Molybdenum in logic BEOL metallization

Abstract

Methods and apparatuses for deposited molybdenum for metallization applications using pulsed chemical vapor deposition are described herein. The method for processing substrates comprises providing a substrate having a negative feature in a low-k dielectric and depositing molybdenum into the negative feature to at least partially fill the negative feature with molybdenum over a copper layer.

Description

MOLYBDENUM IN LOGIC BEOL METALLIZATION CROSS-REFERENCES

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

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

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

[0004] Methods and apparatuses for processing semiconductor substrates are provided herein. One aspect involves a method for processing substrates, the method including: providing a substrate having a negative feature in a low-k dielectric; and depositing molybdenum into the negative feature to at least partially fill the negative feature with molybdenum over a copper layer.

[0005] In various embodiments, the molybdenum is deposited by exposing the substrate to a first hydrogen gas and a molybdenum-containing precursor gas. In some embodiments, the exposing the substrate to the first hydrogen gas and the molybdenum-containing precursor gas are performed in a process chamber housing the substrate and a purge gas is periodically pulsed during the depositing of the molybdenum to purge excess byproducts from the process chamber.

[0006] In various embodiments, the molybdenum is deposited directly on the copper layer for use as a molybdenum M0 layer.

[0007] In various embodiments, the molybdenum is deposited directly on an electromigration layer.

[0008] In any of the above embodiments, the first hydrogen gas may be pulsed. In some embodiments the pulses are temporally sequential pulses. In some embodiments, the temporally sequential pulses of the first hydrogen gas and the purge gas are alternating pulses. In some embodiments, depositing the molybdenum includes pulsing the molybdenum-containing 1 LAMRP922WO-11400-WOprecursor. For example, in some embodiments the pulses of the first hydrogen gas, molybdenum- containing precursor, and purge gas are temporally sequential pulses.

[0009] In any of the above embodiments, the method may also include exposing the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum into the negative feature.

[0010] In various embodiments, the molybdenum is deposited over a tungsten layer, and the molybdenum is deposited on a second copper layer, whereby the second copper layer is between the tungsten layer and the molybdenum. For example, in some embodiments, the molybdenum acts as a V0 layer, and the second copper layer acts as a M0 layer.

[0011] In various embodiments, the molybdenum is deposited directly on tungsten for use as a molybdenum M0 layer. For example, in some embodiments, the molybdenum is also deposited on the molybdenum M0 layer to form a molybdenum V0 layer. In some embodiments, a second copper layer is deposited over the molybdenum M0 layer to form a copper V0 layer.

[0012] In various of the above embodiments, a barrier layer may be formed between the first copper layer and the molybdenum. For example, in some embodiments, the barrier layer includes cobalt and tantalum oxide. In some embodiments, the cobalt is positioned between a first copper layer and a tantalum oxide. In various embodiments, the barrier layer is an electromigration layer. In various embodiments, the barrier layer is a diffusion barrier layer. In various embodiments, the barrier layer includes cobalt. In various embodiments, the barrier layer includes ruthenium. In various embodiments, the barrier layer includes cobalt ruthenium alloy. In various embodiments, the barrier layer includes tantalum nitride.

[0013] Another aspect involves a method for processing substrates, the method including: providing a substrate having a negative feature in a low-k dielectric; depositing molybdenum into the negative feature to at least partially fill the negative feature with molybdenum over a tungsten layer; and depositing copper over the molybdenum to form a copper layer.

[0014] In various embodiments, the molybdenum is deposited by exposing the substrate to a first hydrogen gas and a molybdenum-containing precursor gas. In some embodiments, the exposing the substrate to the first hydrogen gas and the molybdenum-containing precursor gas are performed in a process chamber housing the substrate and a purge gas is periodically pulsed during the depositing of the molybdenum to purge excess byproducts from the process chamber.

[0015] In any of the above embodiments, the first hydrogen gas may be pulsed. In some embodiments the pulses are temporally sequential pulses. In some embodiments, the temporally sequential pulses of the first hydrogen gas and the purge gas are alternating pulses. In some 2 LAMRP922WO-11400-WOembodiments, depositing the molybdenum includes pulsing the molybdenum-containing precursor. For example, in some embodiments the pulses of the first hydrogen gas, molybdenum- containing precursor, and purge gas are temporally sequential pulses.

[0016] In any of the above embodiments, the method may also include exposing the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum into the negative feature.

[0017] In various embodiments, the molybdenum is deposited over a tungsten layer, and the molybdenum is deposited on a second copper layer, whereby the second copper layer is between the tungsten layer and the molybdenum. For example, in some embodiments, the molybdenum acts as a V0 layer, and the second copper layer acts as a M0 layer.

[0018] In various embodiments, the molybdenum is deposited directly on tungsten for use as a molybdenum M0 layer. For example, in some embodiments, the molybdenum is also deposited on the molybdenum M0 layer to form a molybdenum V0 layer. In some embodiments, a second copper layer is deposited over the molybdenum M0 layer to form a copper V0 layer.

[0019] In various of the above embodiments, a barrier layer may be formed between the first copper layer and the molybdenum. For example, in some embodiments, the barrier layer includes cobalt and tantalum oxide. In some embodiments, the cobalt is positioned between a first copper layer and a tantalum oxide. In various embodiments, the barrier layer is an electromigration layer. In various embodiments, the barrier layer is a diffusion barrier layer. In various embodiments, the barrier layer includes cobalt. In various embodiments, the barrier layer includes ruthenium. In various embodiments, the barrier layer includes cobalt ruthenium alloy. In various embodiments, the barrier layer includes tantalum nitride.

[0020] Another aspect involves a method for processing substrates, the method including: providing a substrate having a feature thereon to be used to form a line in a semiconductor device; and depositing molybdenum into the feature to at least partially fill the feature with molybdenum by exposing the substrate to a continuous flow of a first hydrogen gas source and a molybdenum- containing precursor, whereby during the continuous flow of the first hydrogen gas source, the substrate is exposed to one or more deposition cycles of the following temporally sequential pulses: (1) pulse of a second hydrogen gas source, (2) pulse of a first purge gas, (3) pulse of a molybdenum-containing precursor source for delivering the molybdenum-containing precursor, and (4) pulse of a second purge gas.

[0021] In various embodiments, the molybdenum-containing precursor including a structure of Formula (I), Formula (II) or Formula (III): 3 LAMRP922WO-11400-WOMoLn(I), Mo2Ln(II), or LnMo(L’)mMoLn(III), whereby each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3.

[0022] In various embodiments, each L is independently a monodentate ligand. In some embodiments, the monodentate ligand includes 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- C3alkyl)amino, -C(O)O-(C1-C3alkyl), -C(O)NH-(C1-C3alkyl), -CH=NOH, -P(C1-C3alkyl)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, -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.

[0023] In various embodiments, the molybdenum-containing precursor includes a molybdenum halide or a molybdenum oxyhalide. For example, in some embodiments, the molybdenum oxyhalide includes MoqOnYm, whereby Y is a halogen; n is 1 or 2; q is 1, 2 or 4; and m is 1, 2 or 11. In some embodiments, the molybdenum oxyhalide includes MoOF4, Mo4O11I, MoO2I, MoOBr4, MoO2Br2, MoO2Cl2, MoOCl4,Mo2Cl10or combinations thereof. In some embodiments, the molybdenum halide includes MoCl5or MoF6.

[0024] In various embodiments, the molybdenum is deposited over a copper layer.

[0025] In various embodiments, the molybdenum is deposited directly on the copper layer.

[0026] In various embodiments, the molybdenum is deposited directly on an electromigration layer.

[0027] In various embodiments, the molybdenum-containing precursor includes Mo(CO)6or C16H20Mo. In some embodiments, the molybdenum-containing precursor includes a low valent molybdenum-containing precursor. 4 LAMRP922WO-11400-WO

[0028] In various embodiments, the hydrogen gas includes hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and oxygen, hydrogen and nitrogen, ammonia, singly deuterated ammonia, doubly deuterated ammonia, triply deuterated ammonia, hydrazine, an alcohol, an aldehyde or combinations thereof.

[0029] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause a feature of the substrate to be at least partially filled with molybdenum as a V0 or M0 layer over a copper layer.

[0030] In various embodiments, the controller further includes instructions for causing deposition of copper over the molybdenum to form a copper M1 layer to completely fill the feature.

[0031] In various embodiments, the controller further includes instructions for causing the molybdenum to be deposited directly on copper for use as a molybdenum M0 layer.

[0032] In various embodiments, the controller further includes instructions for causing the molybdenum to be deposited directly on an electromigration layer

[0033] In various embodiments, the controller further includes instructions for causing deposition of molybdenum by causing exposure of the substrate to a first hydrogen gas and a molybdenum-containing precursor gas.

[0034] In various embodiments, the exposures are performed in a process chamber housing the substrate and the controller further includes instructions for causing periodic pulsing of a purge gas during the deposition of the molybdenum to purge excess byproducts from the process chamber.

[0035] In various embodiments, the controller further includes instructions for causing the first hydrogen gas to be pulsed in temporally sequential pulses. In some embodiments, the controller further includes instructions for causing alternating of the pulses of the first hydrogen gas and the purge gas. In some embodiments, the controller further includes instructions for causing pulsing of the molybdenum-containing precursor such that the substrate is exposed to the molybdenum- containing precursor when the substrate is not exposed to the purge gas. In some embodiments, the controller further includes pulsing of the first hydrogen gas such that the substrate is exposed 5 LAMRP922WO-11400-WOto the first hydrogen gas when the substrate is neither exposed to the purge gas nor the molybdenum-containing precursor.

[0036] In various embodiments, the controller further includes exposing of the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum into the feature.

[0037] Another aspect involves an apparatus for processing substrates, the apparatus including: one or more process chambers, each process chamber including a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause a feature of the substrate to be at least partially filled with molybdenum as a V0 or M0 layer, and cause deposition of copper over the molybdenum to form a copper M1 layer to completely fill the feature.

[0038] In various embodiments, the controller further includes instructions for causing deposition of molybdenum by causing exposure of the substrate to a first hydrogen gas and a molybdenum-containing precursor gas.

[0039] In various embodiments, the exposures are performed in a process chamber housing the substrate and the controller further includes instructions for causing periodic pulsing of a purge gas during the deposition of the molybdenum to purge excess byproducts from the process chamber.

[0040] In various embodiments, the controller further includes instructions for causing the first hydrogen gas to be pulsed in temporally sequential pulses. In some embodiments, the controller further includes instructions for causing alternating of the pulses of the first hydrogen gas and the purge gas. In some embodiments, the controller further includes instructions for causing pulsing of the molybdenum-containing precursor such that the substrate is exposed to the molybdenum- containing precursor when the substrate is not exposed to the purge gas. In some embodiments, the controller further includes pulsing of the first hydrogen gas such that the substrate is exposed to the first hydrogen gas when the substrate is neither exposed to the purge gas nor the molybdenum-containing precursor.

[0041] In various embodiments, the controller further includes exposing of the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum 6 LAMRP922WO-11400-WOinto the feature.

[0042] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figures 1A, 1B, and 1C are process flow diagrams depicting operations that may be performed in accordance with certain disclosed embodiments.

[0044] Figures 2A, 2B, and 2C are schematic illustrations of features that may be performed using certain disclosed embodiments.

[0045] Figures 3A, 4 and 5 are timing diagrams depicting operations that may be performed using certain disclosed embodiments.

[0046] Figures 3B-3C depict precursors that may be used in accordance with certain disclosed embodiments.

[0047] Figure 6 is a schematic presentation of an apparatus that is suitable for depositing metal- containing films in accordance with certain disclosed embodiments.

[0048] Figure 7 shows a schematic view of a multi-station processing system in accordance with certain disclosed embodiments.

[0049] Figure 8 is a schematic diagram of an example process tool for performing certain disclosed embodiments.

[0050] Figure 9 is a schematic diagram of an example process tool for performing certain disclosed embodiments.

[0051] Figure 10 is a graph showing deposition rate of molybdenum in accordance with certain disclosed embodiments. DETAILED DESCRIPTION

[0052] 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.

[0053] Semiconductor fabrication processes may involve formation of metal-containing features having particular a particular structure. While metal features are often filled with copper metal, as devices shrink, alternative materials may be used, such as molybdenum. In some cases, molybdenum may be a suitable metal for filling trenches in back-end-of-line metallization for logic. In such structures, a dielectric substrate may be patterned to thereby form multiple layers 7 LAMRP922WO-11400-WOwithin it before etching the dielectric to form a negative feature to then be subsequently filled with metal. Each layer may be used to serve a different purpose. A silicon oxide dielectric layer may be present with a first etch stop layer between it and a first low-k dielectric layer. The first low-k dielectric layer may be adjacent to a second etch stop layer, which may be between the first low- k dielectric layer and a second low-k dielectric layer. The second low-k dielectric layer may be adjacent to a third etch stop layer, which may be between the second low-k dielectric layer and second low-k dielectric layer. From bottom to top (or top to bottom), the layer formation may be as follows: silicon oxide layer, first etch stop layer, first low-k dielectric layer, second etch stop layer, second low-k dielectric layer, third etch stop layer, and third low-k dielectric layer.

[0054] The stack of dielectric layers may be etched to form a negative feature or a via in one or more of the dielectric layers. A negative feature may be defined as a removed portion of a material such that there is a hole or negative space where the portion of the material was removed. This may also be referred to as an “unfilled feature” or “recessed feature.” Non-limiting examples of negative features include trenches, vias, and contact holes. The etch stop layers may have been used to form particular structures for each feature. In some cases, the etch stop layers assist in forming self-align features. Each segment of the feature etched into each layer may have different properties, such as different pitch, different sidewall sloping angles, re-entrant features, and other features. In various embodiments, the feature etched in the silicon oxide layer is first filled with tungsten metal.

[0055] Subsequently, in some logic in BEOL applications, the next layer (the layer that included a first low-k dielectric material on sidewalls of the feature) is referred to as the M0 layer. The next layer (the layer that included the second low-k dielectric material on sidewalls of the feature) is referred to as the V0 layer. The third layer (the layer that included the third low-k dielectric material on sidewalls of the feature) is referred to as the M1 layer. In some existing logic BEOL applications, the feature is filled with copper for the M0, V0, and M1 layers and copper is formed over the tungsten layer. However, as devices shrink and variables change, other materials, such as molybdenum may be used.

[0056] Provided herein are methods and apparatuses for forming molybdenum over a tungsten material in at least one or more of the M0 or V0 layers of a feature in a dielectric material. Copper is subsequently deposited over at least one of the molybdenum material. For example, in some embodiments, the composition of the materials in the feature in the M0, V0, M1 layers may be one or more of the following orders, respectively: (1) molybdenum, copper, copper; (2) copper, molybdenum, copper, and (3) molybdenum, molybdenum, copper. In various embodiments, liner 8 LAMRP922WO-11400-WOor barrier material may be deposited between the molybdenum and the copper. In various embodiments, the liner or barrier material is deposited before depositing copper such that the liner or barrier is also deposited on the sidewalls of the feature.

[0057] Molybdenum may be deposited using a pulsed chemical vapor deposition process. Examples are provided in Figures 1A-1C.

[0058] In Figure 1A, in an operation 102, a substrate having a feature is provided to a process chamber. The substrate may include a partially fabricated semiconductor structure on it. The substrate may be a silicon wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semi- conducting material deposited thereon. In various embodiments, the substrate is patterned. In various embodiments, multiple features are present on the substrate. The feature may be previously etched in a dielectric material. The feature may be previously etched down to a metal layer such that the bottom of the feature includes exposed metal. According to various embodiments, the feature profile may narrow gradually and / or include an overhang at the feature opening. A re-entrant profile is one that narrows from the bottom, closed end, or interior of the feature to the feature opening. A re-entrant profile may be generated by asymmetric etching kinetics during patterning and / or the overhang due to non-conformal film step coverage in the previous film deposition, such as deposition of a diffusion barrier. In various examples, the feature may have a width smaller in the opening at the top of the feature than the width of the bottom of the feature.

[0059] The metal may be tungsten in some embodiments. While tungsten is shown and described in these examples herein, it will be understood that in some embodiments, another material may be used instead of tungsten, such as molybdenum, or titanium nitride, or cobalt. The dielectric material may be a silicon oxide material or a low-k material or both. The pitch between features may be about 5 nm to about 14 nm, or less than about 10 nm. In some embodiments, the bottom of a feature may be a metal-containing material. In some embodiments, the substrate was previously etched in multiple layers such that the sidewalls of the feature include multiple materials as well as etch stop layer materials that were previously used to form the features. In some embodiments, the feature has a metal-containing bottom surface, and the sidewalls from bottom to top include low-k dielectric, etch stop layer, low-k dielectric, etch stop layer, and low-k dielectric.

[0060] In an operation 104, the feature may be partially filled with molybdenum to form the M0 layer, which is the layer adjacent to the tungsten layer. The feature may be filled with molybdenum 9 LAMRP922WO-11400-WOusing any suitable molybdenum deposition technique. An example pulsed chemical vapor deposition technique is described elsewhere herein.

[0061] In an operation 106, the feature is partially filled with copper over the molybdenum to form a copper V0 layer. In some embodiments, prior to filling with copper, one or more barrier and / or liner layers are deposited. for example, a tantalum nitride layer may be first deposited such that it contacts the sidewalls of the feature, and a cobalt layer may be subsequently deposited over the tantalum nitride layer, followed by filling of the feature with copper. Copper may be deposited using any suitable technique.

[0062] In an operation 108, the rest of the feature is filled with copper to form a copper V1 layer. In some embodiments, prior to filling the rest of the feature with copper, one or more barrier and / or liner layers are deposited. for example, a tantalum oxide layer may be first deposited such that it contacts the sidewalls of the feature, and a cobalt layer may be subsequently deposited over the tantalum oxide layer, followed by filling of the feature with copper. Copper may be deposited using any suitable technique.

[0063] Figure 2A shows an example schematic illustration of a side view of a feature 201 (outlined in bold line) that may be formed in accordance with certain disclosed embodiments, such as the process flow described with respect to Figure 1A. The substrate includes a feature 201 having, on its sidewalls, dielectric material, including silicon oxide and low-k dielectric, as well as etch stop layers (ESL) that were used to form each layer. The bottom layer of the feature includes tungsten. While tungsten is shown and described in these examples herein, it will be understood that in some embodiments, another material may be used instead of tungsten, such as molybdenum, or titanium nitride, or cobalt. The M0 layer includes molybdenum. The V0 layer includes copper lined with a diffusion barrier (such as tantalum nitride) and an electromigration barrier layer (such as cobalt, cobalt-ruthenium alloy, ruthenium, or cobalt-doped ruthenium). The M1 layer includes copper lined with a diffusion barrier (such as tantalum nitride) and an electromigration barrier layer (such as cobalt, cobalt-ruthenium alloy, ruthenium, or cobalt-doped ruthenium). .

[0064] Figure 1B shows another example process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. In operation 102, a substrate having a via or feature is provided to a process chamber. This may be the same as operation 102 described above with respect to Figure 1A.

[0065] In an operation 114, the via may be partially filled with copper to form the M0 layer, which is the layer adjacent to the tungsten layer. In some embodiments, prior to filling with 10 LAMRP922WO-11400-WOcopper, one or more barrier and / or liner layers are deposited. For example, a diffusion barrier such as a tantalum nitride layer may be first deposited such that it contacts the sidewalls of the feature and the tungsten surface at the bottom of the feature, and a cobalt or electromigration barrier layer may be subsequently deposited over the tantalum nitride layer, followed by filling of the feature with copper. Copper may be deposited using any suitable technique. The electromigration barrier layer may be cobalt, ruthenium, cobalt-ruthenium alloy, or cobalt-doped ruthenium. In some embodiments, in a cobalt-ruthenium alloy or cobalt-doped ruthenium, the cobalt to ruthenium atomic ratio may be about 0.5:1 to about 2:1, or about 0.5:1, or about 1:1, or about 2:1. In various embodiments, electromigration barrier layer 216 is optional. In various embodiments, tantalum nitride diffusion barrier 215 is optional.

[0066] In an operation 116, the via is partially filled with molybdenum over the copper to form a molybdenum V0 layer. The via may be filled with molybdenum using any suitable molybdenum deposition technique. An example pulsed chemical vapor deposition technique is described elsewhere herein.

[0067] In operation 108, the rest of the via is filled with copper to form a copper M1 layer. This operation may be the same as operation 108 described above with respect to Figure 1A. Copper may be deposited using any suitable technique.

[0068] Figure 2B shows an example schematic illustration of a side view of a feature 203 (outlined in bold line) that may be formed in accordance with certain disclosed embodiments, such as the process flow described with respect to Figure 1B. The substrate includes a feature 203 having, on its sidewalls, dielectric material, including silicon oxide and low-k dielectric, as well as etch stop layers that were used to form each layer. The bottom layer of the feature includes tungsten. While tungsten is shown and described in these examples herein, it will be understood that in some embodiments, another material may be used instead of tungsten, such as molybdenum, or titanium nitride, or cobalt. The M0 layer includes copper lined with tantalum nitride and cobalt. The V0 layer includes molybdenum. The M1 layer includes copper lined with tantalum nitride and cobalt. The M0 layer could be lined with ruthenium or a cobalt-ruthenium alloy or a cobalt- doped ruthenium layer instead of cobalt. The M1 layer could be lined with ruthenium or a cobalt- ruthenium alloy or a cobalt-doped ruthenium layer instead of cobalt. In some embodiments, in a cobalt-ruthenium alloy or cobalt-doped ruthenium, the cobalt to ruthenium atomic ratio may be about 0.5:1 to about 2:1, or about 0.5:1, or about 1:1, or about 2:1. In various embodiments, electromigration barrier layer 216 is optional. In various embodiments, tantalum nitride diffusion barrier 215 is optional. 11 LAMRP922WO-11400-WO

[0069] Figure 1C shows another example process flow diagram depicting operations that may be performed in accordance with certain disclosed embodiments. In operation 102, a substrate having a feature is provided to a process chamber. This may be the same as operation 102 described above with respect to Figure 1A and 1B.

[0070] In operation 104, the feature may be partially filled with molybdenum to form the M0 layer, which is the layer adjacent to the tungsten layer. This may be the same as operation 104 described above with respect to Figure 1A. The feature may be filled with molybdenum using any suitable molybdenum deposition technique. An example pulsed chemical vapor deposition technique is described elsewhere herein.

[0071] In operation 116, the via is partially filled with molybdenum over the molybdenum to form a molybdenum V0 layer. The via may be filled with molybdenum using any suitable molybdenum deposition technique. An example pulsed chemical vapor deposition technique is described elsewhere herein.

[0072] In operation 108, the rest of the via is filled with copper to form a copper M1 layer. This operation may be the same as operation 108 described above with respect to Figure 1A. In some embodiments, prior to filling with copper, one or more barrier and / or liner and / or diffusion layers (such as tantalum nitride diffusion layer 215 and electromigration barrier layer 216 in Figure 2C) are deposited. For example, a tantalum nitride diffusion layer 215 may be first deposited such that it contacts the sidewalls of the feature and the molybdenum surface of the V0 layer, and a cobalt layer may be subsequently deposited over the tantalum nitride diffusion layer 215, followed by filling of the feature with copper. Copper may be deposited using any suitable technique. In some embodiments, one or more barrier and / or liner layers may be about 1 nm to about 2 nm in thickness. In some embodiments, the electromigration barrier layer 216 may be cobalt. In some embodiments, the electromigration barrier layer 216 has a different composition than cobalt. For example, it may be another material such as ruthenium, or may be an alloy of one or more metals, or may be a cobalt-ruthenium alloy. It may also be a doped material, such as cobalt-doped ruthenium. In some embodiments, in a cobalt-ruthenium alloy or cobalt-doped ruthenium, the cobalt to ruthenium atomic ratio may be about 0.5:1 to about 2:1, or about 0.5:1, or about 1:1, or about 2:1. In various embodiments, electromigration barrier layer 216 is optional. In various embodiments, tantalum nitride diffusion barrier 215 is optional.

[0073] Figure 2C shows an example schematic illustration of a side view of a feature 205 (outlined in bold line) that may be formed in accordance with certain disclosed embodiments, such as the process flow described with respect to Figure 1C. The substrate includes a feature having, 12 LAMRP922WO-11400-WOon its sidewalls, dielectric material, including silicon oxide and low-k dielectric, as well as etch stop layers that were used to form each layer. The bottom layer of the feature includes tungsten. The M0 layer includes molybdenum. The V0 layer includes molybdenum. The M1 layer includes copper lined with tantalum nitride barrier layer 215 and cobalt.

[0074] Pulsed chemical vapor deposition may be used for depositing molybdenum in the V0 or M0 or both layers in accordance with certain disclosed embodiments. Examples are provided below with respect to Figures 3-5. Each exposure in an “on” or “high” condition may be referred to as a “pulse.” For example, pulsing a molybdenum precursor may be depicted as the bolded line for the molybdenum precursor gas being in a lower then a higher horizontal line in temporally alternating pulses. It will be understood that pulsing may involve repetitions of periods, each of which may last a duration T (time). The duration T includes the duration for pulse ON time (the duration for which the gas is in an ON state) and the duration for OFF time (the duration from which the gas is in an OFF state) during a given period. In Figures 3-5, a pulse may be in the “ON’ state when the horizontal line is positioned higher on the y-axis of each row, and a pulse may be in the “OFF” state when the horizontal line is on the x-axis of each row. The pulse frequency will be understood as 1 / T. For example, for a pulsing period T = 100 µs, frequency is 1 / T = 1 / 100µs, or 10 kHz. The duty cycle or duty ratio is the fraction or percentage in a period T during which the gas is in the ON state such that duty cycle or duty ratio is pulse ON time divided by T. For example, for a pulsing period T = 100 µs, if a pulse ON time is 70 µs (such that the duration for which the gas is in an ON state in a period is 70 µs) and a pulse OFF time is 30 µs (such that the duration for which the gas is in an OFF state in a period is 30 µs), the duty cycle is 70%.

[0075] Figure 3 shows a timing schematic illustration that shows various operations that may be performed in accordance with certain disclosed embodiments. Process 301 includes two deposition cycles 310A and 310B but it will be understood that only one cycle or more than two cycles may be performed in accordance with certain disclosed embodiments. In this example, deposition cycles 310A and 310B include the same operations repeated in each cycle but it will be understood that in some embodiments, various operations, or a variety of operations such as those later described with respect to Figures 4 and 5 may be combined with cycles described here with respect to Figure 3. In the examples in Figures 3-5, during certain phases, gas flow may be pulsed in the “ON” state. In some instances, a phase may correspond to a pulse. The x-axis in each row represents time. Where a gas flow is in the “ON” state, it may be referred to as a “pulse.” Pulses may be temporally separated in that over time, the gas flow will sometimes be in the “ON” state and sometimes in the “OFF” state. When a gas flow is being pulsed in temporally separated pulses, 13 LAMRP922WO-11400-WOit may also be referred to as being “periodically pulsed” in that in various periods, the gas flow is pulsed. In some cases, a gas flow is pulsed sequentially such that the gas flow is first in the “ON” state then in the “OFF” state then in the “ON” state then in the “OFF” state in that order, which may be repeated. Gas flows may be pulsed in temporally sequential pulses where the sequential pulses refer to two “ON” states being performed one after another.

[0076] Figure 3 shows various process conditions during each phase – four process conditions are depicted here but it will be understood that other gases, plasma, temperature, pressure, or other conditions may also be present and may vary or be the same across different phases and across different cycles. The process conditions shown in this example include a first hydrogen-containing gas source (which may be a first source of hydrogen gas (H2), a second hydrogen-containing gas source (which may be a second source of hydrogen gas (H2), argon (which may act as a purge gas, carrier gas, inert gas, or any combination thereof), and molybdenum-containing precursor gas.

[0077] In this example, deposition cycle 310A includes four phases – first phase 320A, first purge phase 340A, second phase 350A, and second purge phase 380A. During first phase 320A, the first hydrogen source gas is turned on, the second hydrogen gas source is turned on, the argon source is turned off, and the molybdenum precursor gas source is turned off. During this operation only hydrogen-containing gas sources may be flowed.

[0078] During first purge phase 340A, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may be turned off or turned down (e.g., lowered flow rate), argon gas source may be turned on, and molybdenum precursor gas source is still turned off.

[0079] During second phase 350A, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may continue to be off (or on the lower flow rate), argon gas source may be turned off (or have reduced flow rate), and molybdenum precursor gas source is turned on.

[0080] During second purge phase 380A, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may be still turned off or turned down (e.g., lowered flow rate), argon gas source may be turned on, and molybdenum precursor gas source is turned off.

[0081] While this process flow shows second hydrogen source turned on followed by molybdenum precursor gas turned on, it will be understood that the alternate may be used instead (e.g., molybdenum precursor gas on, then purge, then second hydrogen source on, then purge).

[0082] Deposition cycle 310A is then repeated in deposition cycle 310B. Deposition cycle 310B 14 LAMRP922WO-11400-WOincludes four phases – first phase 320B, first purge phase 340B, second phase 350B, and second purge phase 380B. First phase 320B may be the same as or may be different from first phase 320A. In this example, first phase 320B is the same as first phase 320A. During first phase 320B, the first hydrogen source gas is still on, the second hydrogen gas source is turned on, the argon source is turned off, and the molybdenum precursor gas source is turned off. During this operation only hydrogen-containing gas sources may be flowed.

[0083] During first purge phase 340B, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may be turned off or turned down (e.g., lowered flow rate), argon gas source may be turned on, and molybdenum precursor gas source is still turned off.

[0084] During second phase 350B, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may continue to be off (or on the lower flow rate), argon gas source may be turned off (or have reduced flow rate), and molybdenum precursor gas source is turned on.

[0085] During second purge phase 380B, the first hydrogen source gas may continue to be on (and may continue to be flowed at the same flow rate), the second hydrogen gas source may be still turned off or turned down (e.g., lowered flow rate), argon gas source may be turned on, and molybdenum precursor gas source is turned off.

[0086] Figure 4 shows an alternative deposition cycle scheme that may be used in some embodiments. Figure 4 shows a timing schematic illustration that shows various operations that may be performed in accordance with certain disclosed embodiments. Process 400 includes two deposition cycles 410A and 410B but it will be understood that only one cycle or more than two cycles may be performed in accordance with certain disclosed embodiments. In this example, deposition cycles 410A and 410B include the same operations repeated in each cycle but it will be understood that in some embodiments, various operations, or a variety of operations such as those described with respect to Figures 3 and 5 may be combined with cycles described here with respect to Figure 4.

[0087] Figure 4 shows various process conditions during each phase – three process conditions are depicted here but it will be understood that other gases, plasma, temperature, pressure, or other conditions may also be present and may vary or be the same across different phases and across different cycles. The process conditions shown in this example include a molybdenum-containing precursor gas, a hydrogen-containing gas source (which may be a source of hydrogen gas (H2), and argon (which may act as a purge gas, carrier gas, inert gas, or any combination thereof). In 15 LAMRP922WO-11400-WOthis example, the molybdenum precursor gas source may be continuously flowed.

[0088] In this example, deposition cycle 410A includes four phases – first phase 420A, first purge phase 440A, second phase 450A, and second purge phase 480A. During first phase 420A, the molybdenum precursor gas is turned on, the hydrogen gas source is turned on, and the argon source is turned off.

[0089] During first purge phase 440A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned off (or have reduced flow rate), and the argon gas is turned on.

[0090] During second phase 450A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned on, and the argon gas is turned off (or have reduced flow rate).

[0091] During second purge phase 480A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned off (or have reduced flow rate), and the argon gas is turned on.

[0092] While this process flow shows the hydrogen source turned on followed by argon gas turned on, it will be understood that the alternate may be used instead (e.g., purge, then hydrogen source on, then purge, then hydrogen source on).

[0093] Deposition cycle 410A is then repeated in deposition cycle 410B. Deposition cycle 410B includes four phases – first phase 420B, first purge phase 440B, second phase 450B, and second purge phase 480B. First phase 420B may be the same as or may be different from first phase 420A. In this example, first phase 420B is the same as first phase 420A. During first phase 420B, the molybdenum precursor gas is turned on, the hydrogen gas source is turned on, and the argon source is turned off.

[0094] During first purge phase 440B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned off (or have reduced flow rate), and the argon gas is turned on.

[0095] During second phase 450B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned on, and the argon gas is turned off (or have reduced flow rate).

[0096] During second purge phase 480B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas may be turned off (or have reduced flow rate), and the argon gas is turned on.

[0097] Figure 5 shows yet another alternative deposition cycle scheme that may be used in some 16 LAMRP922WO-11400-WOembodiments. Figure 5 shows a timing schematic illustration that shows various operations that may be performed in accordance with certain disclosed embodiments. Process 500 includes two deposition cycles 510A and 510B but it will be understood that only one cycle or more than two cycles may be performed in accordance with certain disclosed embodiments. In this example, deposition cycles 510A and 510B include the same operations repeated in each cycle but it will be understood that in some embodiments, various operations, or a variety of operations such as those described with respect to Figures 3 and 4 may be combined with cycles described here with respect to Figure 5.

[0098] Figure 4 shows various process conditions during each phase – three process conditions are depicted here but it will be understood that other gases, plasma, temperature, pressure, or other conditions may also be present and may vary or be the same across different phases and across different cycles. The process conditions shown in this example include a hydrogen-containing gas source (which may be a source of hydrogen gas (H2), a molybdenum-containing precursor gas, and argon (which may act as a purge gas, carrier gas, inert gas, or any combination thereof). In this example, the molybdenum precursor gas source may be continuously flowed. In this example, the hydrogen-containing gas source may be continuously flowed.

[0099] In this example, deposition cycle 510A includes four phases – first phase 520A, first purge phase 540A, second phase 550A, and second purge phase 580A. During first phase 520A, the molybdenum precursor gas is turned on, the hydrogen gas source is turned on, and the argon source is turned off.

[0100] During first purge phase 540A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned on.

[0101] During second phase 550A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned off (or have reduced flow rate).

[0102] During second purge phase 540A, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned on.

[0103] Deposition cycle 510A is then repeated in deposition cycle 510B. Deposition cycle 510B includes four phases – first phase 520B, first purge phase 540B, second phase 550B, and second purge phase 580B. First phase 520B may be the same as or may be different from first phase 520A. In this example, first phase 520B is the same as first phase 520A. During first phase 520B, 17 LAMRP922WO-11400-WOthe molybdenum precursor gas is turned on, the hydrogen gas source is turned on, and the argon source is turned off.

[0104] During first purge phase 540B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned on.

[0105] During second phase 550B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned off (or have reduced flow rate).

[0106] During second purge phase 540B, the molybdenum precursor gas source is still on (and may continue to be flowed at the same flow rate), the hydrogen source gas is still on (and may continue to be flowed at the same flow rate), and the argon gas is turned on.

[0107] The molybdenum-containing precursor used to deposit the molybdenum may be any suitable precursor, such as those listed below in the Precursors section. Examples also include m molybdenum halides, and / or organometallic molybdenum-containing precursors. One or more precursors may be used.

[0108] The first and / or second hydrogen-containing source gas in various embodiments may be hydrogen gas. Hydrogen gas may continue to flow so as to prevent damage to the substrate when the substrate is exposed to the molybdenum-containing precursor.

[0109] Although argon is described with respect to Figures 3-5, it will be understood that other inert gases may be used instead of argon, including and not limited to helium.

[0110] In any one of the above examples with respect to Figures 3-5, the molybdenum precursor gas “on” conditions may involve flowing a molybdenum-containing precursor gas at a flow rate of about 10 sccm to about 5000 sccm, or about 10 sccm to about 1000 sccm. In any one of the above examples with respect to Figures 3-5, the first hydrogen gas “on” conditions may involve flowing a first hydrogen gas at a flow rate of about 100 sccm to about 20000 sccm. In any one of the above examples with respect to Figures 3-5, the second hydrogen gas “on” conditions may involve flowing a second hydrogen gas at a flow rate of about 100 sccm to about 20000 sccm. In any one of the above examples with respect to Figures 3-5, the argon gas “on” conditions may involve flowing an argon gas at a flow rate of about 100 sccm to about 10000 sccm. The “off” conditions may involve turning flow off (e.g., 0 sccm).

[0111] During any one or more deposition cycles for forming molybdenum, the temperature that a pedestal holding the substrate upon which molybdenum is deposited may be set to about 300°C to about 450°C, or about 300°C to about 400°C, or less than about 400°C, or less than about 350°C. 18 LAMRP922WO-11400-WOIn some embodiments, the temperature that the pedestal is set at is referred to as a pedestal temperature or a substrate temperature. During any one or more deposition cycles for forming molybdenum, the pressure of a chamber housing the substrate upon which molybdenum is deposited may be about 10 Torr to about 150 Torr.

[0112] In various embodiments, deposition of molybdenum is performed in plasma-free conditions. In some embodiments, deposition of molybdenum is performed without a plasma. Plasma may not be used during any of the phases in any of Figures 3-5.

[0113] Any one or more of deposition cycles 310A, 310B, 410A, 410B, 510A, or 510B may have a cycle duration, from beginning of the deposition cycle until the deposition cycle is repeated again, of about 0.1 seconds to about 60 seconds, or about 0.1 second to about 2 seconds, or about 0.3 second to 60 seconds, or 0.4 second to 60 seconds, 0.5 second to about 1.5 second, or about 1 second. In some embodiments, about 20 to about 200 deposition cycles or up to 10,000 deposition cycles may be performed. The number of deposition cycles performed may vary depending on precursor concentration and the process temperature, as well as pattern density and feature dimension.

[0114] Purging operations, such as those described above with respect to first purge phase 340A, second purge phase 380A, first purge phase 340B, and second purge phase 380 of Figure 3; first purge phase 440A, second purge phase 480A, first purge phase 440B, and second purge phase 480 of Figure 4; and / or first purge phase 540A, second purge phase 580A, first purge phase 540B, and second purge phase 580 of Figure 5, may each be performed for a particular duration, such as about 0.1 seconds to about 60 seconds. Each of the purge operations may be performed for the same duration or different duration. A single deposition cycle may include purge phases of the same duration. A single deposition cycle may include purge phases of different duration. In some embodiments, purging is optional. For example, in some embodiments, throughput may be increased by reducing or eliminating purging, which may not be used depending on the composition of the surface of the substrate. For example, if eliminating purging but performing the overall deposition using the molybdenum-containing precursor still does not damage the substrate, purging can be eliminated to increase throughput.

[0115] In various embodiments, an air break may be incorporated during the process. For example, in some embodiments, prior to depositing molybdenum, a degas operation and hydrogen- containing plasma preclean may be performed. Degas may be used to form an inner ambient having a particular thermal condition to allow moisture to be removed from the substrate and to thereby vaporize gas in the chamber to prepare it for deposition. During degas, the pedestal 19 LAMRP922WO-11400-WOtemperature may be set to about 300°C, and the process chamber pressure may be set to about 7 Torr. During degas, a mixture of argon and helium may be introduced for a duration of about 30 seconds to about 300 seconds. A hydrogen plasma preclean may be performed prior to molybdenum deposition to reduce any formation of copper oxide that may have formed on an exposed copper surface, such as in embodiments where molybdenum is deposited on a copper surface (such as the example described above with respect to Figure 2B).

[0116] Hydrogen plasma preclean may be performed at a temperature of about 150°C to about 300°C. Hydrogen plasma preclean may be performed at a chamber pressure of about 0.01 Torr to about 10 Torr. Hydrogen plasma preclean may be performed using a flow rate of hydrogen gas of about 25 sccm to about 5000 sccm. Hydrogen plasma preclean may be performed for a duration of about 10 seconds to about 120 seconds. Hydrogen plasma preclean may be performed before every deposition cycle or before any deposition cycles or before certain deposition cycles. Plasma conditions during preclean may be as follows: single or dual frequency plasma, plasma power of about 100W to about 3000W, and plasma frequency of about 13 MHz to about 27 MHz. In some embodiments, plasma preclean may be pulsed, such as with a duty cycle of about 10% to about 50%.

[0117] In various embodiments, soaking with a molybdenum-containing precursor gas may be performed prior to depositing molybdenum so as to decompose molybdenum thermally on a surface of the feature. Such embodiments may help increase nucleation and reduce nucleation delay of molybdenum when it is deposited subsequently using pulsed chemical vapor deposition techniques such as described herein. Soaking may be performed at a temperature of about 100°C to about 350°C. Soaking may be performed at a chamber pressure of about 0.5 Torr to about 150 Torr. Soaking may be performed using a flow rate of about 10 sccm to about 5000 sccm. Soaking may be performed for a duration of about 1 second to about 300 seconds. Soaking may be performed before every deposition cycle or before any deposition cycles or before certain deposition cycles.

[0118] Advantages of certain disclosed embodiments include deposition of molybdenum on a copper-containing feature without damaging copper, deposition of molybdenum on tungsten without damaging tungsten, reducing and / or mitigating copper migration or damage, expansion of thermal budget, mitigating copper reaction chemistry in downstream processes, and reduction and / or elimination of barrier / liner layers as molybdenum may be directly deposited into a via or trench or feature without a barrier or liner layer, thereby depositing more molybdenum into a via of the same size (as compared to copper). For example, copper chloride formation may be 20 LAMRP922WO-11400-WOmitigated by using certain disclosed embodiments. In various embodiments, copper is still used for the M1 layer. APPARATUS

[0119] The deposition methods described herein can be carried out in a variety of apparatuses. A suitable apparatus includes a processing chamber having one or more inlets for introduction of reactants, a substrate holder in the process chamber configured to hold the substrate in place during deposition, and, optionally, a plasma generating mechanism configured for generating a plasma in a process gas. The apparatus may include a controller having program instructions for causing any of the method steps described herein. The deposition methods described herein may be carried out in corresponding atomic layer deposition (ALD) and chemical vapor deposition (CVD) apparatuses.

[0120] For example, in some embodiments the apparatus includes a controller having program instructions that include instructions for: causing an introduction of a molybdenum-containing precursor to the processing chamber, wherein the precursor is any of the precursors described herein; and causing a reaction between the molybdenum-containing precursor and hydrogen- containing gas to form a layer of molybdenum-containing material on a substrate. The controller may include program instructions for causing any of the methods described herein.

[0121] An example of a deposition apparatus suitable for depositing molybdenum-containing films using provided methods is shown in Figure 6 which schematically illustrates an embodiment of a process station 600 that may be used to deposit material using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which may be plasma enhanced. In various embodiments, process station 600 is used for pulsed chemical vapor deposition (pCVD). For simplicity, the process station 600 is depicted as a standalone process station having a process chamber body 602 for maintaining a low-pressure environment. However, it will be appreciated that a plurality of process stations 600 may be included in a common process tool environment. Further, it will be appreciated that, in some embodiments, one or more hardware parameters of process station 600, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers.

[0122] Process station 600 fluidly communicates with reactant delivery system 601 for delivering process gases to a distribution showerhead 606. Reactant delivery system 601 includes a mixing vessel 604 for blending and / or conditioning process gases for delivery to showerhead 606. One or more mixing vessel inlet valves 620 may control introduction of process gases to mixing vessel 604. Similarly, a showerhead inlet valve 605 may control introduction of process 21 LAMRP922WO-11400-WOgasses to the showerhead 606.

[0123] Some molybdenum-containing precursors may be stored in solid or liquid form prior to vaporization and subsequent delivery to the process station. For example, the embodiment of Figure 6 includes a vaporization point 603 for vaporizing solid reactant to be supplied to mixing vessel 604. In some embodiments, vaporization point 603 may be a heated vaporizer. In some embodiments a flow of an inert gas is passed over the heated solid molybdenum precursor, or bubbled through the heated liquid molybdenum precursor, under sub-atmospheric pressure, and carries the precursor vapor to the process chamber. The precursor vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve sweeping and / or evacuating the delivery piping to remove residual reactant. However, sweeping the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of vaporization point 603 may be heat traced. In some examples, mixing vessel 604 may also be heat traced. In one non-limiting example, piping downstream of vaporization point 603 has an increasing temperature profile extending from approximately 100°C to approximately 200°C at mixing vessel 604.

[0124] Showerhead 606 distributes process gases toward substrate 612. In the embodiment shown in Figure 6, substrate 612 is located beneath showerhead 606, and is shown resting on a pedestal 608. It will be appreciated that showerhead 606 may have any suitable shape and may have any suitable number and arrangement of ports for distributing processes gases to substrate 612. While not explicitly shown, in some embodiments the showerhead 606 is a dual plenum showerhead that includes at least two types of conduits, where the first type of conduit is dedicated to delivery of molybdenum-containing precursor vapor, and the second type of conduit is dedicated to delivery of the second (or other) reactant. In these embodiments the molybdenum-containing precursor and the reactant are not allowed to mix in the conduits prior to entry to the process chamber, and do not share the conduits if delivered to the chamber consecutively.

[0125] In some embodiments, a microvolume 607 is located beneath showerhead 606. Performing an ALD and / or CVD process in a microvolume rather than in the entire volume of a process station may reduce reactant exposure and sweep times, may reduce times for altering process conditions (e.g., pressure, temperature, etc.), may limit an exposure of process station robotics to process gases, etc. Example microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. This microvolume also impacts productivity throughput. While 22 LAMRP922WO-11400-WOdeposition rate per cycle drops, the cycle time also simultaneously reduces. In certain cases, the effect of the latter is dramatic enough to improve overall throughput of the module for a given target thickness of film.

[0126] In some embodiments, pedestal 608 may be raised or lowered to expose substrate 612 to microvolume 607 and / or to vary a volume of microvolume 607. For example, in a substrate transfer phase, pedestal 608 may be lowered to allow substrate 612 to be loaded onto pedestal 608. During a deposition process phase, pedestal 608 may be raised to position substrate 612 within microvolume 607. In some embodiments, microvolume 607 may completely enclose substrate 612 as well as a portion of pedestal 608 to create a region of high flow impedance during a deposition process.

[0127] Optionally, pedestal 608 may be lowered and / or raised during portions the deposition process to modulate process pressure, reactant concentration, etc., within microvolume 607. In one scenario where process chamber body 602 remains at a base pressure during the deposition process, lowering pedestal 608 may allow microvolume 607 to be evacuated. Example ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller.

[0128] While the example microvolume variations described herein refer to a height-adjustable pedestal, it will be appreciated that, in some embodiments, a position of showerhead 606 may be adjusted relative to pedestal 608 to vary a volume of microvolume 607. 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.

[0129] Returning to the embodiment shown in Figure 6, showerhead 606 and pedestal 608 electrically communicate with RF power supply 614 and matching network 616 for powering a plasma. In other embodiments apparatuses without a plasma generator are used for depositing molybdenum-containing films using provided methods. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, a radio frequency (RF) source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 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 23 LAMRP922WO-11400-WOsupply 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 50 kHz and 700 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasmas.

[0130] 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.

[0131] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. In one example, the instructions for setting plasma conditions for a plasma process phase may be included in a corresponding plasma activation recipe phase of a deposition process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a deposition process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe phase preceding a plasma process phase such as for plasma preclean. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for enabling the plasma generator and time delay instructions for the second recipe phase. A third recipe phase may include instructions for disabling the plasma generator and time delay instructions for the third recipe phase. It will be appreciated that these recipe phases may be further subdivided and / or iterated in any suitable way within the scope of the present disclosure. 24 LAMRP922WO-11400-WO

[0132] In some embodiments, pedestal 608 may be temperature controlled via heater 610. Further, in some embodiments, pressure control for deposition 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 process station 600.

[0133] Figure 7 shows a schematic view of an embodiment of a multi-station processing tool 700 with an inbound load lock 702 and an outbound load lock 704, either or both of which may include a remote plasma source. Such tool may be used for processing the substrates using the methods provided herein. A robot 706, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 708 into inbound load lock 702 via an atmospheric port 710. A wafer is placed by the robot 706 on a pedestal 712 in the inbound load lock 702, the atmospheric port 710 is closed, and the load lock is pumped down. Where the inbound load lock 702 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 714. Further, the wafer also may be heated in the inbound load lock 702 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 716 to processing chamber 714 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in Figure 7 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.

[0134] The depicted processing chamber 714 includes four process stations, numbered from 1 to 4 in the embodiment shown in Figure 7. Each station has a heated pedestal (shown at 718 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. While the depicted processing chamber 714 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.

[0135] Figure 7 also depicts an embodiment of a wafer handling system 790 for transferring wafers within processing chamber 714. In some embodiments, wafer handling system 790 may transfer wafers between various process stations and / or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. Figure 7 also depicts an embodiment 25 LAMRP922WO-11400-WOof a system controller 750 employed to control process conditions and hardware states of process tool 700. System controller 750 may include one or more memory devices 756, one or more mass storage devices 754, and one or more processors 752. Processor 752 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0136] In some embodiments, system controller 750 controls all of the activities of process tool 700. System controller 750 executes system control software 758 stored in mass storage device 754, loaded into memory device 756, and executed on processor 752. System control software 758 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by process tool 700. System control software 758 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes in accordance with the disclosed methods. System control software 758 may be coded in any suitable computer readable programming language.

[0137] In some embodiments, system control software 758 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of an ALD process may include one or more instructions for execution by system controller 750. The instructions for setting process conditions for an ALD process phase may be included in a corresponding ALD recipe phase. In some embodiments, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase.

[0138] Other computer software and / or programs stored on mass storage device 754 and / or memory device 756 associated with system controller 750 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0139] A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal 718 and to control the spacing between the substrate and other parts of process tool 700.

[0140] A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. The process gas control program may include 26 LAMRP922WO-11400-WOcode for controlling gas composition and flow rates within any of the disclosed ranges. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any of the disclosed pressure ranges.

[0141] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions to maintain the temperature of the substrate within any of the disclosed ranges.

[0142] A plasma control program may include code for setting RF power levels and frequencies applied to the process electrodes in one or more process stations, for example using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0143] In some embodiments, there may be a user interface associated with system controller 750. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0144] In some embodiments, parameters adjusted by system controller 750 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power levels, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.

[0145] Signals for monitoring the process may be provided by analog and / or digital input connections of system controller 750 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 700. Non- limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0146] Any suitable chamber may be used to implement the disclosed embodiments. Two or more of the stations may perform the same functions. Similarly, two or more stations may perform different functions. Each station can be designed / configured to perform a particular function / method as desired.

[0147] As described above, one or more process stations may be included in a multi-station 27 LAMRP922WO-11400-WOprocessing tool. Figure 8 depicts an example processing apparatus according to disclosed embodiments. Tool 800 includes a first processing chamber 802 and a second processing chamber 804. The first processing chamber 802 includes a plurality of processing stations, four stations 880A–D, that each may process a wafer. The first processing chamber 802 is configured to perform plasma treatment operations on the wafers. The second processing chamber 804 is configured to perform deposition on the wafer and may be considered a deposition chamber. The second processing chamber 804 also includes a plurality of processing stations, four stations 882A–D, that each may process a wafer. The first and second processing chambers 802 and 804 may be considered multi-station processing chambers.

[0148] Tool 800 also includes a wafer transfer unit configured to transport one or more wafers within the tool 800. Additional features of tool 800 will be discussed in greater detail below, and various features are discussed here with respect to some of the described techniques. In the depicted illustration, the wafer transfer unit includes a first robotic arm unit 808 in a first wafer transfer module 810 and a second robotic arm unit 812 in a second wafer transfer module 814 that may be considered an equipment front end module (EFEM) configured to received containers for wafers, such as a front opening unified module (FOUP) 816. The first robotic arm unit 808 is configured to transport a wafer between the first processing chamber 802 and the second processing chamber 804, and between the second the second robotic arm unit 812. The second robotic arm unit 812 is configured to transport the wafer between a FOUP and the first robotic arm unit 808. After a wafer has been treated in the first processing chamber 802, the wafer transfer unit is able to transfer the wafer from the first processing chamber 802, to the second processing chamber 804 where one or more layers of encapsulation material may be deposited on one or more wafers.

[0149] Similar to above, the first wafer transfer module 810 may a vacuum transfer module (VTM). Airlock 820, also known as a loadlock or transfer module, is shown and may be individually optimized to perform various fabrication processes. The tool 800 also includes a FOUP 816 that is configured to lower the pressure of the tool 800 to a vacuum or low pressure, e.g., between about 1 mTorr and about 10 Torr, and maintain the tool 800 at this pressure. This includes maintaining the first and second processing chambers 802 and 804, and the first wafer transfer module 810 at the vacuum or low pressure. The second wafer transfer module 814 may be at a different pressure, such as atmospheric. As the wafer is transferred throughout the tool 800, it is therefore maintained at the vacuum or low pressure. For example, as the wafer is transferred from the first processing chamber 802, into the first wafer transfer module 810, and to 28 LAMRP922WO-11400-WOthe second processing chamber 804, the wafer is maintained at the vacuum or low pressure and not exposed to atmospheric pressure.

[0150] In a further example, a substrate is placed in one of the FOUPs 818 and the second robot arm unit 812, or front-end robot, transfers the substrate from the FOUP 818 to an aligner, which allows the substrate to be properly centered before it is etched, or deposited upon, or otherwise processed. After being aligned, the substrate is moved by the second robot arm unit 812 into the airlock 820. Because airlock modules have the ability to match the environment between an ATM and a VTM, the substrate is able to move between the two pressure environments without being damaged. From the airlock 820, the substrate is moved by the first robot arm unit 808 through the first wafer transfer module 810, or VTM 810, and into the first processing chamber 802. In order to achieve this substrate movement, the first robot arm unit 808 uses end effectors on each of its arms.

[0151] Figure 8 also depicts an embodiment of a system controller 829 employed to control process conditions and hardware states of tool 800. System controller 829 may include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). Processors may include a CPU or computer, analog, and / or digital input / output connections, stepper motor controller boards, etc. System controller 829 may have one or more features such as those described above with respect to system controller 750.

[0152] A process station may be included in a single-station chamber or single-chamber tool such as shown in Figure 9. Figure 9 depicts an example processing apparatus according to disclosed embodiments. Tool 900 includes a processing chamber 914 which includes a processing station 990 may process a wafer. The processing chamber 914 is configured to deposit molybdenum, perform preclean, perform degas, and / or perform soaking and the like.

[0153] Tool 900 also includes a wafer transfer unit configured to transport wafers within the tool 900. Additional features of tool 900 will be discussed in greater detail below, and various features are discussed here with respect to some of the described techniques. In the depicted illustration, the wafer transfer unit includes a first robotic arm unit 926 in a first wafer transfer module and a second robotic arm unit 906 in a second wafer transfer module that may be considered an equipment front end module (EFEM) configured to received containers for wafers, such as a front opening unified module (FOUP) 908. The first robotic arm unit 926 is configured to transport a wafer between the processing chamber 914 and the second robotic arm unit via module 904 which may hold multiple wafers such as shown in module 902 with substrate 912. The second robotic arm unit 906 is configured to transport the wafer between a FOUP and module 904, or from module 29 LAMRP922WO-11400-WO902 to FOUP. After a wafer has been prepared in the module 904, the wafer transfer unit is able to transfer the wafer to first processing chamber 914 for deposition and optional anneal in situ.

[0154] Similar to above, the first wafer transfer module may a vacuum transfer module (VTM). Airlock or module 904, also known as a loadlock, is shown and may be individually optimized to perform various fabrication processes. The tool 900 also includes a FOUP 908 that is configured to lower the pressure of the tool 900 to a vacuum or low pressure, e.g., between about 10 Torr to about 150 Torr, and maintain the tool 900 at this pressure. This includes maintaining the processing chamber 914, and the first wafer transfer module at the vacuum or low pressure. The second wafer transfer module may be at a different pressure, such as atmospheric. As the wafer is transferred throughout the tool 900, it is therefore maintained at the vacuum or low pressure.

[0155] In a further example, a substrate is placed in one of the FOUPs 908 and the second robot arm unit 906, or front-end robot, transfers the substrate from the FOUP 918 to an aligner, which allows the substrate to be properly centered before it is etched, or deposited upon, or otherwise processed. After being aligned, the substrate is moved by the second robot arm unit 906 into the airlock module 904. Because airlock modules have the ability to match the environment between an ATM and a VTM, the substrate is able to move between the two pressure environments without being damaged. From the airlock module 904, the substrate is moved by the first robot arm unit 926 through the first wafer transfer module, or VTM, and into the processing chamber 914. In order to achieve this substrate movement, the first robot arm unit 926 uses end effectors on each of its arms.

[0156] Figure 9 also depicts an embodiment of a system controller 950 employed to control process conditions and hardware states of process tool 900. System controller 950 may include one or more memory devices 956, one or more mass storage devices 954, and one or more processors 952. Processor 952 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc. In some embodiments, system controller 950 includes machine-readable instructions for performing operations such as those described above with respect to Figures 7 and 8. EXPERIMENTAL

[0157] An experiment was conducted to evaluate molybdenum thickness of films deposited using pulsed chemical vapor deposition (“pCVD”) such as described in accordance with certain disclosed embodiments. Pulsed chemical vapor deposition was performed at 300°C, at 310°C, at 320°C, and at 360°C. The deposition thickness at 310°C, 320°C, and 360°C exhibited sufficient thickness. At 300°C, the molybdenum thickness was level even as the number of cycles increased, 30 LAMRP922WO-11400-WOwhich indicated that temperatures 310°C and above were more effective. Deposition for all four processes were performed on a substrate that had tungsten that was previously deposited at 50°C using physical vapor deposition. The results are depicted in Figure 10. DEFINITIONS AND PRECURSORS DEFINITIONS

[0158] “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.

[0159] 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.

[0160] The term “semiconductor substrate” as used herein refers to a substrate at any stage of semiconductor device fabrication containing a semiconductor material anywhere within its structure. It is understood that the semiconductor material in the semiconductor substrate does not need to be exposed. Semiconductor wafers having a plurality of layers of other materials (e.g., dielectrics) covering the semiconductor material, are examples of semiconductor substrates. The following detailed description assumes the disclosed implementations are implemented on a semiconductor wafer, such as on a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed implementations are not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of the disclosed implementations include various articles such as printed circuit boards and the like.

[0161] 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- 31 LAMRP922WO-11400-WO10), 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.

[0162] 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. By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenylene group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkenylene groups include - CH=CH- or -CH=CHCH2-.

[0163] 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.

[0164] By “alkyl” and the prefix “alk” is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t- butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic (e.g., C3-24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include 32 LAMRP922WO-11400-WOhaloalkyl, in which the alkyl group is substituted by one or more halo groups, as described herein. In another example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-Ak, wherein Ak is optionally substituted C1-6 alkyl); (2) amino (e.g., -NRN1RN2, where each of RN1 and RN2 is, independently, H or optionally substituted alkyl, or RN1 and 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 C3-8 hydrocarbon group); (10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorous, sulfur, or halo); (12) heterocyclyloxy (e.g., -O-Het, wherein Het is heterocyclyl, as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, wherein Het is heterocyclyl, as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO2); (17) oxo (e.g., =O); (18) -CO2RA, where RA is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, 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) C1-6alkyl (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) C1-6alkyl, (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) C4-18aryl, (g) (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), (h) C3-8cycloalkyl, and (i) (C3-8cycloalkyl) C1-6alkyl (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. 33 LAMRP922WO-11400-WO

[0165] 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.

[0166] 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.

[0167] The term “alkylsilyl”, as used herein, refers to SiR3group, wherein at least one R is an alkyl, and each R is independently selected from H and an alkyl. Alkylsilyls include mono, bis, and tris alkylsilyls. Examples of alkylsilyls include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, and ethylsilyl.

[0168] By “alkynyl” is meant an optionally substituted C2-24alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non- limiting unsubstituted alkynyl groups include C2-8alkynyl, C2-6alkynyl, C2-5alkynyl, C2-4alkynyl, or C2-3alkynyl. 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.

[0169] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C2-24alkyl 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-.

[0170] By “amido” is meant -N(RN1)C(O)-, where RN1is H, optionally substituted alkyl, or optionally substituted aryl.

[0171] 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.

[0172] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino 34 LAMRP922WO-11400-WOgroup, as defined herein.

[0173] By “aminoaryl” is meant an aryl group, as defined herein, substituted by an amino group, as defined herein.

[0174] By “aryl” is meant a group that contains any carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C4-8cycloalkyl radicals (e.g., as defined herein) such as, for instance, indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents, such as any described herein for alkyl.

[0175] By “azido” is meant -N3.

[0176] By “branched alkenyl” is meant an isomer of a straight chain alkenyl compound; one having alkyl groups bonded to the main carbon chain.

[0177] By “cyano” is meant -CN.

[0178] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0179] 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.

[0180] 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 35 LAMRP922WO-11400-WOrepeated for as many cycles necessary to obtain the desired metal thickness.

[0181] By “dicarbonyl” is meant any moiety or compound including two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., RC1-C(O)- C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group); 1,3-dicarbonyl (e.g., RC1-C(O)- C(R1aR2a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1aand R2ais, independently, H or an optional substituent provided for alkyl, as defined herein); and 1,4- dicarbonyl (e.g., RC1-C(O)-C(R1aR2a)-C(R3aR4a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1a, R2a, R3a, and R4ais, independently, H or an optional substituent provided for alkyl, as defined herein).

[0182] The term “fluoroalkyl”, as used herein, refers alkyl groups containing one or more fluorine substituents. In some implementations fluoroalkyls contain exclusively fluorine substituents, such as in CF3, C2F5, C3F7. Fluoroalkyls may be linear, branched and cyclic.

[0183] By “halo” is meant F, Cl, Br, or I.

[0184] By “halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group.

[0185] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.

[0186] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0187] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0188] 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, C1-5haloalkyl, C1-6haloalkyl, C2-3haloalkyl, C2-4haloalkyl, C2-5haloalkyl, C2-6haloalkyl, 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 36 LAMRP922WO-11400-WO(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.

[0189] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo.

[0190] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). The 3- membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, 37 LAMRP922WO-11400-WOdibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and / or 38 LAMRP922WO-11400-WOamino) 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.

[0191] By “hydroxyl” is meant -OH.

[0192] By “imino” is meant -NR-, in which R can be H or optionally substituted alkyl.

[0193] By “isocyanato” is meant -NCO.

[0194] By “isocyano” is meant -N ≡ C -, and includes nitriles of the formula RN≡C-, wherein R is an aliphatic, aryl or heteroaryl group.

[0195] By “isothiocyanato” is meant -N=C=S.

[0196] By “low valent” is meant the lower oxidation states when a metal has multiple oxidation states.

[0197] By “oxo” is meant an =O group.

[0198] By “oxy” is meant -O-.

[0199] 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.

[0200] 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 39 LAMRP922WO-11400-WOeach 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.

[0201] Use of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohols, ethers, esters, amides, sulfones, sulfides, hydroxyl, nitro, cyano, carboxy, amines, heteroatoms, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogens, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl and aralkyaminocarbonyl, or any of the substituents of the preceding paragraphs or any of those substituents either directly attached or by suitable linkers. The linkers are typically short chains of 1-3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or -S(O)O- . Rings may be substituted multiple times.

[0202] The term “lower” modifying “alkyl”, “alkenyl”, “alkynyl”, “alkoxy” or “alkoxycarbonyl” refers to a C1-C6unit for a particular functionality. For example, “lower alkyl” means C1-C6alkyl.

[0203] 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).

[0204] By “thiocyanato” is meant -SCN.

[0205] 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. 40 LAMRP922WO-11400-WO

[0206] 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.

[0207] 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.

[0208] 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.

[0209] The implementations disclosed below describe deposition of a material on a substrate such as a wafer, substrate, or other work piece. The work piece may be of various shapes, sizes, and materials. In this application, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the processing details recited herein (e.g., flow rates, power levels, etc.) are relevant for processing 300 mm diameter substrates, or for treating chambers that are configured to process 300 mm diameter substrates and can be scaled as appropriate for substrates or chambers of other sizes. In addition to semiconductor wafers, other work pieces that may be used implementations disclosed herein include various articles such as printed circuit boards and the like. The processes and apparatuses can be used in the fabrication of semiconductor devices, displays, LEDs, photovoltaic panels and the like.

[0210] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds.

[0211] By “unsaturated substituent” is meant a double or triple bond containing aliphatic chain, cyclic, aryl or heteroaryl group.

[0212] 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. MOLYBDENUM-CONTAINING PRECURSORS

[0213] The metal-containing precursor may be a molybdenum-containing precursor. Generally, 41 LAMRP922WO-11400-WOmolybdenum 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.

[0214] 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.

[0215] 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, MoCl5or MoCl6are used. While the description chiefly refers to MoClxprecursors, 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 MoXzprecursors include molybdenum fluoride (MoF6), molybdenum bromide (MoBr, and molybdenum iodide (MoI3). In some embodiments, a non-fluorine-containing MoXzprecursor is used to prevent fluorine etch or incorporation. In some embodiments, a non-bromine-containing and / or a non-iodine-containing MoXzprecursor is used to prevent etch or bromine or iodine incorporation.

[0216] 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.

[0217] 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.

[0218] 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. 42 LAMRP922WO-11400-WO

[0219] In another aspect a precursor for deposition of molybdenum-containing films includes: molybdenum. at least one substituted or unsubstituted 1,4-diazabuta-1,3-diene (DAD) ligand bound to molybdenum, and at least one second ligand. The DAD ligand in some embodiments is selected from the group consisting of: neutral DAD,and dianionic DAD,wherein each R is independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The second ligand is selected from the group consisting of an anionic ligand and a neutral ligand, with a proviso that the compound does not include CO as the only second ligand. In some embodiments the precursor compound is Mo(DAD)m(L)n(X)p, wherein each L is the neutral ligand, each X is an anionic ligand. m is selected from 1-3, n is selected from 0-4, and p is selected from 0-4. wherein n and p are not simultaneously zero. In some embodiments each neutral ligand L is independently selected from the group consisting of CO, an amine, a phosphine, a nitrile, an isonitrile, and a thioether, and each anionic ligand X is independently selected from the group consisting of a halide. an alkyl, an allyl, a cyclopentadienyl, an alkoxide, an amide, and an imide.

[0220] The molybdenum-containing precursor may also be a low valent molybdenum- containing complex. 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.

[0221] Low valent molybdenum precursors may offer a less circuitous surface redox process to 43 LAMRP922WO-11400-WOobtain 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.

[0222] Mo (0) precursors are advantageous because do not require any reduction steps, and are energetically facile, as their use provides a lower energy barrier to Mo film formation upon exposure to a reducing agent. They are especially amenable in multi-step ALD processes where surface-ligand exchange and conversion (reduction) occurs. Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex existing in the oxidation state of zero.

[0223] A general structure for low valent molybdenum precursors having one molybdenum is MoLn(Formula I), and general structures for low valent molybdenum precursors with two molybdenum atoms are Mo2Ln(Formula II) or LnMo(L’)mMoLn(Formula III). For any of Formulas I-III, each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand and n is an integer of 2 to 6. For Formula III, L’ is a linking moiety such as a bidentate ligand; and m is an integer of 1 to 3.

[0224] 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- C3alkyl)amino, -C(O)O-(C1-C3alkyl), -C(O)NH-(C1-C3alkyl), -CH=NOH, -P(C1-C3alkyl)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.

[0225] 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.

[0226] In some embodiments, the monodentate ligand can include an oxygen atom. In particular embodiments, one or more ligands can be optionally substituted alkoxy. Non-limiting ligands 44 LAMRP922WO-11400-WOinclude, e.g., methoxy, ethoxy, isopropoxy (i-PrO), t-butoxy (t-BuO), and -O=C(CH3)- CH=C(CH3)-O- (acac). Non-limiting molybdenum-containing precursors include, e.g., Mo(CH2F)(t-BuO)3, Mo(CF3)(t-BuO)3, Mo(CH2I)(t-BuO)3, Mo(CI3)(t-BuO)3, Mo(CH2CH2F)(t- BuO)3, Mo(CH2CH2I)(t-BuO)3, Mo(CH2F)2(t-BuO)2, Mo(CF3)2(t-BuO)2, Mo(CH2I)2(t-BuO)2, Mo(CI3)2(t-BuO)2, Mo(CH2CH2F)2(t-BuO)2, Mo(CH2CH2I)2(t-BuO)2, Mo(t-BuO)2, Mo(CH3)(t- BuO)3, Mo(CH2CH3)(t-BuO)3, Mo(CH=CH2)(t-BuO)3, Mo(CH=CHCH3)(t-BuO)3, Mo(CH2- CH=CH2)(t-BuO)3, Mo(C≡CH)(t-BuO)3, Mo(C≡CCH3)(t-BuO)3, Mo(CH2C≡CH)(t-BuO)3, or Mo(acac)2.

[0227] In certain embodiments, the oxygen-containing monodentate ligand may be -OC(CH3)(CF3)2, -OC(CH3)2(CF3), -OC(CH3)3, -OSiR3(such as -OSiPh3), C O (carbonyl ligand) 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.

[0228] In certain embodiments, the ligand is a phosphorous-containing ligand. Suitable complexes may be of the formula R3P where R is a halo, aliphatic or aryl group. Examples include secondary or tertiary organophosphines such as P(t-Bu)3, PMe3, PPh3, P(OMe)3, P(OEt)3, PCl3or PF3. In some embodiments, the phosphorus containing ligand is phosphanetriyltris(benzene sulfonic acid). Other phosphorus containing ligands include -CH2P(CH3)3, -P(O)OH, - P(O)(OCH3)2, -P(O)(OCH2CH3)2, and -CH(Si(CH3)3)(P(CH3)3).

[0229] In some embodiments, the ligand is an isocyano functional group, including isonitriles of 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.

[0230] 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 45 LAMRP922WO-11400-WOpyrimidinyl.

[0231] 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.

[0232] In some embodiments, the molybdenum-containing precursor has at least one optionally substituted haloalkyl group. Non-limiting haloaliphatic group ligands include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; or -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I). Yet other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (- CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (- CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (- CH2CHFI), and the like. In particular embodiments, the C1-2haloalkyl includes β-halo-substituted ethyl. Yet other haloaliphatic groups include C1-4haloalkyl, C2-4haloalkenyl, and C2-4haloalkynyl.

[0233] 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=CH2and the like.

[0234] In some embodiments, the monodentate ligand may be -CH2P(CH3)3, -CH(Si(CH3)3)(P(CH3)3), -C(O)C3F7, or -CHCHSO2C6H5.

[0235] In some embodiments, the monodentate ligand includes a sulfur atom. In particular embodiments, one or more monodentate ligands can be -SO2CF3, -SO2C3N2H3, -CHCHSO2C6H5, 46 LAMRP922WO-11400-WO-SO2OCH3, or -SO2C6H4CH3.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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).

[0241] 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.

[0242] Alkynyl groups are also suitable monodentate ligands in certain embodiments. In some embodiments, the carbon-carbon triple bond is not bound directly to the molybdenum, for example in a formula R1CCCH2MoL3where R1is a C1-C2linear or branched alkane such as methyl or ethyl; and L is an amino (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminiocyclopentane, aminocyclohexane) or alkoxy group (methoxy, ethoxy, n-propoxy, 47 LAMRP922WO-11400-WOisopropoxy, t-butoxy, sec-butoxy, or n-butoxy).

[0243] 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.

[0244] In some embodiments, the monodentate ligand is halo. In particular, the metal- containing precursor can be a metal halide or organometal halide. Non-limiting metal halides and organometal halides include FCH2MoX3, CF3MoX3, ICH2MoX3, CI3MoX3, CH2FCH2MoX3, CH2ICH2MoX3, MoX2, or MoX4, in which each X is, independently, halo. In other embodiments, the metal-containing precursor is RMoX3, in which R is C1-4haloalkyl, C2-4haloalkenyl, or C2-4haloalkynyl; and in which each X is, independently, halo. In yet other embodiments, the metal- containing precursor is RMoX3, in which R is C1-2alkyl, C2-4alkenyl, or C2-4alkynyl; and in which each X is, independently, halo.

[0245] In other embodiments, the monodentate ligand is C1- C3aliphatic (wherein the C1-C3aliphatic may be optionally substituted with a ketone, an alkoxy group, an epoxy group) or a - C(O)C1-C3alkyl group. Ethers, ketones or epoxide-containing ligands on the low valent molybdenum-containing precursors may be advantageous to assist in crosslinking.

[0246] In some embodiments, the monodentate ligand can include a silicon atom. In some embodiments, the monodentate ligand may be -Si(CH3)3, -Si(C2H5)3, -CH2Si(CH3)3, - CH(Si(CH3)3)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.

[0247] In some embodiments, the monodentate ligand includes at least one isocyanato, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, alkoxy or haloalkoxy.

[0248] In some embodiments, the monodentate ligand is at least one allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl or pyrimidinyl.

[0249] For any formula herein, each monodentate ligand may independently be hydrogen, halo, azido, cyano, akylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally 48 LAMRP922WO-11400-WOsubstituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1can be alkyl).

[0250] 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.

[0251] 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

[0252] Suitable ligands for the low valent molybdenum complexes include bidentate ligands. A bidentate ligand (also referred to as a chelating ligand) is one which binds or coordinates to a metal center via two coordination sites of the metal, or via two sites of the ligand. Bidentate ligands are Lewis bases that donate two pairs of electrons to a metal atom. The bidentate ligands may be neutral or anionic. Furthermore, the bidentate ligands may have the same two coordination atoms, or may be unsymmetrical bidentate ligands, where the two coordination atoms are not the same. In some embodiments, the bidentate ligands may be ethylenediamine (en), bipyridyl (bpy), 1,2- bis(dimethylphosphino)ethane (dmpe), phenanthroline (phen), 1,2-bis(diphenylphosphino)ethane (dppe), acetate (OAc), oxalate (ox), or acetylacetonate (acac).

[0253] 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.

[0254] Suitable low valent molybdenum precursors may contain one, two or three bidentate ligands each of which may be the same or different.

[0255] 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

[0256] 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 49 LAMRP922WO-11400-WOphosphorus 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.

[0257] 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.Example structures for molybdenum precursors having three ligands (Formula XIV),Formula XIV four ligands (Formula V and Formula VI)Formula V Formula VI or five ligands (Formula IX and Formula X)Formula IX Formula X in certain embodiments. For Formulas XIV, VI, IX and X, R4, R6, R7and R15are each independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -CF3, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3or -CH2Si(CH3)3, -CH(Si(CH3)3)2,-C(Si(CH3)3)3,-P(CH3)3, -CH2P(CH3)3, -P(O)OH, -P(O)(OCH3)2, -P(O)(OCH2CH3)2, -CH(Si(CH3)3)(P(CH3)3), -SO2CF3, -SO2C3N2H3, 50 LAMRP922WO-11400-WO-C(O)C3F7, -CHCHSO2C6H5, -SO2OCH3,or -SO2C6H4CH3. For Formula IX, G may be =O, =NR, =S or =CR2, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. For Formula X, each R8is independently any of the monodentate, ambidentate or bidentate ligands described above. For Formula V, R1may be aliphatic, R2may be any of the monodentate, ambidentate, bidentate or tridentate ligands described above, and n may be 1, 2, 3, 4 or 5.

[0258] Low valent molybdenum precursors may also have six ligands. Such precursors may have the general formula Mo(X)p(R10)q(XII) where each X independently includes chloro, fluoro, 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.

[0259] Low valent molybdenum precursors having six ligands may also be of 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.

[0260] Structures for low valent molybdenum precursors may have six ligands. In some embodiments, the precursors may 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. In some embodiments, the structures may have one or more PMe3ligands.

[0261] Molybdenum complexes can be prepared using a zero valent starting material such as molybdenum hexacarbonyl. Other synthetic routes include reaction of MoCl3(THF)3with the appropriate ligand followed by reduction and reaction of MoX5(X = Cl, Br, I) with the appropriate 51 LAMRP922WO-11400-WOligand followed by reduction.

[0262] 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.

[0263] 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

[0264] 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. In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a double bond. In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a triple bond. L may be any ligand described above, or may be any one of CO, CNR or PMe3(where R is aliphatic, aryl or heterocyclyl). 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.

[0265] Di-molybdenum precursors described herein can be synthesized using dimolybdenum tetraacetate as a starting material by treatment with a ligand salt such as lithium amidate. In one aspect, a container housing any of the precursors described herein in a solid or liquid form is 52 LAMRP922WO-11400-WOprovided. In another aspect a solution of any of these precursors is provided, where the solvent may include, for example, a high boiling point hydrocarbon solvent, such as a higher alkane. In some embodiments a container holding the molybdenum precursor (in solid or liquid form or in solution) is filled with an inert gas, such as nitrogen (N2), or argon (Ar), to prevent contact of the precursor with air, and possible decomposition due to contact with moisture and / or air. In some embodiments the container is adapted for vaporization of the precursor inside the container. For example, the container may include an inlet and an outlet, where the inlet is adapted to be connected with a source of a carrier gas that can be flowed over or through the precursor thereby assisting in precursor vaporization. The outlet is adapted for removing the carrier gas and the precursor vapor from the container and is configured to be connected to a conduit that can be used to deliver the precursor vapor to the processing chamber. The inlet and the outlet each has a closed position and an open position, and, for example, can include manual valves that can be used to switch from closed to open positions and back. When the container is stored or transported the inlet and the outlet are closed. When the container is fitted to the deposition apparatus for use, the inlet and the outlet valves may be open, and a carrier gas may be flown into the inlet, and out from the outlet carrying the precursor vapor.

[0266] In some embodiments the container has a flow-over design, in which the inlet and the outlet are positioned above the surface of the precursor. For example, in a cylindrical container the inlet and the outlet may be positioned at a similar vertical elevation (e.g., the vertical distance between the inlet and the outlet may be less than about 20% of the cylinder height). In other embodiments the container has a bubbler design, in which the inlet is positioned below the surface of the precursor and the outlet is positioned above the inlet (e.g., above the surface of the precursor). For example, in a cylindrical container the inlet and the outlet may be positioned far from each other in a vertical direction (e.g., the vertical distance between the inlet and the outlet may be more than about 30%, such as more than about 50%, or more than about 80% of the cylinder height.

[0267] 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. 53 LAMRP922WO-11400-WO

[0268] In some embodiments, the low valent dimolybdenum complex may contain two molybdenum atoms both directly bonded to each other and also connected indirectly to each by a linking moiety as described above.

[0269] In some embodiments, the bidentate ligand has a structure of Formula (IV): -(E)e- (IV), wherein each E is independently NR, C(R)n, Si(R)n, S, O or P(R)n; where each R is independently hydrogen, aryl, amino or aliphatic; e is 1, 2, 3, 4 or 5; and n is 0, 1 or 2.

[0270] In some embodiments, the bidentate ligand is -O(C(R)n)mO-, -O(C(R)n)mNR-, -C(R)2P(R)2C(R)2P(R)2-C(R)2- or -C(R)2P(R)2N(R)P(R)2-C(R)2-; where each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or R groups may be linked to form a ring; n is 0, 1 or 2; and m is 1, 2 or 3.

[0271] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL4.

[0272] In some embodiments, the low valent molybdenum precursor has one or two bidentate ligands.

[0273] In some embodiments, the low valent molybdenum precursor has a structure of Formula (V):wherein each R1independently comprises alkyl or haloalkyl; each R2independently comprises carbonyl, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, isocyanato, or isothiocyanato; and n is 0, 1, 2 or 3.

[0274] In some embodiments, each R2independently is -CNR3, and where R3comprises aliphatic, aryl or heterocyclyl.

[0275] In some embodiments, R3is haloalkyl or haloaryl.

[0276] In some embodiments, R3is pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, - CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3or nonafluoro-n-butyl. 54 LAMRP922WO-11400-WO

[0277] In some embodiments, the low valent molybdenum precursor has a structure of Formulawhere each R4is independently aliphatic, alkylsilyl, or haloalkyl; or R4substituents may be linked to form a ring.

[0278] In some embodiments, each R4is independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, - CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, - CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3, -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.

[0001] In some embodiments, the low valent molybdenum precursor has a structure of Formula (VII):where each E independently comprises NR, C(R)n, Si(R)n, S, O or P(R)n, where each R independently comprises hydrogen, aryl, amino or aliphatic; each R5independently comprises halo, hydroxy, aliphatic, alkyl silyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -N(Si(CH3)3)2, -C1-C3alkylamino, alkenylamino, alkynylamino, di(C1-C3alkyl)amino, -C(O)O- (C1-C3alkyl), -C(O)NH-(C1-C3alkyl), -CH=NOH, -P(C1-C3alkyl)3, -PO3H2, -OPO3H2, 55 LAMRP922WO-11400-WO-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, =O, =S, -CO, aralkenyl, aralkyl, sulfonyl, sulfonamido, carbamate, aryloxyalkyl, carboxyl, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, thiocyanato, isothiocyanato, cyano or cyclyl; e is 1, 2, 3, 4 or 5; and n is 0, 1 or 2.

[0279] In some embodiments, the low valent molybdenum precursor has a structure of Formula (VIII):where each E independently comprises NR, C(R)n, Si(R)n, S, O or P(R)n; where each R independently comprises hydrogen, aryl, amino or aliphatic; e is 1, 2, 3, 4 or 5; and n is 0, 1 or 2.

[0280] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL5.

[0281] In some embodiments, the low valent molybdenum precursor has one bidentate ligand or two bidentate ligands.

[0282] In some embodiments, the bidentate ligand has a structure of Formula (IV): -(E)e- (IV), wherein each E is independently NR, C(R)n, Si(R)n, S, O or P(R)n; where each R is independently hydrogen, aryl, amino or aliphatic; e is 1, 2, 3, 4 or 5; and n is 0, 1 or 2.

[0283] In some embodiments, the bidentate ligand is -O(C(R)n)mO-, -O(C(R)n)mNR-, -C(R)2P(R)2C(R)2P(R)2-C(R)2- or -C(R)2P(R)2N(R)P(R)2-C(R)2-; where each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or R groups may be linked to form a ring; n is 0, 1 or 2; and m is 1, 2 or 3.

[0284] In some embodiments, the low valent molybdenum precursor has two bidentate ligands.

[0285] In some embodiments, the low valent molybdenum precursor has a structure of Formula 56 LAMRP922WO-11400-WO(X) or Formula (XI):where each R7is independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3,-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(C H3)3), -SO2CF3, -SO2C3N2H3, -C(O)C3F7, -CHCHSO2C6H5, -SO2OCH3 or -SO2C6H4CH3; and each R8is independently 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 -CNR9, where R9is aliphatic, aryl or heterocyclyl.

[0286] In some embodiments, R9comprises haloalkyl or haloaryl.

[0287] In some embodiments, R9is pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3or nonafluoro-n-butyl.

[0288] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL6.

[0289] In some embodiments, the low valent molybdenum precursor has one, two or three bidentate ligands.

[0290] In some embodiments, the bidentate ligand has a structure of Formula (IV): -(E)e- (IV), where each E is independently NR, C(R)n, Si(R)n, S, O or P(R)n; where each R is independently hydrogen, aryl, amino or aliphatic; e is 1, 2, 3, 4 or 5; and n is 0, 1 or 2.

[0291] In some embodiments, the bidentate ligand is -O(C(R)n)mO-, -O(C(R)n)mNR-, -C(R)2P(R)2C(R)2P(R)2-C(R)2- or -C(R)2P(R)2N(R)P(R)2-C(R)2-; where each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or R groups may be linked to form a ring; n is 0, 1 or 2; and m is 1, 2 or 3.

[0292] In some embodiments, the low valent molybdenum precursor has a structure of Formula 57 LAMRP922WO-11400-WO(XII): Mo(X)p(R10)q(XII), where each X is independently chloro, fluoro, bromo or iodo; each R10is independently 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 R11is aliphatic, aryl or heterocyclyl; p is 1, 2, 3 or 4; q is 2, 3, 4 or 5; and p + q = 6.

[0293] In some embodiments, R11is haloalkyl or haloaryl.

[0294] In some embodiments, R11is pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3or nonafluoro-n-butyl.

[0295] In some embodiments, the low valent molybdenum precursor has a structure of Formula (XIII): Mo(R12)r(R13)s(XIII), where each R12is independently 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 R14is aliphatic, aryl or heterocyclyl; each R13is independently 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, 2, 3, 4, 5 or 6; s is 0, 1, 2, 3, 4 or 5; and r + s = 6.

[0296] In some embodiments, R14is haloalkyl or haloaryl.

[0297] In some embodiments, R14is pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3or nonafluoro-n-butyl.

[0298] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL2.

[0299] In some embodiments, each L is independently allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, or pyrimidinyl.

[0300] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL3.

[0301] In some embodiments, the low valent molybdenum precursor has one bidentate ligand.

[0302] In some embodiments, the low valent molybdenum precursor is a structure of Formula (XIV): 58 LAMRP922WO-11400-WO(XIV),where each R15is independently aliphatic, alkylsilyl or haloalkyl; or R15substituents may be linked to form a ring.

[0303] In some embodiments, each R15is independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, - CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, - CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3,-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, -SO2OCH3or -SO2C6H4CH3.

[0304] In some embodiments, the low valent molybdenum precursor has a structure of Formula (XV): Mo2(OR16)6(XV), where each R16is independently aliphatic.

[0305] In some embodiments, the molybdenum-containing layer is molybdenum metal.

[0306] In some embodiments, the molybdenum-containing layer is molybdenum nitride, molybdenum carbide, molybdenum boride, molybdenum silicide or a combination thereof.

[0307] In some embodiments, the molybdenum-containing layer is a molybdenum-containing film.

[0308] In some embodiments, the at least one reactant is hydrogen, ammonia, diborane, water, hydrogen sulfide, a thiol, an alcohol, an amine, hydrazine, silane or disilane.

[0309] The present disclosure includes a metal coordination complex. In some embodiments, the complex has a structure of Formula (V):wherein each R1is independently alkyl or haloalkyl; each R2is independently carbonyl, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, isocyanato or isothiocyanato; and n is 0, 1, 2 or 3.

[0310] The present disclosure also includes certain metal coordination complexes. In some embodiments, the complex has a structure of Formula (VI), Formula (IX), Formula (X), Formula 59 LAMRP922WO-11400-WO(XI), or Formula (XV):Mo2(OR16)6(XV), where R4, R6, R7and R16are each independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F11, -CH2CF3, - CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3, - 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, -SO2OCH3or -SO2C6H4CH3; G is =O, =NR, =S or =CR2, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group; and each R8is independently 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 -CNR9, where R9is aliphatic, aryl or heterocyclyl.

[0311] The present disclosure includes other metal coordination complexes. In some embodiments, the complex has a structure of Formula (XII) or Formula (XIII):Mo(X)p(R10)q(XII) or Mo(R12)r(R13)s(XIII), where each X is independently chloro, fluoro, bromo or iodo; where R10and R12are each independently 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, - 60 LAMRP922WO-11400-WOP(CH2CH3)3or -CNR14, where R14is aliphatic, aryl or heterocyclyl; each R13is independently 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; p is 1, 2, 3 or 4; q is 2, 3, 4 or 5; p + q=6; r is 1, 2, 3, 4, 5 or 6; s is 0, 1, 2, 3, 4 or 5; and r + s = 6; with the proviso that at least one R10of Formula (XII) is -CNR14; and with the proviso that at least one R12of Formula (XIII) is -CNR14.

[0312] The molybdenum-containing films, and, particularly, high purity molybdenum metal, provided herein can be used in interconnect metallization (e.g., for filling recessed features to form contacts), in logic gate applications in FinFETs, as adhesion layers or diffusion barriers, and in 3D NAND fabrication. Examples of applications include logic and memory contact fill, DRAM buried wordline fill, vertically integrated memory gate, and wordline fill, and 3-D integration using through-silicon vias (TSV). The resistivity of molybdenum scales better than that of tungsten, and in some embodiments, molybdenum is particularly advantageous metal for filling narrow recessed features, e.g., features with widths of less than about 20 nm.

[0313] In one application, molybdenum metal is used for manufacturing barrierless contacts. In this application, molybdenum metal is deposited directly into the recessed features (contact holes) having widths of about 5 – 100 nm, e.g., about 5 – 20 nm, where the recessed features are formed in the dielectric layer, and include exposed dielectric, such as silicon oxide, silicon nitride, or a low-k material such as silicon oxycarbide at the sidewalls and exposed silicon or silicon germanium at the bottom. In alternative embodiments, the contact hole prior to deposition may be lined with a barrier layer, such as WN, MoN, MoC, or TiN onto which the molybdenum metal is deposited. Halide-containing heteroleptic molybdenum compounds

[0314] In one aspect, halide-containing heteroleptic molybdenum compounds (i.e., compounds having different types of ligands) are used as precursors for deposition of molybdenum-containing films, such as for deposition of molybdenum metal, molybdenum nitride or molybdenum carbide. In one embodiment, the precursor is a compound that includes molybdenum, at least one halide forming a bond with molybdenum, and at least one organic ligand having any of the N, O, and S elements, where an atom of any of these elements forms a bond with molybdenum. Examples of suitable organic ligands that provide nitrogen or oxygen bonding include amidinates, amidates, iminopyrrolidinates, diazadienes, beta-imino amides, alpha-imino alkoxides, beta-amino alkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates. 61 LAMRP922WO-11400-WOExamples of suitable organic ligands that provide sulfur bonding include thioethers, thiolates, dithiolenes, dithiolates, and α-imino thiolenes. These ligands may be substituted or unsubstituted. In some embodiments, these ligands include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The organic ligands can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in a variety of oxidation states, such as +1, +2, +3, +4, +5, and +6.

[0315] Structures of exemplary suitable N and / or O containing organic ligands 1-17 are shown in Figure 3B, and structures of exemplary suitable S-containing organic ligands 18-26 are shown in Figure 3C, where each R is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy. In some embodiments, each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments each R is independently selected from H, methyl, ethyl, n- propyl, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, and cyclobutylethyl. In some embodiments each R is an independently selected alkyl. In some embodiments ligands with branched alkyl substituents, such as isopropyl, and isobutyl are preferred, because such ligands provide more volatile molybdenum precursors.

[0316] In some embodiments at least one organic ligand in the precursor is an amine. Suitable amines include unidentate amines (e.g., monoalkylamines, dialkylamines), bidentate amines (e.g., unsubstituted or N-alkyl substituted ethylenediamines), and amines of higher denticities (e.g., substituted or unsubstituted diethylenetriamine). An example of a monodentate amine is amine 1, shown in Figure 1, where at least one R is an alkyl or fluoroalkyl, and each R is independently selected from the group consisting of H, alkyl, and fluoroalkyl. In some embodiments at least one R is an alkyl, and each R is independently selected from H, and an alkyl. In some embodiments, the at least one organic ligand is an amide, such as a monoanionic amide 16, wherein at least one R is an alkyl or fluoroalkyl, and each R is independently selected from H, alkyl, and a fluoroalkyl. In some embodiments, the at least one organic ligand is an imide, such as a dianionic imide 17, wherein R is an alkyl or fluoroalkyl. While in general imide-containing precursors can be used for deposition of a variety of molybdenum-containing films (including molybdenum metal), in some embodiments they are more preferred for deposition of molybdenum nitride and molybdenum carbonitride, as they form strong molybdenum-nitrogen bonds, and can serve as sources of nitrogen for the resulting film. In some embodiments, at least one organic ligand in the precursor is an amidinate. An example of an amidinate is an amidinate 2 shown in Figure 3B, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidinate 2 is a 62 LAMRP922WO-11400-WOmonoanionic ligand that can form two molybdenum-nitrogen bonds, serving as a bidentate ligand.

[0317] In some embodiments, at least one organic ligand in the precursor is an amidate. An example of an amidate is an amidate 3 shown in Figure 3B, where each R is independently selected from H, alkyl, and fluoroalkyl. Amidate 3 is a monoanionic ligand that can form one molybdenum- nitrogen, and one molybdenum-oxygen bond, serving as a bidentate ligand.

[0318] In some embodiments, at least one organic ligand in the precursor is a diazadiene. Examples of diazadienes are 1,4-diazabuta-1,3-dienes (DAD) 5, 6, and 7, where each R is independently selected from H, alkyl, and fluoroalkyl. An interesting property of this ligand is that it can exist in neutral form 5, monoanionic radical form 6, and dianionic form 7. Due to redox activity of monoanionic (radical) form 6, it can be relatively easily removed during deposition making complexes of DAD 6 particularly useful for deposition of molybdenum metal and high purity molybdenum metal. DAD ligands 5, 6, and 7 can serve as bidentate ligands, each forming two molybdenum-nitrogen bonds. In some embodiments the molybdenum precursor includes DAD ligand 5, 6, or 7 as an organic ligand, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl.

[0319] In some embodiments, the at least one organic precursor is an iminopyrrolidinate (such as an iminopyrrolidinate 4, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-imino amide (such as beta-imino amide 8, where each R is independently selected from H, alkyl, and fluoroalkyl), an alpha-imino alkoxide (such as an alpha-imino alkoxide 9, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-diketiminate (such as an beta- diketiminate 10, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta- ketoiminate (such as beta-ketoiminate 11, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-diketonate 12 (such as beta-diketonate 12, where each R is independently selected from H, alkyl, and fluoroalkyl), a pyrazolate (such as pyrazolate 13, where each R is independently selected from H, alkyl, and fluoroalkyl), a beta-aminoalkoxide (such as beta- aminoalkoxide 14, where each R is independently selected from H, alkyl, and fluoroalkyl), or a guadinidate 15 (such as guadinidate 15, where each R is independently selected from H, alkyl, and fluoroalkyl). These are monoanionic ligands that are capable of binding to molybdenum in bidentate manner.

[0320] In some embodiments, the at least one organic precursor is a sulfur containing ligand that is capable of forming molybdenum-sulfur bond. In some embodiments the at least one organic ligand in the precursor is a thioether. The term “thioether” is used herein broadly to include to include both unidentate and multidentate (e.g. bidentate or tridentate) thioethers, as well as ligands 63 LAMRP922WO-11400-WOthat contain both thioether and thiolate (or other) moieties. An example of a unidentate thioether is dialkylsulfide R2S, where each R is an alkyl, such as dimethylsulfide, diethylsulfide, diisobutyl sulfide, and the like. An example of a multidentate thioether ligand that also includes thiolate moieties is (SCH2CH2SCH2CH2S)2-An example of a monodentate thioether is thioether 18, shown in Figure 3C, where each R is independently selected from the group consisting of alkyl, and fluoroalkyl. In some embodiments each R is independently selected from the group consisting of methyl, ethyl, n-propyl, isoropyl, n-butyl, isobutyl, sec-butyl, and t-butyl. In some embodiments, the at least one organic ligand is a thiolate, such as a monoanionic thiolate 19, wherein R is an alkyl or fluoroalkyl. For example, R can be methyl, ethyl, n-propyl, isoropyl, n-butyl, sec-butyl, isobutyl, or t-butyl. In some embodiments the thiolate is a dithiolate, such as dianionic alpha- dithiolate 24, (where each R is independently selected from H, alkyl, and fluoroalkyl) or dianionic beta-dithiolate 25 (where each R is independently selected from H, alkyl, and fluoroalkyl). Dithiolates are capable of forming two molybdenum-sulfur bonds with molybdenum.

[0321] In some embodiments, the at least one organic ligand in the precursor is a dithiolene. Examples of dithiolenes are structures 20, 21, and 22, where each R is independently selected from H, alkyl, and fluoroalkyl. This ligand (similarly to DAD) can exist in a neutral form 20, monoanionic radical form 21, and dianionic form 22. Due to redox activity of the monoanionic radical form 21, it can be relatively easily removed during deposition and reduction of molybdenum precursor, making complexes of dithiolene 21 particularly useful for deposition of molybdenum metal and high purity molybdenum metal. Dithiolene ligands 20, 21, and 22 can serve as bidentate ligands, each capable of forming two molybdenum-sulfur bonds. In some embodiments the molybdenum precursor includes dithiolene ligand 20, 21, and / or 22 as an organic ligand, where each R is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec- butyl, isobutyl, and t-butyl.

[0322] In some embodiments, the at least one organic ligand in the precursor is an alpha- iminothiolene, such as structure 23, where each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments each R substituent at the carbon atoms is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents, while R substituent at the nitrogen is independently selected from an alkyl and fluoroalkyl. In some embodiments R substituent at the nitrogen is independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. This ligand (similarly to DAD, and dithiolene) has a monoanionic radical form, as shown in structure 23, is redox-active, and easily removable during reduction processes. 64 LAMRP922WO-11400-WO

[0323] In some embodiments, the molybdenum-containing precursor preferably does not include molybdenum-oxygen or molybdenum-nitrogen double bonds. In some embodiments the molybdenum compound does not include concurrently both imide and guanidinidate ligands. In some embodiments the molybdenum compound does not include imide ligands or guanidinate ligands. In some embodiments the molybdenum compound does not include CO, alkyl, or cyclopentadienyl ligands.

[0324] In some embodiments the precursor is a compound having a formula Mo(X)m(L)n, where m is from 1-4, n is from 1-3, each X is a halide independently selected from F, Cl, Br, and I and each L is an organic ligand as described above, e.g., a ligand independently selected from amidinates, amidates, iminopyrrolidinates, diazadienes, beta-imino amides, alpha-imino alkoxides, beta-amino alkoxides, beta-diketiminates, beta-ketoiminates, beta-diketonates, amines, and pyrazolates, thioethers, thiolates, dithiolenes, dithiolates, and α-imino thiolenes. In some embodiments in the named ligands each R is independently selected from H, alkyl, and fluoroalkyl.

[0325] In some embodiments L is a bidentate ligand. Examples of suitable precursors of formula Mo(L)Cl4, that utilize bidentate ligands are shown in Figure 3C. These are Mo(V) compounds and include an amidinate molybdenum complex 27, a DAD complex 28, a beta-diketiminate complex 29, a pyrazolate complex 30, an amidate complex 31, a beta-imino amide complex 32, a beta- ketoiminate complex 33, a beta-amino alkoxide complex 34, an iminopyrrolidinate complex 35, an alpha-imino alkoxide complex 36, and a beta-diketonate complex 37.

[0326] The heteroleptic complexes with molybdenum-halide bonds and organic ligands described herein can be synthesized using a reaction of molybdenum halide starting materials with the compounds comprising organic ligands in neutral or anionic form. For example molybdenum(V) precursors may be prepared using MoCl5as a starting material. Mo(III) precursors may be prepared using MoX3(THF)3as a starting material, where X is selected from chloride, bromide, and iodide, and THF is tetrahydrofuran. The starting materials can be treated with the ligand in a neutral or anionic form (e.g. a salt, such as lithium or sodium salt), to form the heteroleptic complexes described herein. Equation 1 illustrates preparation of amidinato- tetrachloromolybdenum(V) using a reaction of molybdenum pentachloride with lithium amidinate. Equation 2 illustrates preparation of bis-amidinato-trichloromolybdenum(V) using a reaction of molybdenum pentachloride with two equivalents of lithium amidinate. The stoichiometry of the molybdenum precursors (the number of halides and organic ligands in the resulting precursor) can be controlled by controlling the stoichiometric ratios of starting materials.

[0327] The reactions may be conducted in a variety of non-protic solvents. For example the 65 LAMRP922WO-11400-WOreaction 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.

[0328] The heteroleptic molybdenum compounds containing molybdenum-halide bonds and organic ligands described herein can advantageously provide high purity molybdenum metal in CVD and ALD deposition. Further, the use of these compounds can be associated with reduced etching of the substrate materials as compared with conventional homoleptic molybdenum halides. These advantages are described for illustration purposes and do not limit the use of these compounds solely to molybdenum metal deposition or to deposition on etching-sensitive substrates.

[0329] In some embodiments, when deposition is conducted on fluorine-sensitive materials (e.g., silicon-containing materials) the precursors are selected to be fluorine free, e.g., include any of the Cl, Br, and I as the halides in the complex. Further, the use of compounds with fluoroalkyl substituents may be avoided in these embodiments. Sulfur-containing molybdenum compounds

[0330] In one aspect, sulfur-containing molybdenum compounds are used as precursors for deposition of molybdenum-containing films, such as for deposition of molybdenum metal, molybdenum sulfide, molybdenum nitride or molybdenum carbide. In some embodiments, the molybdenum compounds include molybdenum, and at least one sulfur-containing ligand providing molybdenum-sulfur bonding. Molybdenum precursors which are based on sulfur-containing ligands can be used to deposit molybdenum-containing films which are substantially free of impurities due to the ease of removal of sulfur impurities compared to oxygen, carbon, and nitrogen impurities. In some embodiments, the molybdenum compounds do not include molybdenum-carbon bonds and / or do not include molybdenum-oxygen double bonds. In some embodiments the molybdenum compounds do not include molybdenum-nitrogen double bonds. In some embodiments in the provided molybdenum precursors molybdenum forms bonds only with sulfur atoms. 66 LAMRP922WO-11400-WO

[0331] Examples of suitable sulfur-containing ligands that provide sulfur bonding include thioethers, thiolates, dithiolenes, dithiolates, thiocarbamates, and α-imino thiolenes. The ligands can include one or more substituents independently selected from the group consisting of H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. The ligands can be neutral or anionic (e.g., monoanionic or dianionic), and molybdenum can be in a variety of oxidation states, such as 0, +1, +2, +3, +4, +5, and +6.

[0332] In some embodiments the sulfur-containing ligands are ligands 18-25 shown in Figure 3C, where R substituents are as previously described. Examples of suitable molybdenum precursors include molybdenum thiolates Mo(SR)4, wherein R is an alkyl, e.g., methyl, ethyl propyl, butyl. In one specific example, the precursor is tetrakis(tert- butylthiolato)molybdenum(IV): Mo(SR)4, wherein R is t-butyl. Another example of suitable molybdenum precursors are molybdenum thiocarbamates, such as tetrakis(diethyldithiocarbamato)molybdenum(IV):where each R is independently selected from alkyl (e.g., ethyl, methyl, propyl, butyl), and fluoroalkyl (e.g., CF3). In one specific example the precursor is tetrakis(diethyldithiocarbamato)molybdenum(IV).

[0333] In some embodiments dithiolene complexes of molybdenum are provided, where dithiolene may be in a neutral form 20, anion-radical form 21, and dianionic form 22, where each R is independently H, alkyl or fluoroalkyl.

[0334] Dithiolene complexes are redox-active and can support molybdenum in a variety of oxidation states. Redox reactions of dithiolene ligands 20, 21, and 22 are shown in Equation 3: (Equation 3)

[0335] In one implementation, the precursor is Mo(21)3, where each R in 21 is independently selected from H, alkyl, and fluoroalkyl. For example, R may be methyl, ethyl, CF3, etc. This is a homoleptic Mo(III) compound containing exclusively molybdenum-sulfur bonds.

[0336] In some embodiments, the ligands may provide nitrogen bonding in addition to sulfur 67 LAMRP922WO-11400-WObonding. One example of such ligand is alpha-iminothiolene 23, which is a redox-active radical anion ligand that can exhibit behavior similar to that of thiolenes. In some embodiments the precursor is Mo(III) compound Mo(23)3, where each R in compound 23 is independently selected from H, alkyl, and fluoroalkyl.

[0337] In some embodiments, the precursor is MoLncompound, where n is from 2 to 6, and L is a sulfur-containing ligand, such as any of the sulfur-containing ligands described herein. In some embodiments each L is the same sulfur-containing ligand. In other embodiments the precursor may include different sulfur containing ligands L. Examples of precursors include Mo(19)2, Mo(19)3, Mo(19)4, Mo(19)5, Mo(19)6, Mo(19)2(18)2, Mo(19)3(18), Mo(19)4(18)2, Mo(21)3,Mo(20)(21)2, Mo(22)3,Mo(21)(22)2, Mo(20)(22)2, Mo(23)3, Mo(24)3, Mo(25)3.The sulfur-containing molybdenum compounds described herein can be synthesized using a reaction of molybdenum halide starting materials with the compounds comprising organic sulfur-containing ligands in neutral or anionic form. For example molybdenum(V) precursors may be prepared using MoCl5as a starting material. Mo(III) or Mo(IV) precursors may be prepared using corresponding halides or MoX3(L)3or MoX4(L)2as a starting material, where X is selected from chloride, bromide, and iodide, and L is a neutral Lewis base such as tetrahydrofuran or diethyl ether. The starting materials can be treated with the desired sulfur-containing ligand in a neutral or anionic form (e.g. a salt, such as lithium or sodium salt), to form the sulfur-containing complexes described herein.

[0338] In one example, Mo(IV) thiolato complexes are prepared by reacting molybdenum tetrachloride with lithium thiolates. For example MoCl4can be reacted with t-BuSLi in 1,2- dimethoxythane solvent to form Mo(t-BuS)4compound.

[0339] α-Iminothiolene ligands can be prepared from the corresponding α-iminoketone by thionation using a suitable reagent such as Lawesson’s reagent. The radical anionic form of the α- iminothiolene can be prepared subsequently by treatment with an alkali metal, such as lithium. The resulting ligands and ligand salts can be reacted with molybdenum halides to form α- iminothiolene-containing molybdenum compounds.

[0340] Molybdenum complexes can also be prepared using a zero valent starting material such as molybdenum hexacarbonyl. 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.

[0341] The reactions may be conducted in a variety of non-protic solvents. For example the 68 LAMRP922WO-11400-WOreaction 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. 1,4-Diazabutadiene (DAD) Containing Precursors

[0342] In another aspect, DAD-containing molybdenum precursors are provided. DAD can bind to molybdenum in its neutral form 5, in its radical-anionic form 6, and in its dianionic form 7. In some embodiments, homoleptic DAD complexes are provided of formula Mo(DAD)m, where m is from 1 to 3, and each DAD is independently selected from neutral DAD 5, radical-anionic DAD 6, and dianionic DAD 7. The oxidation state of molybdenum in these complexes can range from 0 to +6. Non-limiting examples of suitable homoleptic DAD complexes include tris-DAD Mo(III) precursor Mo(6)3, bis-DAD Mo(IV) precursor Mo(7)2, bis-DAD Mo(III) precursor Mo(6)(7), and bis-DAD Mo(II) precursor Mo(6)2.

[0343] In some embodiments homoleptic DAD complexes (i.e., compounds having the same ligands) are prepared using a reaction between molybdenum halide and a source of DAD ligand in the required electronic configuration. For example, tris-DAD Mo(III) precursor Mo(6)3can be synthesized by reacting MoCl3with three equivalents of the radical anion form of the DAD ligand, which can be prepared from the neutral form of the DAD ligand by treatment with an alkali metal, such as lithium, in a solvent, such as THF, as shown in Equation 4(Equation 4)

[0344] In some embodiments, heteroleptic DAD-containing molybdenum compounds are provided. In some implementations the precursor includes molybdenum, at least one DAD ligand bound to molybdenum, and at least one second ligand, wherein the DAD may be neutral DAD 6, radical anionic DAD 7, or dianionic DAD 8, and the second ligand is independently selected from 69 LAMRP922WO-11400-WOanionic ligands and neutral ligands. In some embodiments the precursor does not contain CO ligands as the only second ligands. In some embodiments the precursor is Mo(DAD)m(L)n(X)p, where L is a neutral Lewis base ligand and each L is independently selected from CO, an amine, a phosphine, a thioether, a nitrile, and an isonitrile, and X is an anionic ligand, and each X is independently selected from a halide, an alkyl, an allyl, and a cyclopentadienyl, and m is 1-3, n is 0-4, and p is 0-4. Nitriles are RCN compounds, where R is an alkyl. Isonitriles are RNC compounds, where R is an alkyl. Other suitable anionic ligands include alkoxides, amides, imides, and any other anionic ligands that include a donor atom chosen from C, N, O, B, S, Si, Al, and P.

[0345] Examples of heteroleptic DAD-containing precursors include without limitation Mo(7)2(RCN)Cl, Mo(7)2(RNC)Cl, Mo(8)(CO)3,Mo(6)(13)Cl, Mo(6)(18)Cl2, Mo(6)2Cl, Mo(6)2(14), Mo(6)2(19), Mo(6)2(24).

[0346] Heteroleptic DAD-containing precursors can be prepared by sequential salt metathesis reactions in one pot or using multiple steps. Molybdenum halide starting materials such as Mo(V), Mo(IV), or Mo(III) halides can be treated with anionic forms of a DAD ligand or other anionic ligands. Neutral Lewis base ligands can be exchanged using thermal treatment or photoexcitation.

[0347] Heteroleptic DAD-containing precursors can also be prepared using a zero valent molybdenum starting material, such as molybdenum hexacarbonyl, which can undergo oxidative addition with redox active ligands, such as DAD ligands.

[0348] In some embodiments, the precursors containing radical anionic DAD ligand 8 are particularly preferred for deposition of molybdenum metal and high purity molybdenum metal. In the radical anionic form 7, the DAD ligand is electronically coupled to vacant molybdenum d- orbitals and is believed to serve as a source of electrons which reduce the molybdenum ions to the zerovalent metallic state. After ligand-to-metal electron transfer, the volatile, neutral DAD ligand 6 can be purged away from the molybdenum metal growth surface. Since the DAD ligand can be removed intact from the growth surface, incorporation of impurity elements such as C and N are reduced when using DAD precursors as compared to other metalorganic precursors. Therefore, molybdenum precursors containing radical anionic DAD ligands can be used for depositing high purity molybdenum metal at low temperatures. Di-Molybdenum Precursors

[0349] In another aspect, precursors for deposition of molybdenum-containing films are di- molybdenum compounds containing a 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). Such precursors are particularly useful for deposition of molybdenum metal and high 70 LAMRP922WO-11400-WOpurity molybdenum metal because it is easier to reduce such compounds to metallic molybdenum than many mononuclear molybdenum compounds.

[0350] In some embodiments, a precursor for deposition of molybdenum-containing films is provided, wherein the precursor is Mo2Ln, wherein each L is independently selected from amidate, amidinate, and guanidinate ligands, n is 2-5, and where the precursor includes a multiple molybdenum-molybdenum bond. In some embodiments each L is independently selected from an amidinate ligand 2, amidate ligand 3, and a guanidinate ligand 15, wherein each R in the amidinate, amidate, and guanidinate is independently selected from H, alkyl, fluoroalkyl, alkylsilyl, alkylamino, and alkoxy substituents. In some embodiments each R is independently selected from H, alkyl, and fluoroalkyl. In some embodiments each L is an amidinate and the precursor has a formula Mo2(L)3or Mo2(L)4. In some embodiments each L is an amidinate and the precursor has a formula Mo2(L)3or Mo2(L)4. In some embodiments each L is a guanidinate and the precursor has a formula Mo2(L)3or Mo2(L)4.In these complexes molybdenum has a low oxidation state 2+ (in Mo2(L)3) and 3+ in (Mo2(L)4) making these complexes particularly suitable for facile reduction to molybdenum metal.

[0351] One exemplary structure of an amidate paddlewheel di-Mo (II) precursor having a quadruple molybdenum-molybdenum bond is shown by structure 38:Mo(II) amidate precursor 38

[0352] In some embodiments each of R and R’ is independently selected from alkyls, such as methyl, ethyl, isopropyl, and t-butyl. In some embodiments one, two, three or four amidate ligands in 38 may be substituted by amidinate or guanidinidate ligands.

[0353] Di-molybdenum precursors described herein can be synthesized using dimolybdenum tetraacetate as a starting material by treatment with a ligand salt such as lithium amidate. In one aspect, a container housing any of the precursors described herein in a solid or liquid form is provided. In another aspect a solution of any of these precursors is provided, where the solvent may include, for example, a high boiling point hydrocarbon solvent, such as a higher alkane. In some embodiments a container holding the molybdenum precursor (in solid or liquid form or in solution) is filled with an inert gas, such as nitrogen (N2), or argon (Ar), to prevent contact of the 71 LAMRP922WO-11400-WOprecursor with air, and possible decomposition due to contact with moisture and / or air. In some embodiments the container is adapted for vaporization of the precursor inside the container. For example, the container may include an inlet and an outlet, where the inlet is adapted to be connected with a source of a carrier gas that can be flowed over or through the precursor thereby assisting in precursor vaporization. The outlet is adapted for removing the carrier gas and the precursor vapor from the container and is configured to be connected to a conduit that can be used to deliver the precursor vapor to the processing chamber. The inlet and the outlet each has a closed position and an open position, and, for example, can include manual valves that can be used to switch from closed to open positions and back. When the container is stored or transported the inlet and the outlet are closed. When the container is fitted to the deposition apparatus for use, the inlet and the outlet valves may be open, and a carrier gas may be flown into the inlet, and out from the outlet carrying the precursor vapor. In some embodiments the container has a flow-over design, in which the inlet and the outlet are positioned above the surface of the precursor. For example in a cylindrical container the inlet and the outlet may be positioned at a similar vertical elevation (e.g., the vertical distance between the inlet and the outlet may be less than about 20% of the cylinder height). In other embodiments the container has a bubbler design, in which the inlet is positioned below the surface of the precursor and the outlet is positioned above the inlet (e.g., above the surface of the precursor). For example in a cylindrical container the inlet and the outlet may be positioned far from each other in a vertical direction (e.g., the vertical distance between the inlet and the outlet may be more than about 30%, such as more than about 50%, or more than about 80% of the cylinder height. COPPER PRECURSORS

[0354] Copper metal can be deposited using a variety of copper precursors, where copper may be in +1 or +2 oxidation states. The precursors may be cuprous (copper (I)) compounds such as acetylacetonates, ketoiminates, diiminates, cyclopentadienyl compounds, amidinates, guanidinates or amides; or cupric (copper (II)) compounds such as acetylacetonates, ketominates or aminoalkoxides. In some embodiments the precursors are coordination complexes, where copper coordinates to a multiple bond such as a double or triple bond; or coordinates to the oxygen of a carbonyl group for example.

[0355] Examples of copper precursors include Cu(acac)2where acac = acetylacetonato; Cu(thd)2where thd = tetrahydrodionato); hexafluoroacetylacteonate-copper-trimethylsilane; cyclopentadienyl (Cp) compounds such as CpCu(CNMe), CpCu(CNCMe3), CpCuCO, CPCuPR3(where R = Me, Et or Ph) and CpCu(CSiMe3)2; alkyl or aryl compounds such as MeCu(PPh3)3, 72 LAMRP922WO-11400-WOCuMe, CuCCH( ethynylcopper), CuCMe3(methylacetylide copper), (H2C=CMeCC)Cu(3- methyl-3-buten-1ynylcopper), CuCCPh, C6H5Cu (phenyl copper), (Me)3CCCCu (3,3-dimethyl-1- butynyl) copper, Me3SiCCCH2Cu; and other compounds such as CuCN, [Cu(OAc]n(where OAc = acetate), Cu2Cl2(butadiene), C7H7CuO(2-methoxyphenylcopper), (MeCN)4CuX (where X is a halide, an alkyl, an amine or a phenyl group), Me3SiOCu(PMe3)3, Cu(C4H4S) and Cu-carbene compounds such as those derived from imidazolium. COBALT PRECURSORS

[0356] Cobalt metal can be deposited using a variety of cobalt precursors, where cobalt may be in +1, +2 or +3 oxidation states. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonates (e.g., cobalt (III) bis(acetylacetonate)), cobalt amidinates (e.g., bis(N-t-butyl-N’- ethylpropanimidamidato)cobalt(II),) cobaltocene, and carbonyl-containing cobalt precursors (e.g., cobalt tricarbonyl nitrosyl, and cyclopentadienylcobalt dicarbonyl). An example of a halogen- containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N′,N′tetramethylethylenediamine. RUTHENIUM PRECURSORS

[0357] Ruthenium metal can be deposited, for example, using vaporizable ruthenium precursors, such as bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienylpropylcyclopentadienylruthenium(II). CONCLUSION

[0358] 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. 73 LAMRP922WO-11400-WO

Claims

CLAIMS What is claimed is:

1. A method for processing substrates, the method comprising: providing a substrate having a negative feature in a low-k dielectric; and depositing molybdenum into the negative feature to at least partially fill the negative feature with molybdenum over a copper layer.

2. The method of claim 1, wherein the molybdenum is deposited by exposing the substrate to a first hydrogen gas and a molybdenum-containing precursor gas.

3. The method of claim 2, wherein the exposing the substrate to the first hydrogen gas and the molybdenum-containing precursor gas are performed in a process chamber housing the substrate and a purge gas is periodically pulsed during the depositing of the molybdenum to purge excess byproducts from the process chamber.

4. The method of any of claims 2 or 3, wherein the first hydrogen gas is pulsed.

5. The method of claim 4, when depending from claim 3, wherein the pulses of the first hydrogen gas and the purge gas are alternating pulses.

6. The method of claim 5, wherein depositing the molybdenum comprises pulsing the molybdenum-containing precursor.

7. The method of claim 6, wherein the pulses of the first hydrogen gas, molybdenum- containing precursor, and purge gas are temporally sequential pulses.

8. The method of any of claims 5-7, further comprising exposing the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum into the negative feature.

9. The method of claim 1, wherein the molybdenum is deposited over a tungsten layer, and wherein the molybdenum is deposited on a second copper layer, wherein the second copper layer is between the tungsten layer and the molybdenum. 74 LAMRP922WO-11400-WO10. The method of claim 9, wherein the molybdenum acts as a V0 layer, and the second copper layer acts as a M0 layer.

11. The method of claim 1, wherein the molybdenum is deposited directly on tungsten for use as a molybdenum M0 layer.

12. The method of claim 1, wherein the molybdenum is deposited directly on the copper layer for use as a molybdenum M0 layer.

13. The method of claim 1, wherein the molybdenum is deposited directly on an electromigration layer.

14. The method of claim 11, wherein the molybdenum is also deposited on the molybdenum M0 layer to form a molybdenum V0 layer.

15. The method of claim 11, wherein a second copper layer is deposited over the molybdenum M0 layer to form a copper V0 layer.

16. The method of any of claims 1, 9, 10, or 15, wherein a barrier layer is formed between the first copper layer and the molybdenum.

17. The method of claim 16, wherein the barrier layer is an electromigration layer.

18. The method of claim 16, wherein the barrier layer is a diffusion barrier layer.

19. The method of claim 16, wherein the barrier layer comprises cobalt.

20. The method of claim 16, wherein the barrier layer comprises ruthenium.

21. The method of claim 16, wherein the barrier layer comprises cobalt ruthenium alloy.

22. The method of claim 17, wherein the barrier layer comprises tantalum nitride. 75 LAMRP922WO-11400-WO23. The method of claim 17, wherein the cobalt is positioned between a first copper layer and a tantalum oxide.

24. A method for processing substrates, the method comprising: providing a substrate having a feature thereon to be used to form a line in a semiconductor device; and depositing molybdenum into the feature to at least partially fill the feature with molybdenum by exposing the substrate to a continuous flow of a first hydrogen gas source and a molybdenum-containing precursor, wherein during the continuous flow of the first hydrogen gas source, the substrate is exposed to one or more deposition cycles of the following temporally sequential pulses: (1) pulse of a second hydrogen gas source, (2) pulse of a first purge gas, (3) pulse of a molybdenum-containing precursor source for delivering the molybdenum-containing precursor, and (4) pulse of a second purge gas.

25. The method of any of claims 1-24, wherein the molybdenum-containing precursor comprises a structure of Formula (I), Formula (II) or Formula (III): MoLn(I), Mo2Ln(II), or LnMo(L’)mMoLn(III), wherein each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3.

26. The method of claim 25, wherein each L is independently a monodentate ligand.

27. The method of claim 26, wherein the monodentate ligand comprises hydrogen, halo, hydroxy, alkyl silyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, 76 LAMRP922WO-11400-WOaliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3alkyl)C(O)(C1-C3alkyl), -C1-C3alkylamino, alkenylamino, alkynylamino, di(C1-C3alkyl)amino, -C(O)O-(C1-C3alkyl), -C(O)NH-(C1-C3alkyl), -CH=NOH, -P(C1-C3alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-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, -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.

28. The method of any of claims 1-25, wherein the molybdenum-containing precursor comprises a molybdenum halide or a molybdenum oxyhalide.

29. The method of claim 28, wherein the molybdenum oxyhalide comprises MoqOnYm, wherein Y is a halogen; n is 1 or 2; q is 1, 2 or 4; and m is 1, 2 or 11.

30. The method of claim 29, wherein the molybdenum oxyhalide comprises MoOF4, Mo4O11I, MoO2I, MoOBr4, MoO2Br2, MoO2Cl2, MoOCl4,Mo2Cl10or combinations thereof.

31. The method of claim 28, wherein the molybdenum halide comprises MoCl5or MoF6.

32. The method of claim 28, wherein the molybdenum is deposited over a copper layer.

33. The method of claim 32, wherein the molybdenum is deposited directly on the copper layer.

34. The method of claim 28, wherein the molybdenum is deposited directly on an electromigration layer.

35. The method of any of claims 1-25, wherein the molybdenum-containing precursor comprises Mo(CO)6or C16H20Mo. 77 LAMRP922WO-11400-WO36. The method of claim 25, wherein the molybdenum-containing precursor comprises a low valent molybdenum-containing precursor.

37. The method of any of claims 24-36, wherein the hydrogen gas comprises hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and oxygen, hydrogen and nitrogen, ammonia, singly deuterated ammonia, doubly deuterated ammonia, triply deuterated ammonia, hydrazine, an alcohol, an aldehyde or combinations thereof.

38. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising a chuck; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with the flow-control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause a feature of the substrate to be at least partially filled with molybdenum as a V0 or M0 layer over a copper layer.

39. The apparatus of claim 38, wherein the controller further comprises instructions for causing deposition of copper over the molybdenum to form a copper M1 layer to completely fill the feature.

40. The apparatus of claim 38, wherein the controller further comprises instructions for causing the molybdenum to be deposited directly on copper for use as a molybdenum M0 layer.

41. The apparatus of claim 38, wherein the controller further comprises instructions for causing the molybdenum to be deposited directly on an electromigration layer.

42. The apparatus of claim 38, wherein the controller further comprises instructions for 78 LAMRP922WO-11400-WOcausing deposition of molybdenum by causing exposure of the substrate to a first hydrogen gas and a molybdenum-containing precursor gas.

43. The apparatus of claim 42, wherein the exposures are performed in a process chamber housing the substrate and the controller further comprises instructions for causing periodic pulsing of a purge gas during the deposition of the molybdenum to purge excess byproducts from the process chamber.

44. The apparatus of any of claims 42 or 43, wherein the controller further comprises instructions for causing the first hydrogen gas to be pulsed in temporally sequential pulses.

45. The apparatus of claim 44, wherein the controller further comprises instructions for causing alternating of the pulses of the first hydrogen gas and the purge gas.

46. The apparatus of claim 45, wherein the controller further comprises instructions for causing pulsing of the molybdenum-containing precursor such that the substrate is exposed to the molybdenum-containing precursor when the substrate is not exposed to the purge gas.

47. The apparatus of claim 46, wherein the controller further comprises pulsing of the first hydrogen gas such that the substrate is exposed to the first hydrogen gas when the substrate is neither exposed to the purge gas nor the molybdenum-containing precursor.

48. The apparatus of any of claims 45-47, wherein the controller further comprises exposing of the substrate to a continuous flow of a second hydrogen gas throughout a duration for depositing the molybdenum into the feature. 79 LAMRP922WO-11400-WO

Images