 608 may include a rotational axis for rotating an orientation of substrate 612. 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 650. The computer controller 650Attorney Docket No. LAM1P033WO-11869JD-1WO may include any of the features described below with respect to controller 650 of Figure 6.

[0068] In some embodiments where plasma may be used as discussed above, showerhead 606 and pedestal 608 electrically communicate with a radio frequency (RF) power supply 614 and matching network 616 for powering a plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 614 and matching network 616 may be operated at any suitable power to form a plasma having a desired composition of radical species. Likewise, RF power supply 614 may provide RF power of any suitable frequency. In some embodiments, RF power supply 614 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 0 kHz and 900 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 80 MHz, or greater than 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.

[0069] 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.

[0070] In some embodiments, instructions for a controller 650 may be provided via input / output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a reactant gas (e.g., an isonitrile inhibitor), instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or a reactant gas, and instructionsAttorney Docket No. LAM1P033WO-11869JD-1WO for modulating a flow rate of a carrier or purge gas and time delay instructions for the second recipe phase. A third recipe phase may include instructions for modulating a flow rate of a second reactant gas such as H2, instructions for modulating the flow rate of a carrier or purge gas, instructions for igniting a plasma, and time delay instructions for the third recipe phase. A fourth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fourth 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.

[0071] Further, in some embodiments, pressure control for process station 600 may be provided by butterfly valve 618. As shown in the embodiment of Figure 6, butterfly valve 618 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 600 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 600.

[0072] Figure 7A and Figure 7B show examples of processing systems. Figure 7A shows an example of a processing system including multiple chambers. The system 700 includes a transfer module 703. The transfer module 703 provides a clean, vacuum environment to minimize risk of contamination of substrates being processed as they are moved between various modules. Mounted on the transfer module 703 is a multi-station chamber 709 capable of performing in-situ clean and / or ALD processes described above. Isonitrile inhibition may be performed in the same or different station or chamber as the subsequent dielectric deposition.

[0073] Chamber 709 may include multiple stations 711, 713, 715, and 717 that may sequentially perform operations in accordance with disclosed embodiments. For example, chamber 709 may be configured such that station 711 performs an isonitrile inhibition operation. Station 713 may be configured to perform ALD and stations 715 and 717 may be configured to introduce a reducing agent to remove the inhibitor. In another example, the chamber 709 may be configured to do parallel processing of substrates, with each station performing multiple processes sequentially.

[0074] Two or more stations may be included in a multi-station chamber, e.g., 2–6, with the operations appropriately distributed. For example, a two-station chamber may be configured to perform isonitrile inhibition in a first station followed by ALD of dielectric in a second station. Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate.

[0075] Also mounted on the transfer module 703 may be one or more single or multi-station modules 707. In some embodiments, a preclean as described above may be performed in a module 707, after which the substrate is transferred under vacuum to another module (e.g., another module 707 or chamber 709) for ALD. In another example, a module for selective treatment of a film mayAttorney Docket No. LAM1P033WO-11869JD-1WO be mounted on the transfer module.

[0076] The system 700 also includes one or more wafer source modules 701, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 719 may first remove wafers from the source modules 701 to loadlocks 721. A wafer transfer device (generally a robot arm unit) in the transfer module 703 moves the wafers from loadlocks 721 to and among the modules mounted on the transfer module 703.

[0077] In some embodiments, isonitrile inhibition is performed in a first chamber, which may be part of a system like system 700, with ALD of dielectric performed in another chamber, which may not be coupled to a common transfer module, but part of another system.

[0078] Figure 7B is an embodiment of a system 700. The system 700 in Figure 7B has wafer source modules 701, a transfer module 703, atmospheric transfer chamber 719, and loadlocks 721, as described above with reference to Figure 7A. The system in Figure 7B has three single station modules 757a–757c. The system 700 may be configured to sequentially perform operations in accordance with disclosed embodiments. For example, the single station modules 757a–757c may be configured so that a first module 757a performs an isonitrile inhibition, a second module 757b performs ALD of dielectric, and a third module 757c performs reducing agent plasma exposure. In another example, the single station modules 757a–757c may be configured so that a first module 757a performs isonitrile inhibition, a second module 757b performs deposition, and a third module 757c performs removal by reducing agent plasma. In yet another example, one module may be configured for inhibition, another module for selective deposition, and another module for removal of inhibitor.

[0079] Returning to Figure 7A and 7B, in various embodiments, a system controller 729 is employed to control process conditions during deposition. The controller 729 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. Such a system controller may be employed in control of any of the processes and apparatus described herein.

[0080] The controller 729 may control all the activities of the apparatus. The system controller 729 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 729 may be employed in some embodiments.

[0081] Typically, there will be a user interface associated with the controller 729. The user interface may include a display screen, graphical software displays of the apparatus and / or processAttorney Docket No. LAM1P033WO-11869JD-1WO conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0082] System control logic may be configured in any suitable way. In general, 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.

[0083] The computer program code for controlling the Mo precursor pulses, hydrogen pulses, and argon flow, 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.

[0084] 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 and may be entered utilizing the user interface.

[0085] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 729. The signals for controlling the process are output on the analog and digital output connections of the deposition apparatus.

[0086] The system software may be designed or configured in many 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 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.

[0087] In some implementations, a controller 729 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. TheAttorney Docket No. LAM1P033WO-11869JD-1WO controller 729, depending on the processing requirements and / or the type of system, may be programmed to 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.

[0088] 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 embodiments, 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.

[0089] The controller 729, 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 729 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. 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. 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 including one or more discrete controllers that are networked togetherAttorney Docket No. LAM1P033WO-11869JD-1WO 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.

[0090] 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 PVD chamber or module, a CVD chamber or module, an 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.

[0091] As noted above, depending on the process step or steps to be performed by the tool, the controller 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.

[0092] The controller 729 may include various programs. A substrate positioning program may include program code for controlling chamber components that are used to load the substrate onto a pedestal or chuck and to control the spacing between the substrate and other parts of the chamber such as a gas inlet. A substrate tilt and rotation program may include tilt and rotation. A process gas control program may include code for controlling gas composition, flow rates, pulse times, and optionally for flowing gas into the chamber prior to deposition to stabilize the pressure in the chamber. A pressure control program may include code for controlling the pressure in the chamber by regulating, e.g., a throttle valve in the exhaust system of the chamber. 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 wafer chuck.

[0093] Examples of chamber sensors that may be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the pedestal or chuck. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions.

[0094] The foregoing describes implementation of disclosed embodiments in a single or multi- chamber semiconductor processing tool. The apparatus and process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication orAttorney Docket No. LAM1P033WO-11869JD-1WO manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such tools / processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following steps, each step provided with a number of possible tools: (1) application of photoresist on a workpiece, i.e., 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 workpiece 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. DEFINITIONS

[0095] “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.

[0096] 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.

[0097] 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,Attorney Docket No. LAM1P033WO-11869JD-1WO 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.

[0098] 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 alkenes (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.

[0099] 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., C3-24 cycloalkenyl) 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.

[0100] 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., C3-24cycloalkenyl) 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-.

[0101] 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.

[0102] 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 beAttorney Docket No. LAM1P033WO-11869JD-1WO cyclic (e.g., C3-24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyl 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) C1-6alkoxy (e.g., -O-Ak, wherein Ak is optionally substituted C1-6alkyl); (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) C3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C3-8hydrocarbon 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) C1-6alkyl, (b) C4-18aryl, and (c) (C4-18aryl) 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, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24alkyl group.Attorney Docket No. LAM1P033WO-11869JD-1WO

[0103] 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 C2-24alkylene 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.

[0104] 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.

[0105] The term “alkylsilyl”, as used herein, refers to SiR3 group, 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.

[0106] By “alkynyl” is meant an optionally substituted C2-24 alkyl 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 C2-8 alkynyl, C2-6 alkynyl, C2-5 alkynyl, C2-4 alkynyl, or C2-3alkynyl. 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.

[0107] 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-.

[0108] By “amido” is meant -N(RN1)C(O)-, where RN1is H, optionally substituted alkyl, or optionally substituted aryl.

[0109] 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.

[0110] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0111] By “aminoaryl” is meant an aryl group, as defined herein, substituted by an amino group,Attorney Docket No. LAM1P033WO-11869JD-1WO as defined herein.

[0112] 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-C4-8 cycloalkyl 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.

[0113] By “azido” is meant -N3.

[0114] By “branched alkenyl” is meant an isomer of a straight chain alkenyl compound; one having alkyl groups bonded to the main carbon chain.

[0115] By “cyano” is meant -CN.

[0116] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0117] 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.

[0118] 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 the 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.

[0119] 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,Attorney Docket No. LAM1P033WO-11869JD-1WO 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).

[0120] The term “fluoroalkyl”, as used herein, refers to 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.

[0121] By “halo” is meant F, Cl, Br, or I.

[0122] By “halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group.

[0123] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.

[0124] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0125] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0126] 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 C3-6haloalkyl. 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 z2 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.

[0127] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo.

[0128] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwiseAttorney Docket No. LAM1P033WO-11869JD-1WO 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 bond, 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, dibenzophenazinyl, 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,Attorney Docket No. LAM1P033WO-11869JD-1WO 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, xanthionyl, 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.

[0129] By “hydroxyl” is meant -OH.

[0130] By “imino” is meant -NR-, in which R can be H or optionally substituted alkyl.

[0131] By “isocyanato” is meant -NCO.

[0132] By “isocyano” is meant -N ≡ C -, and includes nitriles of the formula RN≡C-,wherein R is an aliphatic, aryl or heteroaryl group.

[0133] By “isothiocyanato” is meant -N=C=S.

[0134] By “low valent” is meant the lower oxidation states when a metal has multiple oxidationAttorney Docket No. LAM1P033WO-11869JD-1WO states.

[0135] By “oxo” is meant an =O group.

[0136] By “oxy” is meant -O-.

[0137] 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.

[0138] 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 substituted 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.

[0139] 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 thoseAttorney Docket No. LAM1P033WO-11869JD-1WO 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.

[0140] 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.

[0141] 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).

[0142] By “thiocyanato” is meant -SCN.

[0143] 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 other) moieties.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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 ordinaryAttorney Docket No. LAM1P033WO-11869JD-1WO 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.

[0148] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds.

[0149] By “unsaturated substituent” is meant a double or triple bond containing aliphatic chain, cyclic, aryl or heteroaryl group.

[0150] 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.

[0151] Generally, molybdenum precursors 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.

[0152] Suitable molybdenum containing precursors include molybdenum halides and oxyhalides, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides, and oxybromides where molybdenum may be in any of the oxidation states from +2 to +6.

[0153] Molybdenum chloride precursors are given by the formula MoClx, where x is 2, 3, 4, 5, or 6, and include molybdenum dichloride (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoCl6 are used. While the description chiefly refers to MoClx precursors, in other embodiments, other molybdenum halide precursors may be used. Molybdenum halide precursors are given by the formula MoXz, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and z is 2, 3, 4, 5, or 6. Examples of MoXz precursors include molybdenum fluoride (MoF6). In some embodiments, a non-fluorine- containing MoXz precursor is used to prevent fluorine etch or incorporation. In some embodiments, a non-bromine-containing and / or a non-iodine-containing MoXzprecursor is usedAttorney Docket No. LAM1P033WO-11869JD-1WO to prevent etch or bromine or iodine incorporation.

[0154] Molybdenum oxyhalide precursors are given by the formula MoOyXz, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and y and z are numbers greater than 0 such that MoOyXzforms a stable compound. Examples of molybdenum oxyhalides include molybdenum dichloride dioxide (MoO2Cl2), molybdenum tetrachloride oxide (MoOCl4), molybdenum tetrafluoride oxide (MoOF4), molybdenum dibromide dioxide (MoO2Br2), and the molybdenum iodides MoO2I, and Mo4O11I.

[0155] In some embodiments discussed herein, the precursors having molecular weights of less than about 450 g / mol, such as less than about 400 g / mol.

[0156] In some embodiments the molybdenum-containing precursor has a formula MoXnYm, wherein X is a chalcogen (e.g., oxygen or sulfur), Y is a halogen (e.g., fluorine, chlorine, bromine, or iodine), n is 0, 1, or 2 and m is 2, 3, 4, 5, or 6. Examples of halogen-containing molybdenum- containing precursors include without limitation MoCl5, Mo2Cl10, MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6. LOW-VALENTMOLYBDENUMCOMPLEXES

[0157] 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.

[0158] 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. MOLYBDENUM ZERO COMPLEXES

[0159] 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) occur. Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex existing in the oxidation state of zero.

[0160] 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 aAttorney Docket No. LAM1P033WO-11869JD-1WO bidentate ligand; and m is an integer of 1 to 3. MONODENTATELIGANDS

[0161] 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-C3alkyl)C(O)(C1-C3alkyl), -C1-C3alkylamino, alkenylamino, alkynylamino, di(C1- C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, - PO3H2, -OPO3H2, -C(O)N(C1-C3alkyl)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 independently an aliphatic such as haloalkyl or aryl such as a haloaryl group.

[0162] 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.

[0163] In some embodiments, the monodentate ligand can include an oxygen atom. In particular embodiments, one or more ligands can be optionally substituted with alkoxy. Non-limiting ligands include, e.g., methoxy, ethoxy, isopropoxy (i-PrO) and t-butoxy (t-BuO). 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.

[0164] 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.Attorney Docket No. LAM1P033WO-11869JD-1WO

[0165] 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, PCl3 or 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).

[0166] 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.

[0167] 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.

[0168] 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, =CR2or CR, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group.

[0169] 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 (-Attorney Docket No. LAM1P033WO-11869JD-1WO CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (- CH2CHFI), and the like. In particular embodiments, the C1-2haloalkyl includes β-halo-substituted ethyl. Yet other haloaliphatic groups include C1-4 haloalkyl, C2-4 haloalkenyl, and C2-4 haloalkynyl.

[0170] 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 (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), 2-methyl-1-propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2, 1-methylallyl (CH(CH3)CH=CH2 and the like.

[0171] In some embodiments, the monodentate ligand may be -CH2P(CH3)3, -CH(Si(CH3)3)(P(CH3)3), -C(O)C3F7, or -CHCHSO2C6H5.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.Attorney Docket No. LAM1P033WO-11869JD-1WO

[0177] 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).

[0178] 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, 1- propynyl, 2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0179] 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 R1CCCH2MoL3 where R1is a C1-C2 linear 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).

[0180] 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.

[0181] 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 C1-4 haloalkyl, C2-4 haloalkenyl, or C2-4 haloalkynyl; and in which each X is, independently, halo. In yet other embodiments, the metal- containing precursor is RMoX3, in which R is C1-2 alkyl, C2-4 alkenyl, or C2-4 alkynyl; and in which each X is, independently, halo.

[0182] In other embodiments, the monodentate ligand is C1- C3 aliphatic (wherein the C1-C3 aliphatic may be optionally substituted with a ketone, an alkoxy group, an epoxy group) or a - C(O)C1-C3 alkyl group. Ethers, ketones or epoxide-containing ligands on the low valent molybdenum-containing precursors may be advantageous to assist in crosslinking.

[0183] In some embodiments, the monodentate ligand can include a silicon atom. In someAttorney Docket No. LAM1P033WO-11869JD-1WO embodiments, the monodentate ligand may be -Si(CH3)3, -Si(C2H5)3, -CH2Si(CH3)3, - CH(Si(CH3)3)2or -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.

[0184] For any formula herein, each monodentate ligand may independently be hydrogen, halo, azido, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1can be alkyl).

[0185] 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.

[0186] 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

[0187] 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), trifluoroacetate (O2CCF3, TFA), oxalate (ox), or acetylacetonate (acac). Precursors with bidentate ligands include, but are not limited to, molybdenum diacetylacetonate dioxide (MoO2(acac)2).

[0188] Example structures containing the bidentate ligand include, but are not limited to .Attorney Docket No. LAM1P033WO-11869JD-1WO

[0189] The bidentate ligand may be a linking moiety 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.

[0190] Suitable low valent molybdenum precursors may contain one, two or three bidentate ligands each of which may be the same or different.

[0191] The bidentate ligand may be an amidinate, an amidate, an iminopyrrolidinate, a diazabutadiene, 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

[0192] 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.

[0193] 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. Precursors with two ligands include, but are not limited to, bis(ethylbenzene)molybdenum (C16H20Mo).

[0194] FIG. 8 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)3 or -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,Attorney Docket No. LAM1P033WO-11869JD-1WO =S or =CR2, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. Suitable precursors having four ligands include, but are not limited to, Mo(NtBu)2(OBu)2and (iPrCp)2MoH2. Suitable precursors having five ligands include, but are not limited to, MoO(OiPr)4.

[0195] 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.

[0196] Low valent molybdenum precursors may also have six ligands. Precursors with six ligands include, but are not limited to, molybdenum hexafluoride (MoF6) and molybdenum hexacarbonyl (Mo(CO)6). In some embodiments, such precursors may have the general formula Mo(X)p(R10)q (XII) where each X independently includes chloro, fluoro, bromo 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.

[0197] 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)3or -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.

[0198] FIG. 9 illustrates example structures for low valent molybdenum precursors having six ligands. Structures 1-9 have one or more CNR ligands which may be isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, or isocyanohaloaryl groups. 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, -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. Structures 10-18 have one or more PMe3 ligands.

[0199] Molybdenum complexes can be prepared using a zero valent starting material such as molybdenum hexacarbonyl. Other synthetic routes include reaction of MoCl3(THF)3with theAttorney Docket No. LAM1P033WO-11869JD-1WO appropriate ligand followed by reduction and reaction of MoX5 (X = Cl, Br, I) with the appropriate ligand followed by reduction.

[0200] The starting material can be treated with a neutral ligand, such as a thioether (dialkylsulfide), to induce redox neutral ligand exchange. The zero valent starting material can also be treated with a ligand precursor, such as bis(diethylthiocarbamoyl)disulfide or bis(trifluoromethyl)-1,2-dithiete, to induce oxidative addition and form the sulfur-containing complexes described herein.

[0201] The reactions may be conducted in a variety of non-protic solvents. For example the reaction may be conducted in an ether solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, in a hydrocarbon solvent such as toluene, benzene, heptane, hexane, pentane, or in a halocarbon solvent such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc. The reactions can be conducted in a wide temperature range depending on the boiling point of the solvent and on solubility of the products. In some embodiments, the starting materials, reaction intermediates, and the desired products are unstable toward moisture and oxygen. Accordingly, the reaction process should be conducted using anhydrous and air-free conditions using a protective inert gas, such as nitrogen or argon. DIMOLYBDENUM COMPLEXES

[0202] In another aspect, precursors for deposition of molybdenum-containing films are di- molybdenum compounds containing a direct molybdenum-molybdenum bond (e.g., a multiple molybdenum-molybdenum bond, such as a double bond, or any multiple bond with a bond order of 2-5). The directly bonded dimolybdenum precursors may be of the structure Mo2Ln (II), where each occurrence of L is independently a monodentate, ambidentate, bidentate or tridentate ligand as described above, and n is 2 to 6. One example precursor is Mo2(O-isopropyl)6. Other example precursors are shown in FIG. 10, and include Mo2(OAc)4, Mo2(TFA)4and other di-molybdenum carboxylates. In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a double bond (such as structure 19). In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a triple bond (such as structures 20-23). For structures 20 and 21, R may be an aliphatic group such as an alkyl group, a haloalkyl group or a silyl group. For structure 23, L may be any ligand described above, or may be any one of CO, CNR or PMe3 (where R is aliphatic, aryl or heterocyclyl) and X is halo. Such precursors are particularly useful for deposition of molybdenum metal and high purity molybdenum metal because it may be easier to reduce such compounds to metallic molybdenum than some monoatomic molybdenum compounds.Attorney Docket No. LAM1P033WO-11869JD-1WO

[0203] A low valent dimolybdenum complex may also contain two molybdenum atoms connected indirectly to each other by a linking moiety. Such precursors may be of the formula LnMo(L’)mMoLn (III) where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand as described above; L’ is a linking moiety; n is 2 to 6; and m is 1 to 3. The linking moiety L’ may be of the structure –(E)e- where each E independently includes C(R)n, NR, 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. CONCLUSION

[0204] 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.

Claims

Attorney Docket No. LAM1P033WO-11869JD-1WO CLAIMS What is claimed is:

1. A method for processing substrates, the method comprising: providing a substrate having a first material and a second material thereon to a process chamber; exposing the substrate to an isonitrile inhibitor to adsorb onto the first material to inhibit deposition on the first material; and depositing a dielectric film on the second material.

2. The method of claim 1, wherein the isonitrile inhibitor is a metal-containing isonitrile precursor.

3. The method of claim 1, wherein the isonitrile inhibitor is a polyfluorinated isonitrile precursor.

4. The method of claim 1, wherein the isonitrile inhibitor is a molybdenum-containing isonitrile precursor.

5. The method of claim 1, wherein the isonitrile inhibitor is 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8- septadecafluoro-9-isocyanononane.

6. The method of claim 1, wherein the second material comprises a metal capable of forming carbonyl bonds.

7. The method of claim 1, wherein exposing the substrate to the isonitrile inhibitor is performed at a temperature of about 0°C to about 150°C.

8. The method of claim 1, wherein exposing the substrate to the isonitrile inhibitor is performed thermally.

9. The method of claim 1, wherein exposing the substrate to the isonitrile inhibitor is performed using a plasma.Attorney Docket No. LAM1P033WO-11869JD-1WO 10. The method of claim 9, further comprising repeating exposing the substrate to the isonitrile inhibitor and depositing the dielectric film in cycles.

11. The method of claim 1, wherein the isonitrile inhibitor comprises a mixture of two or more isonitrile inhibitors.

12. A method for processing substrates, the method comprising: providing a substrate having a first material and a second material thereon to a process chamber; exposing the substrate to an isocyanide precursor to adsorb onto the first material to inhibit deposition on the first material; and depositing a dielectric film on the second material.

13. The method of claims 1-12, further comprising depositing a metal-containing material on the first material while depositing the dielectric film on the second material.

14. The method of claims 1-12, wherein the first material comprises a metal.

15. The method of claim 13, wherein depositing the metal-containing material comprises exposing the substrate to a reducing agent.

16. The method of claim 15, wherein the substrate is exposed to the reducing agent in a plasma.

17. The method of any of claims 1-15, further comprising annealing the substrate.

18. The method of any of claims 1-15, wherein depositing the dielectric film is performed by atomic layer deposition.

19. The method of any of claims 1-15, wherein depositing the dielectric film is performed by chemical vapor deposition.

20. The method of any of claims 1-15, wherein the substrate comprises a recessed feature.Attorney Docket No. LAM1P033WO-11869JD-1WO 21. The method of claim 20, wherein the recessed feature comprises dielectric sidewalls and a metal-containing bottom surface.

22. A method for processing substrates, the method comprising: providing a substrate having a metal surface comprising a first metal and a dielectric surface thereon to a process chamber; exposing the substrate to a metal-containing isocyanide precursor comprising a second metal to adsorb onto the metal surface to form an adsorbed layer; exposing the adsorbed layer to a reducing agent to form a surface comprising a complex comprising the second metal; and exposing the complex to a halogen-containing precursor.

23. The method of claim 22, wherein the halogen-containing precursor comprises molybdenum pentachloride, molybdenum hexachloride, or molybdenum tetrachloride.

24. The method of claim 22, wherein the halogen-containing precursor comprises molybdenum oxychloride.

25. The method of any of claims 22-24, further comprising annealing the substrate.

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