Deposition of metal-containing films

Abstract

A method is provided for depositing a metal-containing film by using an iodine-containing reagent and a metal-containing precursor to generate an iodine-bonded metal species in situ, followed by reduction at a process temperature below 400°C. In particular, the film can be a molybdenum-containing film. The method may also include simultaneous introduction of the reagent and precursor, or an optional pretreatment using a passivating gas. Also provided is a method for depositing a molybdenum-containing film on a semiconductor using a low-valent molybdenum-containing precursor. The low-valent molybdenum precursor, which has one or two molybdenum atoms, may have at least one ligand, which is an isocyanohaloalkyl group, an allyl group, an aryl group, a tertiary organophosphino group, or an alkoxide group.

Description

[Technical Field]

[0001] [Incorporated by reference] A PCT application is filed concurrently herewith as part of this application. Each application identified in the concurrently filed PCT application to which this application claims benefit or priority is incorporated herein by reference in its entirety for all purposes.

[0002] FIELD OF THE DISCLOSURE The present disclosure relates to methods of producing semiconductor devices. In particular, embodiments of the present disclosure relate to precursors used in the deposition of molybdenum-containing films in semiconductor processing. [Background technology]

[0003] In integrated circuit (IC) manufacturing, deposition and etching techniques are used to form patterns of materials, such as forming metal lines embedded in a dielectric layer. Some patterning schemes require conformal deposition of materials, requiring the deposited layer to follow the contours of protruding and / or recessed features on the substrate's surface. Atomic layer deposition (ALD) is often the preferred method for forming conformal films on substrates because it relies on the adsorption of one or more reactants (precursors) onto the substrate's surface, followed by chemical conversion of the adsorbed layer into the desired material. Because ALD employs sequential reactions occurring at the substrate's surface that are separated in time and typically limited by the amount of adsorbed reactants, this method can provide thin conformal layers with excellent step coverage.

[0004] Atomic layer deposition (ALD) is a known method for thin film deposition. It is a unique self-limiting, continuous film growth technique based on surface reactions, allowing atomic layer control and the deposition of conformal thin films of precursor-delivered materials onto substrates of various compositions. In ALD, each precursor is traditionally separated during the reaction. The first precursor is passed over the substrate, creating a monolayer on the substrate. Any excess unreacted precursor is pumped out of the process chamber. The second precursor is then passed over the substrate, reacting with the first precursor to form a monolayer film on the substrate surface. This cycle is repeated to create a film of the desired thickness, often at process temperatures exceeding 450°C.

[0005] Deposition of metal-containing films at lower temperatures (below 400° C.) would be advantageous for certain applications. At these reduced temperatures, the potential for impurities increases. Therefore, ALD processes that can be performed at lower temperatures and minimize impurities are desirable.

[0006] Chemical vapor deposition (CVD) is another deposition method widely used in semiconductor processing. In CVD, the reaction occurs within the volume of the process chamber and is not limited by the amount of reactant adsorbed on the substrate. As a result, CVD-deposited films are often less conformal than ALD-deposited films. CVD is typically used in applications where step coverage is less important.

[0007] ALD and CVD may use a plasma to promote the reaction of deposition precursors, resulting in the formation of the desired film. Methods that utilize a plasma are known as plasma-enhanced ALD (PEALD) and plasma-enhanced CVD (PECVD). Methods that do not employ a plasma are called thermal ALD and thermal CVD.

[0008] Although ALD and CVD are most commonly used for the deposition of silicon-containing films such as silicon oxide, silicon nitride, and silicon carbide, these methods are also suitable for the deposition of some metals, most notably tungsten and cobalt.

[0009] The background discussion provided herein is intended to present the contents of the present disclosure generally. Work by the currently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be considered prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present disclosure. Summary of the Invention

[0010] A method for depositing a metal-containing film is provided by using an iodine-containing reagent and a metal-containing precursor to generate an iodine-bonded metal species in situ (generated within the process chamber) and then reducing it at a process temperature below 400°C. In some cases, the method may also include co-introduction of the iodine-containing reagent and the metal-containing precursor, or an optional pretreatment with a passivating gas. In particular, the precursor can be a molybdenum-containing precursor, such as a low-valent molybdenum precursor, and the film can be a molybdenum-containing film. The method may advantageously produce metal-containing films with low halogen-based or other impurities. Also provided are low-valent molybdenum precursors containing one or two molybdenum atoms, having at least one ligand that is an isocyanohaloalkyl group, an allyl group, an aryl group, a tertiary organophosphino group, or an alkoxide group. Additionally, molybdenum metal, molybdenum nitride (MoN), and other molybdenum-containing films are also provided. x ), molybdenum carbide (MoC x ), molybdenum boride (MoB x ), molybdenum disilicide (MoSi x ), and their combinations (molybdenum carbonitride (MoC x N y ), molybdenum boride carbide (MoB x C y The present invention provides a method for depositing a molybdenum-containing film, such as a molybdenum-containing film.

[0011] Thus, in a first aspect, the present disclosure encompasses a method for depositing a film on a semiconductor substrate. In some embodiments, the method includes providing a semiconductor substrate in a process chamber, forming an iodine-bond-containing metal species in the process chamber, and exposing the iodine-bond-containing metal species to a reducing agent to form a metal-containing film on the semiconductor substrate, wherein the reducing agent comprises a hydrogen-containing gas source.

[0012] In some embodiments, forming the iodine bond-containing metal species comprises (i) introducing a metal-containing precursor into a process chamber comprising a semiconductor substrate; and (ii) introducing an iodine-containing reagent to react with the metal-containing precursor.

[0013] In some embodiments, forming the iodine bond-containing metal species comprises (i) introducing an iodine-containing reagent into a process chamber containing a semiconductor substrate; and (ii) introducing a metal-containing precursor to react with the iodine-containing reagent.

[0014] In some embodiments, the metal-containing precursor is a vanadium-containing precursor, a niobium-containing precursor, a tantalum-containing precursor, a chromium-containing precursor, a cobalt-containing precursor, a titanium-containing precursor, a hafnium-containing precursor, a tungsten-containing precursor, an iron-containing precursor, a ruthenium-containing precursor, a nickel-containing precursor, a zinc-containing precursor, a zirconium-containing precursor, a copper-containing precursor, a molybdenum-containing precursor, or a combination thereof.

[0015] In some embodiments, the metal-containing precursor is a molybdenum-containing precursor.

[0016] In some embodiments, the molybdenum precursor is represented by Formula (I), Formula (II), or Formula (III): MoL n (I), Mo2L n (II), or L n Mo(L') m MoL n(III), where each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L′ is a linking moiety; n is 2, 3, 4, 5, or 6; and m is 1, 2, or 3.

[0017] In some embodiments, each L is independently a monodentate ligand.

[0018] In some embodiments, the monodentate ligand is hydrogen, halo, hydroxy, alkylsilyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH= NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, ═O, ═S, = N, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimide, carbamate, aryloxyalkyl, carboxyl, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, or cyclyl.

[0019] In some embodiments, the molybdenum-containing precursor is a molybdenum halide or a molybdenum oxyhalide.

[0020] In some embodiments, the molybdenum oxyhalide is Mo q O n Y m (Y is a halogen, n is 1 or 2, q is 1, 2, or 4, and m is 1, 2, or 11).

[0021] In some embodiments, the molybdenum oxyhalide is selected from the group consisting of MoOF, MoO 11 I, MoO2I, MoOBr4, MoO2Br2, MoO2Cl2, MoOCl4, Mo2Cl 10 , or a combination thereof.

[0022] In some embodiments, the molybdenum halide is MoCl5 or MoF6.

[0023] In some embodiments, the molybdenum-containing precursor is Mo(CO) or C 16 H 20 This is Mo.

[0024] In some embodiments, the molybdenum-containing precursor is a low-valent molybdenum-containing precursor.

[0025] In some embodiments, the low valent molybdenum precursor has a 0, 1, 2, or 3 oxidation state.

[0026] In some embodiments, the iodine-containing reagent is hydrogen iodide, iodine, an alkyl iodide, an iodosilane, an alkyliodosilane, a metal iodide, or a metal bromide.

[0027] In some embodiments, the alkyl iodide is CH3I, C2H5I, C3H7I, C4H9I, CH2I2, C2H4I2, C3H6I2, or C4H8I2.

[0028] In some embodiments, the iodosilane is SiH3I, SiH2I2, SiHI3, SiI4, or Si2I6.

[0029] In some embodiments, the alkyliodosilane is Si(CH3)I3, Si(CH3)2I2, Si(CH3)3I, Si(CH3)(H)I2, Si(CH3)2(H)I, or Si(CH3)(H)2I.

[0030] In some embodiments, the metal iodide is TiI4 or AlI3.

[0031] In some embodiments, the iodine-containing reagent is BI3.

[0032] In some embodiments, the iodine bond-containing metal species is MoI2, MoI3, or a combination thereof.

[0033] In some embodiments, the reducing agent is a hydrogen-containing gas source.

[0034] In some embodiments, the hydrogen-containing gas source is hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and oxygen, hydrogen and nitrogen, ammonia, mono-deuterated ammonia, di-deuterated ammonia, tri-deuterated ammonia, hydrazine, alcohol, aldehyde, or a combination thereof.

[0035] In some embodiments, (i), (ii), and exposing the iodine bond-containing metal species to a reducing agent are performed sequentially.

[0036] In some embodiments, the method also includes purging the process chamber with an inert gas after at least one of (i) and (ii).

[0037] In some embodiments, forming the iodine bond-containing metal species and exposing the iodine bond-containing metal species to a reducing agent are performed simultaneously.

[0038] In some embodiments, (ii) and exposing the iodine bond-containing metal species to a reducing agent are carried out simultaneously.

[0039] In some embodiments, the method also includes (i) and purging the process chamber with an inert gas after at least one of simultaneously forming the iodine bond-containing metal species and exposing the iodine bond-containing metal species to the reducing agent.

[0040] In some embodiments, the method also includes purging the process chamber with an inert gas after at least one of (i) and (ii).

[0041] In some embodiments, the method also includes (iii) a pretreatment before (i) with an iodine-containing reagent, a passivating gas, or both an iodine-containing reagent and a passivating gas.

[0042] In some embodiments, the method also includes a simultaneous pretreatment during (i) with a passivating gas.

[0043] In some embodiments, the method also includes purging the process chamber with an inert gas after at least one of (i), (ii), and (iii).

[0044] In some embodiments, the method also includes forming a metal-containing film by cycling (i), (ii), and exposing the iodine bond-containing metal species to a reducing agent.

[0045] In some embodiments, the method also includes forming a metal-containing film by cycling (i) and simultaneously forming an iodine bond-containing metal species and exposing the iodine bond-containing metal species to a reducing agent.

[0046] In some embodiments, the method also includes forming a metal-containing film by repeating (i) and (ii) in a cycle.

[0047] In some embodiments, the method also includes repeating (i) and (ii), and forming a metal-containing film by cycling (i), (ii), and exposing the iodine bond-containing metal species to a reducing agent.

[0048] In some embodiments, the method also includes forming a metal-containing film by cycling (i), (ii), and exposing the iodine bond-containing metal species to a reducing agent.

[0049] In some embodiments, the method also includes forming a metal-containing film by cycling (i), (ii), (iii), and exposing the iodine bond-containing metal species to a reducing agent.

[0050] In some embodiments, the metal-containing film is an elemental molybdenum film, the semiconductor substrate has a plurality of recessed features, and sidewalls of the recessed features comprise a dielectric material.

[0051] In some embodiments, the metal-containing film is a molybdenum nitride film, the semiconductor substrate has a plurality of recessed features, and sidewalls of the recessed features comprise a dielectric material.

[0052] In some embodiments, the temperature of the process chamber is maintained below about 400°C.

[0053] In some embodiments, the temperature of the process chamber is maintained between about 200° C. and about 300° C., and the pressure of the process chamber is less than about 500 Torr.

[0054] In some embodiments, at least one of forming the iodine bond-containing metal species and forming the metal-containing film is atomic layer deposition, no-purge atomic layer deposition, pulsed chemical vapor deposition, or plasma-enhanced atomic layer deposition.

[0055] In a second aspect, the present disclosure encompasses an apparatus for depositing a metal-containing layer on a semiconductor substrate. In some embodiments, the apparatus includes a process chamber, a substrate support for a semiconductor substrate located within the process chamber, a plasma generator configured to generate a plasma within the process chamber, one or more gas inlets into the process chamber and associated flow control hardware, and a controller having at least one processor and memory, wherein the at least one processor and memory are communicatively coupled to each other, and the at least one processor is at least operably coupled to the associated flow control hardware, and the memory stores computer-executable instructions for controlling the at least one processor to form an iodine-bond-containing metal species within the process chamber and form a metal-containing film on the semiconductor substrate by exposing the iodine-bond-containing metal species to a reducing agent.

[0056] In a third aspect, the present disclosure encompasses a method of forming a molybdenum-containing layer on a substrate. In some embodiments, the method includes providing a substrate in a process chamber and introducing a low-valent molybdenum precursor and at least one reactant into the process chamber, wherein the low-valent molybdenum precursor is in an oxidation state of 0, 1, 2, or 3, and the low-valent molybdenum precursor is represented by Formula (I), Formula (II), or Formula (III): MoL n (I), Mo2L n (II), or L n Mo(L') m MoL n (III) wherein each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L' is a linking moiety; n is 2, 3, 4, 5, or 6; and m is 1, 2, or 3; and forming a molybdenum-containing layer on the substrate by reacting a low-valent molybdenum precursor with at least one reactant.

[0057] In some embodiments, the monodentate ligand is hydrogen, halo, hydroxy, alkylsilyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxyal and aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, ═O, ═S, ≡N, —NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimide, carbamate, aryloxyalkyl, carboxyl, carboxy, —C(O)NH(benzyl), amido, azide, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, or cyclyl.

[0058] In some embodiments, the monodentate ligand comprises at least one isocyanato, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, alkoxy, or haloalkoxy.

[0059] In some embodiments, the monodentate ligand is an isocyanohaloalkyl.

[0060] 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.

[0061] In some embodiments, the bidentate ligand has a structure of formula (IV): -(E)e-, where each E is independently NR, C(R) n , Si(R) n , S, O, or P(R) n wherein each R is independently hydrogen, aryl, amino, or aliphatic; e is 1, 2, 3, 4, or 5; and n is 0, 1, or 2.

[0062] In some embodiments, the bidentate ligand is —O(C(R) n ) m O-, -O(C(R) n ) m NR-, -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 the R groups can be joined to form a ring; n is 0, 1, or 2; and m is 1, 2, or 3.

[0063] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL4.

[0064] In some embodiments, the low valent molybdenum precursor has one or two bidentate ligands.

[0065] In some embodiments, the low valent molybdenum precursor has the formula (V): [ka] It has the following structure.

[0066] In the formula, each R 1 independently comprises alkyl or haloalkyl, and each R 2 independently includes carbonyl, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, isocyanato, or isothiocyanato; and n is 0, 1, 2, or 3.

[0067] In some embodiments, each R 2 is independently -CNR 3 and R 3 includes aliphatic, aryl, or heterocyclyl.

[0068] In some embodiments, R 3 is haloalkyl or haloaryl.

[0069] In some embodiments, R 3 is pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C4F9, -C5F 11 , -CH2CF3, -CH(CF3)2, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, or nonafluoro-n-butyl.

[0070] In some embodiments, the low valent molybdenum precursor has formula (VI): [ka] It has the following structure.

[0071] In the formula, each R 4 are independently aliphatic, alkylsilyl, or haloalkyl, or R 4 The substitution moieties may be linked to form a ring.

[0072] In some embodiments, each R 4are independently -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , -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.

[0073] In some embodiments, the low valent molybdenum precursor has formula (VII): [ka] wherein each E is independently NR, C(R) n , Si(R) n , S, O, or P(R) n each R independently comprises hydrogen, aryl, amino, or aliphatic; and each R 5are independently halo, hydroxy, aliphatic, alkylsilyl, 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-C3 alkylamino, alkenylamino, alkynylamino, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, e is 1, 2, 3, 4, or 5; and n is 0, 1, or 2.

[0074] In some embodiments, the low valent molybdenum precursor has formula (VIII): [ka] wherein each E is independently NR, C(R) n , Si(R) n , S, O, or P(R) n wherein each R independently comprises hydrogen, aryl, amino, or aliphatic; e is 1, 2, 3, 4, or 5; and n is 0, 1, or 2.

[0075] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL5.

[0076] In some embodiments, the low valent molybdenum precursor has one bidentate ligand or two bidentate ligands.

[0077] In some embodiments, the bidentate ligand has the formula (IV):-(E) e wherein each E is independently NR, C(R) n , Si(R) n , S, O, or P(R) n wherein each R is independently hydrogen, aryl, amino, or aliphatic; e is 1, 2, 3, 4, or 5; and n is 0, 1, or 2.

[0078] In some embodiments, the bidentate ligand is —O(C(R) n ) m O-, -O(C(R) n ) m NR-, -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 the R groups can be joined to form a ring; n is 0, 1, or 2; and m is 1, 2, or 3.

[0079] In some embodiments, the low valent molybdenum precursor has two bidentate ligands.

[0080] In some embodiments, the low valent molybdenum precursor has formula (X) or formula (XI): [ka] [ka] wherein each R 7 are independently -CH3, -C2H5, -C3H7, -C4H9, -C5H11 , -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , -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(C H3)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, and each R 8 are 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)3, or -CNR 9 and R 9 is aliphatic, aryl, or heterocyclyl.

[0081] In some embodiments, R 9 includes haloalkyl or haloaryl.

[0082] In some embodiments, R 9 are pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , —CH2CF3, —CH(CF3)2, —CH(CH3)(CF3), —C(CH3)2(CF3), —C(CF3)3, or nonafluoro-n-butyl.

[0083] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL6.

[0084] In some embodiments, the low valent molybdenum precursor has one, two, or three bidentate ligands.

[0085] In some embodiments, the bidentate ligand has the formula (IV):-(E) e wherein each E is independently NR, C(R) n , Si(R) n , S, O, or P(R) n wherein each R is independently hydrogen, aryl, amino, or aliphatic; e is 1, 2, 3, 4, or 5; and n is 0, 1, or 2.

[0086] In some embodiments, the bidentate ligand is —O(C(R) n ) m O-, -O(C(R) n ) m NR-, -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 the R groups can be joined to form a ring; n is 0, 1, or 2; and m is 1, 2, or 3.

[0087] In some embodiments, the low valent molybdenum precursor has the formula (XII): Mo(X) p (R10) q wherein each X is independently chloro, fluoro, bromo, or iodo; and each R 10 are 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)3, or -CNR 11 and R 11is aliphatic, aryl, or heterocyclyl; p is 1, 2, 3, or 4; q is 2, 3, 4, or 5; and p+q=6.

[0088] In some embodiments, R 11 is haloalkyl or haloaryl.

[0089] In some embodiments, R 11 are pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , —CH2CF3, —CH(CF3)2, —CH(CH3)(CF3), —C(CH3)2(CF3), —C(CF3)3, or nonafluoro-n-butyl.

[0090] In some embodiments, the low valent molybdenum precursor has the formula (XIII): Mo(R 12 ) r (R 13 ) s wherein each R 12 are 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)3, or -CNR 14 and R 14 is aliphatic, aryl, or heterocyclyl, and each R 13are independently trimethylphosphine, triethylphosphine, tri-i-propylphosphine, 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.

[0091] In some embodiments, R 14 is haloalkyl or haloaryl.

[0092] In some embodiments, R 14 are pentafluoroethyl, heptafluoro-n-propyl, pentafluorobenzyl, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , —CH2CF3, —CH(CF3)2, —CH(CH3)(CF3), —C(CH3)2(CF3), —C(CF3)3, or nonafluoro-n-butyl.

[0093] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL2.

[0094] 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.

[0095] In some embodiments, the low valent molybdenum precursor has a structure of formula MoL3.

[0096] In some embodiments, the low valent molybdenum precursor has one bidentate ligand.

[0097] In some embodiments, the low valent molybdenum precursor has formula (XIV): [ka] wherein each R 15 are independently aliphatic, alkylsilyl, or haloalkyl, or R 15 The substitution moieties may be linked to form a ring.

[0098] In some embodiments, each R 15 are independently -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , -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.

[0099] In some embodiments, the low valent molybdenum precursor has the formula (XV): Mo(OR 16 ) 6, wherein each R 16 are independently aliphatic.

[0100] In some embodiments, the molybdenum-containing layer is molybdenum metal.

[0101] In some embodiments, the molybdenum-containing layer is molybdenum nitride, molybdenum carbide, molybdenum boride, molybdenum silicide, or a combination thereof.

[0102] In some embodiments, the molybdenum-containing layer is a molybdenum-containing film.

[0103] In some embodiments, at least one reactant is hydrogen, ammonia, diborane, water, hydrogen sulfide, a thiol, an alcohol, an amine, hydrazine, a silane, or a disilane.

[0104] In a fourth aspect, the present disclosure encompasses a metal coordination complex. In some embodiments, the complex has the formula (V): [ka] wherein each R 1 is independently alkyl or haloalkyl, and each R 2 is independently carbonyl, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, isocyanato, or isothiocyanato; and n is 0, 1, 2, or 3.

[0105] In a fifth aspect, the present disclosure encompasses metal coordination complexes. In some embodiments, the complexes are represented by Formula (VI), Formula (IX), Formula (X), Formula (XI): [ka] [ka] [ka] [ka] or formula (XV): Mo2(OR 16 ) 6, wherein R 4 , R 6 , R 7 , and R 16 are each independently -CH3, -C2H5, -C3H7, -C4H9, -C5H 11, -CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -C4F9, -C5F 11 , -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; G is =O, =NR, =S, or =CR2; each R is independently an aliphatic group, an aryl group, a haloalkyl group, or a haloaryl group; and each R 8 are 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)3, or -CNR 9 and R 9 is aliphatic, aryl, or heterocyclyl.

[0106] In a sixth aspect, the present disclosure encompasses a metal coordination complex. In some embodiments, the complex has formula (XII) or formula (XIII): Mo(X) p (R 10 ) q (XII) or Mo(R 12 )r(R 13 ) s (XIII), wherein each X is independently chloro, fluoro, bromo, or iodo; and R 10 and R 12each independently represents allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3, or -CNR 14 and R 14 is aliphatic, aryl, or heterocyclyl, and each R 13 are independently trimethylphosphine, triethylphosphine, tri-i-propylphosphine, 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, and 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, and at least one R of formula (XII) 10 Ga-CNR 14 and at least one R of formula (XIII) 12 Ga-CNR 14 This is subject to the condition that:

[0107] In a seventh aspect, the present disclosure encompasses an apparatus for processing a substrate. In some embodiments, the apparatus includes a process chamber having a substrate holder and one or more inlets for introduction of reactants into the process chamber, and an apparatus controller including program instructions for introducing a low-valent molybdenum-containing precursor into the process chamber, where the low-valent molybdenum precursor is in an oxidation state of 0, 1, 2, or 3, and the low-valent molybdenum precursor is represented by Formula (I), Formula (II), or Formula (III): MoL n (I), Mo2L n (II), or L n Mo(L') m MoLn (III) (wherein each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L' is a linking moiety; n is 2, 3, 4, 5, or 6; and m is 1, 2, or 3), and a low-valent molybdenum precursor to form a molybdenum-containing layer on a substrate.

[0108] In another aspect, a non-transitory computer machine readable medium is provided that includes program instructions for control of a deposition tool, where the program instructions include code for causing any of the methods described herein.

[0109] The methods and apparatus described herein can be integrated with processes and apparatus for performing photolithographic patterning. In one aspect, a system is provided, where the system includes any of the apparatus described herein and a stepper.

[0110] The molybdenum-containing precursors described herein can be used in ALD and CVD to deposit molybdenum-containing films in a variety of applications. In some embodiments, the precursors are used to form conformal films. In other embodiments, the precursors are used to fill recessed features with molybdenum-containing materials (e.g., molybdenum metal). For example, the provided precursors and methods can be used to fill contact holes with high-purity molybdenum metal.

[0111] In an eighth aspect, the present disclosure encompasses a method for depositing a film on a semiconductor substrate. In some embodiments, the method includes providing a semiconductor substrate in a process chamber, forming an iodine-bond-containing metal species in the process chamber, and forming a metal-containing film on the semiconductor substrate by exposing the iodine-bond-containing metal species to a reducing agent, wherein forming the iodine-bond-containing metal species includes (i) introducing a metal-containing precursor into a process chamber comprising the semiconductor substrate and (ii) introducing an iodine-containing reagent to react with the metal-containing precursor, or forming the iodine-bond-containing metal species includes (i) introducing an iodine-containing reagent into a process chamber comprising the semiconductor substrate and (ii) introducing the metal-containing precursor to react with the iodine-containing reagent, wherein the metal-containing precursor includes a low-valent molybdenum precursor, the low-valent molybdenum precursor having an oxidation state of 0, 1, 2, or 3, and the low-valent molybdenum precursor is represented by Formula (I), Formula (II), or Formula (III): MoL n (I), Mo2L n (II), or L n Mo(L') m MoL n (III), where each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L′ is a linking moiety; n is 2, 3, 4, 5, or 6; and m is 1, 2, or 3.

[0112] These and other examples of the subject matter described herein are set forth in the accompanying drawings and the description below. [Brief explanation of the drawings]

[0113] [Figure 1A] FIG. 1A is a cross-sectional view of a substrate during deposition of a metal-containing film in accordance with certain disclosed embodiments. [Figure 1B] FIG. 1B is a cross-sectional view of a substrate during deposition of a metal-containing film, according to certain disclosed embodiments. [Figure 1C] FIG. 1C is a cross-sectional view of a substrate during deposition of a metal-containing film, according to certain disclosed embodiments.

[0114] [Figure 2A] FIG. 2A is a process flow diagram of a method for forming a metal-containing film by exposure to a metal-containing precursor, an iodine-containing reagent, and a reducing agent, according to certain disclosed embodiments.

[0115] [Figure 2B] FIG. 2B provides an example of the general structure of a molybdenum precursor according to certain disclosed embodiments.

[0116] [Figure 2C] FIG. 2C provides an example of a low-valent molybdenum precursor of formula Mo(L) 6 according to certain disclosed embodiments.

[0117] [Figure 2D] FIG. 2D provides an example of a low-valent dimolybdenum precursor according to certain disclosed embodiments.

[0118] [Figure 3] FIG. 3 is a process flow diagram of a method for forming a metal-containing film by exposure to a metal-containing precursor and simultaneous exposure to an iodine-containing reagent and a reducing agent, according to certain disclosed embodiments.

[0119] [Figure 4] FIG. 4 is a process flow diagram of a method for forming a metal-containing film by a cyclic deposition process, according to certain disclosed embodiments.

[0120] [Figure 5] FIG. 5 is a process flow diagram of a method for forming a metal-containing film by a cyclic deposition process that includes a pretreatment with an iodine-containing reagent or passivating gas, according to certain disclosed embodiments.

[0121] [Figure 6]FIG. 6 is a process flow diagram of a method for forming a metal-containing film by a cyclic deposition process that includes simultaneous pretreatment with an iodine-containing reagent and a passivating gas, according to certain disclosed embodiments.

[0122] [Figure 7] FIG. 7 is a process flow diagram of a method of forming a molybdenum-containing film in accordance with certain disclosed embodiments.

[0123] [Figure 8] FIG. 8 is a process flow diagram of a method for forming a molybdenum metal film in accordance with certain disclosed embodiments.

[0124] [Figure 9] FIG. 9 is a schematic representation of an apparatus suitable for depositing molybdenum-containing films in accordance with certain disclosed embodiments.

[0125] [Figure 10] FIG. 10 is a schematic diagram of a multi-station processing system in accordance with certain disclosed embodiments.

[0126] [Figure 11] FIG. 11 is a schematic diagram of a multi-station processing system in accordance with certain disclosed embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0127] In the following description, numerous specific details are set forth to provide a thorough understanding of each presented embodiment. 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 so as not to unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with specific embodiments, it will be understood that no limitation of the disclosed embodiments is intended.

[0128] Methods and precursors are provided for depositing molybdenum-containing films on semiconductor substrates. These methods and precursors can be used, for example, to deposit blanket molybdenum-containing layers on planar substrates, to deposit conformal molybdenum-containing layers on substrates having one or more recessed or raised features, and to fill recessed features with molybdenum-containing materials. In some embodiments, methods and precursors are provided for selectively depositing a molybdenum-containing layer on a dielectric in the presence of exposed metal, or for selectively depositing a molybdenum-containing layer on a metal in the presence of exposed dielectric.

[0129] The method involves the production of molybdenum metal, molybdenum nitride (MoN x ), molybdenum carbide (MoC x ), molybdenum boride (MoB x ), molybdenum disilicide (MoSi x ), molybdenum boride carbide (MoB x C y ), molybdenum carbonitride (MoC x N y ) (x and y indicate that the stoichiometry of these compounds can vary). The provided precursors are particularly suitable for depositing molybdenum metal, such as high purity molybdenum metal, having low levels of incorporation of other elements.

[0130] definition As used herein, "molybdenum metal" or "metallic molybdenum" refers to a material consisting essentially of molybdenum (Mo). Small amounts of other elements (e.g., C, N, or O) may be present in the molybdenum metal (e.g., less than about 15 atomic % total, or less than about 10 atomic %, not including hydrogen). As used herein, "high-purity molybdenum metal" refers to molybdenum metal containing less than about 5% of other elements (e.g., less than about 1% of other elements), not including hydrogen.

[0131] Molybdenum nitride (MoN x ), molybdenum carbide (MoCx ), molybdenum boride (MoB x ), molybdenum disilicide (MoSi x ), molybdenum boride carbide (MoB x C y ), and molybdenum carbonitride (MoC x N y ) is a compound of molybdenum and nitrogen (MoN x Molybdenum and carbon (MoCx), molybdenum and boron (MoBx), molybdenum and silicon (MoSix), molybdenum, boron, and carbon (MoBxCy), and molybdenum, carbon, and nitrogen (MoCxNy). Other elements may be present in these compounds in small amounts, for example, less than about 10 atomic percent (hydrogen is excluded from this calculation).

[0132] As used herein, the term "semiconductor substrate" refers to a substrate at any stage in the fabrication of a semiconductor device that includes semiconductor material somewhere within its structure. It is understood that the semiconductor material in a semiconductor substrate need not be exposed. A semiconductor wafer having multiple layers of other materials (e.g., dielectrics) covering the semiconductor material is an example of a semiconductor substrate. The following detailed description assumes that the disclosed embodiments are practiced on a semiconductor wafer, such as a 200 mm, 300 mm, or 450 mm semiconductor wafer. However, the disclosed embodiments are not so limited. Workpieces may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that may take advantage of the disclosed embodiments include various articles, such as printed circuit boards.

[0133] "Aliphatic" means a group of at least 1 to 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10), including saturated groups such as alkanes (or alkyls) and unsaturated groups such as alkenes (or alkenyls), alkynes (or alkynyls), and cyclic versions thereof, as well as straight-chain and branched-chain configurations and all stereoisomers and positional isomers. Such hydrocarbons can be unsubstituted or substituted with one or more groups, such as those described herein for halogens or alkyl groups.

[0134] "Alkenyl" means an optionally substituted C alkyl group having one or more double bonds. 2-24 Alkenyl groups are cyclic (e.g., C 3-24 The alkenyl group can be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substituents, as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include C 2-8 Alkenyl, C 2-6 Alkenyl, C 2-5 Alkenyl, C 2-4 Alkenyl, or C 2-3 Exemplary non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH), 1-propenyl (-CH=CHCH), allyl or 2-propenyl (-CH-CH=CH), 1-butenyl (-CH=CHCHCH), 2-butenyl (-CHCH=CHCH), 3-butenyl (e.g., -CHCHCH=CH), 2-butenylidene (e.g., =CH-CH=CHCH), and the like.

[0135] By "alkenylene" is meant a polyvalent (e.g., divalent) form of the alkenyl group, which is an optionally substituted C alkyl group having one or more double bonds. 2-24 Alkenylene groups are cyclic (e.g., C 3-24The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substituents as described herein for alkyl. Exemplary non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0136] "Alkoxy" means -OR, where R is an alkyl group, optionally substituted as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples include alkoxy groups.

[0137] The terms "alkyl" and "alk" refer to 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. An alkyl group can be cyclic (e.g., C 3-24The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include haloalkyl, in which the alkyl group is substituted with 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 having two or more carbon atoms, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -O-Ak, where Ak is an optionally substituted C 1-6 (2) amino (e.g., —NR N1 R N2 (R N1 and R N2 are each independently H or optionally substituted alkyl, or R N1 and R N2 each taken together with the nitrogen atom to which it is attached forms a heterocyclyl group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl and Ar is an optionally substituted aryl); (5) aryloyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -COH); (9) C 3-8 Cycloalkyl (e.g., monovalent saturated or unsaturated non-aromatic cyclic C 3-8(10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a three-, four-, five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, or halo, unless otherwise specified); (12) heterocyclyloxy (e.g., -O-Het, where Het is heterocyclyl as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, where Het is heterocyclyl as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO); (17) oxo (e.g., =O); (18) -COR A (R A is selected from the group consisting of: (a) C 1-6 alkyl; (b) C 4-18 aryl; and (c) (C 4-18 Aryl)C 1-6 Alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (19) -C(O)NR B R C (R B Yobi R C are each independently selected from the group consisting of: (a) hydrogen; (b) C 1-6 alkyl; (c) C 4-18 aryl; and (d) (C 4-18 Aryl)C 1-6 alkyl (e.g., -Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); and (20) -NR G R H (R G and R H are each independently selected from the group consisting of: (a) hydrogen; (b) an N-protecting group; (c) C 1-6 alkyl; (d) C 2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds); (e) C 2-6Alkynyl (e.g., optionally substituted alkyl having one or more triple bonds); (f) C 4-18 Aryl; (g) (C 4-18 Aryl)C 1-6 alkyl (e.g., Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl); (h) C 3-8 cycloalkyl; and (i) (C 3-8 Cycloalkyl)C 1-6 Alkyl (e.g., -Lk-Cy (where Lk is a divalent form of an optionally substituted alkyl group as described herein and Cy is an optionally substituted cycloalkyl), in one embodiment, the two groups are not attached 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 substitution moieties (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is C 1-2 , C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 It is an alkyl group.

[0138] By "alkylene" is meant a polyvalent (e.g., divalent) form of an alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is a C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C2-16 , C 2-18 , C 2-20 , or C 2-24 It is an alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents as described herein for alkyl.

[0139] "Alkylcarbonyl" means an alkyl group, as defined above, appended to the parent molecular moiety through a carbonyl group. Exemplary non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl, among others.

[0140] The term "alkylsilyl" as used herein refers to the SiR group, where at least one R is alkyl and each R is independently selected from H and alkyl. Alkylsilyl includes mono-, bis-, and tris-alkylsilyl. Examples of alkylsilyl include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, and ethylsilyl.

[0141] "Alkynyl" means an optionally substituted C alkyl group having one or more triple bonds. 2-24 Alkynyl groups are alkyl groups. Alkynyl groups can be cyclic or acyclic, and examples include ethynyl, 1-propynyl, and the like. Alkynyl groups can be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents as described herein for alkyl. Non-limiting examples of unsubstituted alkynyl groups include C 2-8 Alkynyl, C 2-6 Alkynyl, C 2-5 Alkynyl, C 2-4 Alkynyl, or C 2-3Exemplary non-limiting alkynyl groups include ethynyl (-C≡CH), 1-propynyl (-C≡CCH), 2-propynyl or propargyl (-CHC≡CH), 1-butynyl (C≡CCHCH), 2-butynyl (-CHC≡CCH), 3-butynyl (-CHCHC≡CH), and the like.

[0142] By "alkynylene" is meant a polyvalent (e.g., divalent) form of the alkynyl group, which is an optionally substituted C alkyl group having one or more triple bonds. 2-24 It is an alkyl group. An alkynylene group can be cyclic or acyclic. An alkynylene group can be substituted or unsubstituted. For example, an alkylene group can be substituted with one or more substituents as described herein for alkyl. Exemplary non-limiting alkynylene groups include -C≡C- or -C≡CCH2-.

[0143] "Amide" means -N(R N1 )C(O)- and R N1 is H, optionally substituted alkyl, or optionally substituted aryl.

[0144] "Amino" means -NR N1 R N2 and R N1 and R N2 are each independently H, optionally substituted alkyl, or optionally substituted aryl, or R N1 and R N2 taken together with the nitrogen atom to which each is attached, form a heterocyclyl group as defined herein.

[0145] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amino group, as defined herein.

[0146] "Aminoaryl" means an aryl group, as defined herein, substituted with an amino group, as defined herein.

[0147] "Aryl" means a group containing a 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, e.g., fused benzo-C groups such as indanyl, tetrahydronaphthyl, fluorenyl, etc. 4-8 It includes cycloalkyl radicals (e.g., as defined herein). The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group incorporating at least one heteroatom within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl defines a group that is also included in the term aryl but contains an aromatic group that does not contain a heteroatom. Aryl groups can be substituted or unsubstituted. Aryl groups can be substituted with 1, 2, 3, 4, or 5 substituents, for example, any of those described herein for alkyl.

[0148] "Azido" means -N3.

[0149] "Branched alkenyl" means an isomer of a straight-chain alkenyl compound that has an alkyl group attached to the main carbon chain.

[0150] "Cyano" means -CN.

[0151] By "carbonyl" is meant the radical -C(O)-, which can also be represented as >C=O.

[0152] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated, non-aromatic or aromatic cyclic hydrocarbon radical of 3 to 8 carbon atoms, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups as described herein for alkyl.

[0153] "Deposition" or "vapor deposition" refers to the process of forming a metal layer on one or more surfaces of a substrate from vaporized precursor composition(s) containing 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., a 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 this method is one cycle, and the process can be repeated as many times as necessary to obtain the desired metal thickness.

[0154] By "dicarbonyl," as defined herein, is meant any moiety or compound containing two carbonyl groups. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., R C1 -C(O)-C(O)R C2 (R C1 and R C2 are each independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group), 1,3-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(O)R C2 (R C1 and R C2are each independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group; R 1a and R 2a are each independently H or an optional substitution moiety provided for alkyl as defined herein), and 1,4-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(R 3a R 4a )-C(O)R C2 and R C1 and R C2 are each independently an optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group; R 1a , R 2a , R 3a , and R 4a are each independently H or an optional substitution moiety provided for alkyl as defined herein.

[0155] The term "fluoroalkyl," as used herein, refers to an alkyl group having one or more fluorine-substituted moieties. In some examples, the fluoroalkyl contains exclusively fluorine-substituted moieties, such as CF, C2F5, C3F7, etc. The fluoroalkyl can be linear, branched, and cyclic.

[0156] "Halo" means F, Cl, Br, or I.

[0157] By "halo-containing substituent moiety" is meant a group that contains a halo, such as a haloaliphatic group or a haloalkyl group.

[0158] "Haloaliphatic" means an aliphatic group, as defined herein, that is substituted with one or more halo.

[0159] "Haloalkenyl" means an alkenyl group, as defined herein, that is substituted with one or more halo.

[0160] "Haloalkynyl" means an alkynyl group, as defined herein, that is substituted with one or more halo.

[0161] "Haloalkyl" means an alkyl group, as defined herein, that is substituted with one or more halogens. Non-limiting unsubstituted haloalkyl groups include C 1-2 Haloalkyl, C 1-3 Haloalkyl, C 1-4 Haloalkyl, C 1-5 Haloalkyl, C 1-6 Haloalkyl, C 2-3 Haloalkyl, C 2-4 Haloalkyl, C 2-5 Haloalkyl, C 2-6 Haloalkyl, or C 3-6 Other non-limiting examples of haloalkyl groups include -CX y H 3-y wherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), -CX z H 2-z CX y H 3-y wherein z is 0, 1, or 2, y is 0, 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; —CHCX y H 3-y wherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), -CX z1 H 2-z1 CX z2 H 2-z2 CX y H 3-y wherein z1 and z2 are each independently 0, 1, or 2; y is 0, 1, 2, or 3; each X is independently halo (F, Cl, Br, or I); and at least one of z1, z2, or y is not 0; and -CX z H 1-z [CX y1 H 3-y1 ][CXy2 H 3-y2 ] (z is 0 or 1, y1 and y2 are each independently 0, 1, 2, or 3, each X is independently halo (F, Cl, Br, or I), and at least one of z, y1, or y2 is not 0).

[0162] "Haloalkylene" means an alkylene group, as defined herein, that is substituted with one or more halo.

[0163] "Heterocyclyl," unless otherwise specified, refers to a three-, four-, five-, six-, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, selenium, or halo). Three-membered rings have zero to one double bond; four- and five-membered rings have zero to two double bonds; and six- and seven-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles 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 heterocycle (e.g., indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc.). Examples of heterocycles include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaidazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxolyl, benzodithiepinyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxolyl, benzodithiepinyl, benzisothiazolyl ... 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, benzoxathicinyl,Benzoxazepinyl, benzoxazinyl, benzoxazosinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cythinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, di Aziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydropyridyl, dihydroquinolinyl, dihydrothienyl, dihydro Indolyl, 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, indo lysinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazolyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidinyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthyridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl,Naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanoyl, oxetanyl, oxetyl, octenyl, oxindolyl, oxiranyl, oxobenzisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, pheno Thienyl (benzothiofuranyl), phenoxathinyl, 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, pyrronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolidizinyl , pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfonyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyridinyl, tetrahydropyridinyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydropyryl, tetrahydrothion ... 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, thiethyl, 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, urisyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, etc., and modified forms thereof (e.g., containing one or more oxo and / or amino groups), and salts thereof. Heterocyclyl groups can be substituted or unsubstituted. For example, heterocyclyl groups can be substituted with one or more substituent moieties, as described herein for aryl.

[0164] By "hydroxyl" is meant --OH.

[0165] By "imino" is meant --NR--, where R can be H or optionally substituted alkyl.

[0166] By "isocyanato" is meant --NCO.

[0167] What does "isocyano" mean? [ka] and includes nitriles of the formula RN≡C—, where R is an aliphatic, aryl, or heteroaryl group.

[0168] "Isothiocyanato" means -N=C=S.

[0169] By "low valent" is meant the lower oxidation state when the metal has multiple oxidation states.

[0170] "Oxo" means the =O group.

[0171] "Oxy" means -O-.

[0172] "Syril" means -SiR 1 R2 R 3 group or -SiR 1 R 2 In some embodiments, R 1 , R 2 , and R 3 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3 are each 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 wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and a, b, and c are each ≧0, and a+b+c=3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0173] "Silyloxy" means -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 and R 1 , R 2 , and R 3are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3 are each 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 wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and a, b, and c are each ≧0, and a+b+c=3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0174] When used, each of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohol, ether, ester, amide, sulfone, sulfide, hydroxyl, nitro, cyano, carboxy, amine, heteroatom, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogen, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl, and aralkylaminocarbonyl, or any of the substitution moieties in the preceding paragraph, or any of these substitution moieties joined directly or via a suitable linker. The linker is typically a short chain of 1 to 3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)-, or -S(O)O-. The ring may be substituted multiple times.

[0175] The term "lower" modifying "alkyl," "alkenyl," "alkynyl," "alkoxy," or "alkoxycarbonyl" refers to a C1-C6 unit of the particular functionality. For example, "lower alkyl" means a C1-C6 alkyl.

[0176] By "substituted" is meant having one or more substitution moieties whose presence does not interfere with the desired function or reactivity. Examples of substitution moieties include alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amido, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonate, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclyl, ether, ester, silicon-containing moiety, thioester, or combinations thereof. The substitution moiety may itself be substituted. For example, the amino-substituted moiety may itself be mono-substituted or independently di-substituted with further substituted moieties as defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic rings).

[0177] "Thiocyanato" means -SCN.

[0178] By "thioether" it is meant to include both monodentate and polydentate (e.g., bidentate or tridentate) thioethers, as well as ligands containing both thioether and thiolate (or other) moieties.

[0179] "Unsubstituted" means that the atom's open valence is occupied by a hydrogen. Also, if an atom's open valence position is not specified as occupying it, it is a hydrogen.

[0180] As used herein, the term "about" is understood to account for minor increases and / or decreases beyond the recited value, but these variations do not significantly affect the desired function of the parameter beyond the recited value(s). In some cases, "about" encompasses ±10% of the recited value. As used herein, the term modifies any recited value, range of values, or endpoints of one or more ranges.

[0181] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to establish relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be in a particular location within a device.

[0182] The embodiments disclosed below describe the deposition of materials onto a substrate, such as a wafer, substrate, or other workpiece. The workpiece 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. Those skilled in the art will appreciate that the term "partially fabricated integrated circuit" can refer to a silicon wafer at any of the many stages of integrated circuit fabrication thereon. Wafers or substrates used in the semiconductor device industry typically have diameters of 200 mm, 300 mm, or 450 mm. Unless otherwise noted, the process specifications (e.g., flow rates, power levels, etc.) listed herein relate to the processing of 300 mm diameter substrates or chambers configured to handle 300 mm diameter substrates, but can be appropriately scaled for substrates or chambers of other sizes. In addition to semiconductor wafers, other workpieces for which the embodiments disclosed herein may be used include various articles, such as printed circuit boards. The processes and apparatus can be used in the manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like.

[0183] By "unsaturated" is meant a moiety that contains double or triple carbon-carbon bonds.

[0184] By "unsaturated substituent moiety" is meant a double or triple bond containing aliphatic chains, cyclic groups, aryl groups, or heteroaryl groups.

[0185] The term "independently selected," when describing the selection of R substituents in a molecule containing multiple R groups, means that the selection of R substituents at different atoms of the molecule is independent, and also that the selection of R substituents at an atom having multiple R substituents is independent.

[0186] Introduction and Background ALD is a technique for depositing thin layers of materials using a sequence of self-limiting reactions. The ALD process uses surface-mediated deposition reactions to deposit films in cycles, layer by layer. As an example, an ALD cycle may include the following operations: (i) precursor delivery / adsorption, (ii) purging the precursor from the chamber, (iii) delivery of a second reactant and optionally igniting a plasma, and (iv) purging by-products from the chamber. Forming a film on the surface of a substrate through the reaction of the second reactant with the adsorbed precursor affects the film's composition and properties, such as its non-uniformity, stress, wet etch rate, dry etch rate, and electrical properties (e.g., breakdown voltage and leakage current).

[0187] Unlike chemical vapor deposition (CVD) techniques, ALD processes deposit films layer by layer using a surface-mediated deposition reaction. In one example of an ALD process, a substrate surface containing a population of surface-active sites is exposed to a gas-phase distribution of a dose of a first precursor (e.g., a silicon-containing precursor) provided to a chamber housing the substrate. Molecules of this first precursor adsorb onto the substrate surface, including chemisorbed and / or physisorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include derivatives of the compound in addition to the compound. After the first precursor is administered, the chamber is evacuated to remove most or all of the first precursor remaining in the gas phase, leaving most or only the adsorbed species. In some embodiments, the chamber need not be completely evacuated. For example, the reactor may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to mitigate reaction. A second reactant (e.g., an oxygen-containing reactant) is introduced into the chamber, causing some of these molecules to react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a brief application of an activation source. The chamber may then be evacuated again to remove unbound second reactant molecules. As noted above, in some embodiments, the chamber may not be fully evacuated. Additional ALD cycles may be used to increase film thickness.

[0188] In some embodiments, the ALD method includes plasma activation. As described herein, the ALD methods and apparatus described herein may be conformal film deposition (CFD) methods.

[0189] FIG. 1A shows a cross-sectional view 100 of a substrate during a deposition process. This view shows a substrate 101 having a recessed feature 103. The recessed feature may have sidewalls and a bottom. In general, the substrate 101 may comprise a variety of materials, such as dielectrics, metals, and metal nitrides. A conformal layer of a metal-containing film 105 is deposited on the substrate 101 using methods and precursors described below. The resulting structure is shown in FIG. 1B. In some applications, this process continues to fill the recessed feature 103 with a metal-containing material 105, as shown in FIG. 1C. The metal-containing film is deposited within the recessed feature, in some embodiments, using multiple depositions of conformal films as shown in FIGS. 1A-1C using a sequence of ALD or pulsed chemical vapor deposition cycles. In other embodiments, the recessed feature may be filled using bottom-up film growth.

[0190] Method for introducing metal-containing precursors as the first step FIG. 2A is a flowchart illustrating a continuous and optionally cyclical method 200 for depositing a metal-containing film, beginning with the introduction of a metal-containing precursor into a process chamber in operation 210. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. The metal-containing precursor may be flowed into a chamber containing a substrate at a flow rate of about 100 sccm to about 5000 sccm (e.g., about 100-2000 sccm). The precursor may be flowed for any useful duration (e.g., about 0.1-10 seconds) and at any useful pressure (e.g., about 1-500 Torr). The temperature of the process chamber may be maintained between 100°C and 500°C in some embodiments, or at or below about 400°C in other embodiments. In certain embodiments, the temperature may be ultralow, between about 200°C and 300°C.

[0191] A push gas may be flowed during operation 210. The push gas may be any inert gas, such as nitrogen (N), argon (Ar), or any other gas listed herein. The push gas may be provided to assist in pressure and / or temperature control of the process chamber, vaporization of liquid reactants, faster delivery of reactants, and / or as a sweep gas to remove process gas from the process chamber and / or process chamber piping. In some embodiments, the push gas is flowed into the chamber containing the substrate at a flow rate of about 100 sccm to about 5000 sccm (e.g., about 500 to about 2000 sccm). Flowing the push gas with the metal-containing precursor not only stabilizes the pressure during operation, but also dilutes the precursor.

[0192] In some embodiments, the metal-containing precursor may be a vanadium-containing precursor, a niobium-containing precursor, a tantalum-containing precursor, a chromium-containing precursor, a cobalt-containing precursor, a titanium-containing precursor, a hafnium-containing precursor, a tungsten-containing precursor, an iron-containing precursor, a ruthenium-containing precursor, a nickel-containing precursor, a zinc-containing precursor, a zirconium-containing precursor, a copper-containing precursor, a molybdenum-containing precursor, or a combination thereof. The metal-containing precursors are described in the following paragraphs, starting with the molybdenum-containing precursor.

[0193] Molybdenum metal films have not been widely used in semiconductor processing. This is at least in part due to the difficulty of obtaining molybdenum metal with low levels of impurity incorporation, and therefore low resistivity, due to molybdenum's high affinity for carbon, nitrogen, and oxygen. Many common molybdenum deposition precursors exhibit low thermal stability, resulting in poor step coverage in high-aspect-ratio features. Existing organometallic molybdenum precursors with molybdenum-carbon bonds can incorporate high levels of carbon into the deposited molybdenum, leading to high resistivity. For example, when using molybdenum carbonyl compounds such as Mo(CO)6, the molybdenum acts as a catalyst for CO dissociation, resulting in the incorporation of large amounts of carbon (e.g., at least 5 atomic %) into the growing molybdenum metal film. While molybdenum halides do not suffer from these problems, existing halide-based molybdenum-containing deposition precursors have many other undesirable properties. For example, the use of molybdenum hexafluoride (MoF6) requires a fluorine barrier and etch-stop layer when the molybdenum is deposited on a substrate containing an exposed fluorine-sensitive layer (e.g., a silicon-containing material such as a silicon oxide-based dielectric). Molybdenum pentachloride (MoCl5) is another conventional precursor that suffers from several drawbacks, including a high melting point that can induce etching of the growing molybdenum film. While volatility can be increased by modifying homoleptic halide precursors by exchanging halide ligands for oxo ligands, such as the molybdenum oxychlorides MoOCl4 and MoO2Cl2, these precursors are difficult to reduce to pure molybdenum metal due to the strong molybdenum-oxygen double bond. Furthermore, MoCl5, MoOCl4, and MoO2Cl2 are all high-melting, corrosive solids, making them undesirable for mass production.

[0194] The molybdenum precursors and deposition methods provided herein can overcome one or more of these deficiencies. In some embodiments, high-purity molybdenum metal films are deposited using the provided precursors and methods, and the deposited high-purity molybdenum metal films consist essentially of molybdenum and have less than about 5 atomic % of other elements, e.g., less than about 3 atomic % of other elements, or less than about 1 atomic % of other elements (excluding hydrogen). In some embodiments, molybdenum metal films are provided having resistivities of less than about 50 μΩ·cm (e.g., less than about 30 μΩ·cm for a 100 Å thick film). In some embodiments, particularly when fluorine-free precursors are used, molybdenum metal can be deposited directly on substrates containing exposed fluorine-sensitive materials without the need for a protective etch-stop layer. For example, molybdenum metal or other molybdenum-containing films can be deposited on exposed silicon-containing dielectrics such as silicon oxide-based dielectrics, silicon nitride, and silicon carbide, or on amorphous silicon- or crystalline silicon- or silicon germanium-containing substrates. As used herein, silicon oxide-based dielectrics refer to dielectrics containing silicon-oxygen bonds, including thermally grown silicon oxides, silicates, silane (and related) deposited oxides, TEOS (tetraethyl orthosilicate) deposited oxides, and the like.

[0195] The precursors provided herein are suitable for vaporization and are stable at target temperatures and pressures, for example, in some embodiments, the precursors are used in deposition reactions at temperatures below about 450°C, e.g., below about 400°C.

[0196] To maintain suitable volatility, in many embodiments described herein, the precursor has a molecular weight of less than about 450 g / mol, for example, less than about 400 g / mol.

[0197] The low-valent molybdenum compounds described herein can advantageously provide high-purity molybdenum metal in CVD and ALD depositions. Furthermore, the use of these compounds can be associated with reduced etching of substrate materials. These advantages are provided for illustrative purposes and are not intended to limit the use of these compounds solely to molybdenum metal deposition and deposition on substrates susceptible to etching.

[0198] Typically, the molybdenum precursor may have from two (MoL2) to six (MoL6) ligands and may contain molybdenum in a wide range of oxidation states from 0 to +6. The molybdenum precursor may also be a dimolybdenum compound in which (1) two molybdenum atoms are single- or multiple-bonded to each other, or (2) two molybdenum atoms are joined by a linking group such as a bidentate ligand.

[0199] Suitable molybdenum-containing precursors include molybdenum halides and oxyhalides, such as fluoride, chloride, bromide, oxyfluoride, oxychloride, and oxybromide, where the molybdenum can be in any oxidation state from +2 to +6.

[0200] Molybdenum chloride precursors are represented by the formula MoClx (where x is 2, 3, 4, 5, or 6) and include molybdenum dichloride (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoCl6 is used. While this description primarily refers to MoClx precursors, other molybdenum halide precursors may be used in other embodiments. Molybdenum halide precursors are represented by the formula MoX z where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and z is 2, 3, 4, 5, or 6. MoX z An example of a precursor is molybdenum fluoride (MoF6). In some embodiments, fluorine-free MoX zPrecursors are used to prevent etching or incorporation of fluorine. In some embodiments, bromine-free and / or iodine-free MoX z The precursors are used to prevent etching or incorporation of bromine or iodine.

[0201] The molybdenum oxyhalide precursor has the formula MoO y X z where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)), and y and z are each independently selected from the group consisting of MoO y X z is a number greater than zero so that a stable compound is formed. Examples of molybdenum oxyhalides include molybdenum dioxide dichloride (MoO2Cl2), molybdenum oxide tetrachloride (MoOCl4), molybdenum oxide tetrafluoride (MoOF4), molybdenum dioxide dibromide (MoO2Br2), and molybdenum iodide (MoO2I, Mo4O 11 I) can be mentioned.

[0202] In some embodiments described herein, the precursor has a molecular weight of less than about 450 g / mol, for example, less than about 400 g / mol.

[0203] In some embodiments, the molybdenum-containing precursor has the formula MoX n Y m where 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 MoCl5, Mo2Cl 10 , MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6.

[0204] Low-valent molybdenum complexes Low-valent molybdenum complexes or compounds are those in which molybdenum is in the low oxidation state 0, +1, +2, or +3. In certain embodiments, low-valent molybdenum complexes can be effective precursors because 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.

[0205] Low valent molybdenum precursors may provide a surface oxidation-reduction process with fewer circuits to obtain fully reduced molybdenum metal films with minimal impurities. Without wishing to be bound by theory, this is believed to be a result of the ease of reduction of low valent molybdenum precursors.

[0206] Molybdenum Zero Complex

[0207] Mo(0) precursors are advantageous because they do not require a reduction step and their use lowers the energy barrier for Mo film formation upon exposure to reducing agents, making them energetically easier. Mo(0) precursors are particularly suited to multi-step ALD processes in which surface-ligand exchange and transformation (reduction) occur. Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex that exists in the 0 oxidation state.

[0208] The general structure of the low-valent molybdenum precursor containing one molybdenum atom is MoL n (Formula I), and the general structure of the low-valent molybdenum precursor having two molybdenum atoms is Mo2L n (Formula II) or L n Mo(L') m MoL n (Formula III). For any of Formulas I-III, each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand, and n is an integer from 2 to 6. For Formula III, L' is a linking moiety such as a bidentate ligand, and m is an integer from 1 to 3.

[0209] monodentate ligand Suitable ligands for low-valent molybdenum complexes include monodentate ligands (also called unidentate ligands), which are ligands that bond or coordinate to the metal center through only one coordination site on the metal or through only one site on the ligand. Monodentate ligands can have a wide variety of substituent moieties, such as hydrogen, halo, hydroxy, alkylsilyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde ... and aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, ═O, ═S, ≡N, ≡CR, ═CR2, —NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimide, carbamate, aryloxyalkyl, carboxyl, carboxy, —C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyano, or cyclyl groups, where each R is independently aliphatic, such as a haloalkyl, or aryl, such as a haloaryl group.

[0210] In some embodiments, the low valent molybdenum precursor comprises at least one OR, P(R), CNR, allyl, or aryl group, where each R is independently an aliphatic group, an aryl group, a haloalkyl group, or a haloaryl group.

[0211] In some embodiments, the monodentate ligand can include an oxygen atom. In certain embodiments, one or more of the ligands can be an optionally substituted alkoxy. Non-limiting ligands include, for example, methoxy, ethoxy, isopropoxy (i-PrO), and t-butoxy (t-BuO). Non-limiting molybdenum-containing precursors include, for example, Mo(CHF)(t-BuO), Mo(CF)(t-BuO), Mo(CHI)(t-BuO), Mo(CI)(t-BuO), Mo(CHCHF)(t-BuO), Mo(CHCHI)(t-BuO), Mo(CHF)(t-BuO), Mo(CF)(t-BuO), Mo(CHI)(t-BuO), Mo(CI)(t-BuO), Mo(CHCH 2F)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=CH CH3)(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.

[0212] In certain embodiments, the oxygen-containing monodentate ligand can be -OC(CH)(CF), -OC(CH)(CF), -OC(CH), -OSiR (such as -OSiPh), C≡O (carbonyl ligand), or -OAr (Ar groups include, but are not limited to, phenyl, mesitylenyl, 2,6-iPrC, hexa-isopropyl-tert-phenyl, and 2,3,5,6-PhC). In certain embodiments, the oxygen-containing ligand is an ether, epoxide, or ketone. In some cases, the oxygen-containing ligand can be a silyloxy group.

[0213] In certain embodiments, the ligand is a phosphorus-containing ligand. Suitable complexes may be of the formula R3P, where R is a halo, aliphatic, or aryl group. Examples include secondary or tertiary organophosphines such as P(t-Bu)3, PMe3, PPh3, P(OMe)3, P(OEt)3, PCl3, or PF3. In some embodiments, the phosphorus-containing ligand is phosphanetryltris(benzenesulfonic 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).

[0214] In some embodiments, the ligand is an isocyano-functional group, including isonitriles of the formula -C≡NR, such as isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, and the like. In some embodiments, R is an aliphatic group, such as haloalkyl, or an aryl group, such as haloaryl. In certain embodiments, R can be -CHCF, -C(F)=CF, -C(F)=C(F)CF, -CFC(F)=CF, -CH(CF), -CH(CH)(CF), or -C(CH)(CF). In certain embodiments, R is a perfluoroalkyl-substituted moiety having 1 to 10 carbon atoms, such as a perfluorinated methyl group, ethyl group, i-propyl group, n-propyl group, t-butyl group, sec-butyl group, n-butyl group, cyclopentyl group, n-pentyl group, cyclohexyl group, or n-hexyl group.

[0215] In some embodiments, the monodentate ligand is an sp aryl group, such as an allyl group, an allenyl group, an ethenyl group, an indenyl group, or a cyclopentadienyl group. 2The ligands are of a hybrid orbital nature. Two of the same or two different such substituents may be used to form precursors with sandwich structures. In some embodiments, one such substituent is used to form a half-sandwich complex. In certain embodiments, the ligand may be mesitylenyl, tolyl, xylyl, benzyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, or pyrimidinyl.

[0216] In some embodiments, the ligand is an atom directly connected to the molybdenum through a multiple bond, such as a double or triple bond. Examples include =O, =NR, =S, ≡N, =CR2, or CR, where each R is independently an aliphatic group, an aryl group, a haloalkyl group, or a haloaryl group.

[0217] In some embodiments, the molybdenum-containing precursor has at least one optionally substituted haloalkyl group. Non-limiting haloaliphatic group ligands include -CX y H 3-y wherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), -CX z H 2-z CX y H 3-y wherein z is 0, 1, or 2, y is 0, 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; or —CHCX y H 3-ywhere y is 1, 2, or 3 and each X is independently halo (F, Cl, Br, or I). Further non-limiting haloalkyl groups include fluoromethyl (-CHF), difluoromethyl (-CHF), trifluoromethyl (-CF), chloromethyl (-CHCl), dichloromethyl (-CHCl), trichloromethyl (-CCl), bromomethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CBr), iodomethyl (-CHI), diiodomethyl (-CHI), triiodomethyl (-CI), bromofluoromethyl (-CHFBr), chloromethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CBr), iodomethyl (-CHI), diiodomethyl (-CI), triiodomethyl (-CI), bromofluoromethyl (-CHFBr), chloromethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CBr), iodomethyl (-CHI), diiodomethyl (-CI), triiodomethyl (-CI), bromofluoromethyl (-CHFBr), chloromethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CBr), chloromethyl (-CHBr), dibromomethyl (-CH ... chloromethyl (-CHBr), dibromomethyl (-CHBr), chloromethyl (-CHBr), chloromethyl (-CHBr), dibromomethyl (-CHBr), chloromethyl (-CHBr), chloro Examples of iodomethyl groups include chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CHCHF), 2-chloroethyl (-CHCHCl), 2-bromoethyl (-CHCHBr), 2-iodoethyl (-CHCHI), 2,2-difluoroethyl (-CHCHF), 2,2-dichloroethyl (-CHCHCl), 2,2-dibromoethyl (-CHCHBr), 2,2-diiodoethyl (-CHCHI), 2,2-fluoroiodoethyl (-CHCHFI), and the like. 1-2 Haloalkyl includes beta-halosubstituted ethyl. Still other haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 Haloalkynyl is exemplified.

[0218] In other embodiments, the ligand is an optionally substituted alkyl group, an optionally substituted alkenyl, or an optionally substituted alkynyl. Non-limiting groups include -C n H 2n+1 (n is 1 or 2), -C n H 2n-1 (n is 2, 3, or 4), or -C n H 2n-3(n is 2, 3, or 4). Still other non-limiting groups include methyl (-CH), ethyl (-CHCH), vinyl or ethenyl (-CH=CH), 1-propenyl (-CH=CHCH), allyl or 2-propenyl (-CH-CH=CH), 1-butenyl (-CH=CHCHCH), 2-butenyl (-CHCH=CHCH), 3-butenyl (e.g., -CHCHCH=CH), ethynyl Examples include allyl (-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), and 1-methylallyl (CH(CH3)CH=CH2).

[0219] In some embodiments, the monodentate ligand may be —CH 2 P(CH 3 ) 3 , —CH(Si(CH 3 ) 3 )(P(CH 3 ) 3 ), —C(O)C 3 F 7 , or —CHCHSO 2 C 6 H 5 .

[0220] In some embodiments, the monodentate ligand comprises a sulfur atom. In particular embodiments, one or more monodentate ligands can be -SO2CF3, -SO2C3N2H3, -CHCHSO2C6H5, -SO2OCH3, or -SO2C6H4CH3.

[0221] In some embodiments, the monodentate ligand comprises a nitrogen atom. In certain embodiments, one or more of the monodentate ligands can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino. Non-limiting examples of the monodentate ligands include, for example, -NMe2, -NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)-(tbba), -N(SiMe3)2, and -N(SiEt3)2.

[0222] In some embodiments, the optionally substituted amino is —NR 1 R2 and R 1 and R 2 are each independently H or alkyl, or R 1 and R 2 taken together with the nitrogen atom to which each is attached, form a heterocyclyl group, as defined herein. In other embodiments, an optionally substituted bis(trialkylsilyl)amino is —N(SiR 1 R 2 R 3 )2 and R 1 , R 2 , and R 3 In yet other embodiments, the optionally substituted trialkylsilyl is —SiR 1 R 2 R 3 and R 1 , R 2 , and R 3 are each independently alkyl.

[0223] In other embodiments, the low valent molybdenum precursor is —NR 1 R 2 a first ligand which is -NR 1 R 2 and a second ligand, R 1 and R 2 are each independently H or alkyl. In yet other embodiments, the formula is -OR 1 a first ligand which is -OR 1 and a second ligand, wherein each R 1 are independently H or alkyl.

[0224] In some embodiments, the monodentate ligand is an optionally substituted alkyl. Non-limiting alkyl groups include, for example, C n H 2n+1(n is 1, 2, 3, or more), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl, etc. In various embodiments, the ligand has at least one β hydrogen or β halogen.

[0225] In some embodiments, at least one monodentate ligand is an optionally substituted haloalkyl. Non-limiting examples of haloalkyl groups include, for example, C n H 2n+1-z X z wherein n is 1, 2, 3, or more, z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7), and each X is independently halo (F, Cl, Br, or I).

[0226] In some embodiments, at least one monodentate ligand is an optionally substituted alkenyl or an optionally substituted alkynyl. Non-limiting alkenyl groups include, for example, C n H 2n-1 (n is 2, 3, 4, or more), for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl. Non-limiting alkynyl groups include, for example, C n H 2n-3 (n is 2, 3, 4, or more), for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl.

[0227] Alkynyl groups are also suitable monodentate ligands in certain embodiments. In some embodiments, for example, groups of formula R 1 CCCH2MoL3(R 1is a C1-C2 straight-chain or branched alkane such as methyl or ethyl, and L is an amino group (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminocyclopentane, aminocyclohexane) or an alkoxy group (methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy) in which the carbon-carbon triple bond is not directly attached to a monodentate ligand.

[0228] Alkyne compounds with a carbon-carbon triple bond directly attached to the molybdenum atom hydrolyze in the presence of water as well, although much slower than amino and alkoxy groups. 1 C≡C)3MoR 2 and (R 1 C≡C)4Mo(R 1 is a simple alkane such as methyl or ethyl, and R 2 Compounds such as (R is a C1-C2 hydrocarbon) are precursors with monodentate ligands according to certain embodiments. 1 C≡C)3MoR 2 In the molybdenum center, three alkynes are attached by carbon-carbon triple bonds to the molybdenum center. Tetraalkynes are (R 1 C≡C)4Mo.

[0229] In some embodiments, the monodentate ligand is halo. In particular, the metal-containing precursor can be a metal halide or organometallic halide. Non-limiting metal halides and organometallic halides include FCH2MoX3, CF3MoX3, ICH2MoX3, CI3MoX3, CH2FCH2MoX3, CH2ICH2MoX3, MoX2, or MoX4, where each X is independently halo. In other embodiments, the metal-containing precursor is RMoX3, where R is C 1-4 Haloalkyl, C 2-4 Haloalkenyl, or C 2-4 In yet another embodiment, the metal-containing precursor is RMoX3, where R is C 1-2Alkyl, C 2-4 Alkenyl, or C 2-4 alkynyl and each X is independently halo.

[0230] In other embodiments, the monodentate ligand is a C1-C3 aliphatic (wherein the C1-C3 aliphatic is optionally substituted with a ketone, alkoxy group, or epoxy group) or a -C(O)C1-C3 alkyl group. Ether, ketone, or epoxide-containing ligands on low-valent molybdenum-containing precursors may be advantageous to aid crosslinking.

[0231] In some embodiments, the monodentate ligand can include a silicon atom. In some embodiments, the monodentate ligand can be -Si(CH), -Si(C,H), -CH, Si(CH), -CH(Si(CH), or -C(Si(CH). In certain embodiments, one or more ligands can be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl). Non-limiting ligands include, for example, -SiMe, -SiEt, -N(SiMe), and -N(SiEt).

[0232] For any formula herein, each monodentate ligand is independently oxygen, halo, azido, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR 1 and R 1 can be alkyl).

[0233] The present disclosure also encompasses hydrogen as a monodentate ligand. An example of a complex with a monodentate hydrogen ligand is a molybdenum hydride precursor such as Mo(Cp)2H2 (Cp is cyclopentadienyl).

[0234] The monodentate ligand may be ambidentate, which has two potential donor atoms but is bound to the metal through only one of the two. In certain embodiments, the ambidentate ligand is NO2 - which may be bonded to the metal by either the nitrogen or oxygen atom.

[0235] bidentate ligand Suitable ligands for low-valent molybdenum complexes include bidentate ligands. A bidentate ligand (also called a chelating ligand) is a ligand that binds or coordinates to a metal center through two coordination sites on the metal or through two sites on the ligand. A bidentate ligand is a Lewis base that donates two pairs of electrons to the metal atom. A bidentate ligand can be neutral or anionic. Furthermore, a bidentate ligand can have two identical coordination atoms or can be an asymmetric bidentate ligand in which the two coordination atoms are not identical. In some embodiments, the bidentate ligand can 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). Precursors with bidentate ligands include, but are not limited to, molybdenum dioxide diacetylacetonate (MoO2(acac)2).

[0236] Exemplary structures containing bidentate ligands include: [ka] and [ka] These include, but are not limited to:

[0237] Bidentate ligands have the structure -(E) e -, wherein each E is independently NR, C(R) n , Si(R) n , S, O, or P(R)n wherein each R independently comprises hydrogen, aryl, amino, or aliphatic; n is 0, 1, or 2; and e is 1, 2, 3, 4, or 5.

[0238] Suitable low valent molybdenum precursors may contain one, two, or three bidentate ligands, each of which may be the same or different.

[0239] The bidentate ligand may be an amidinate, an amidate, an iminopyrrolidinate, a diazabutadiene, a β-iminoamide, an α-iminoalkoxide, a β-dikeminate, a β-ketoiminate, a β-diketonate, a pyrazolate, a β-aminoalkoxide, a guanidinitate, a dithiolene, an α-iminothiolene, an α-dithiolate, or a β-dithiolate. Other examples of suitable materials include the bidentate ligands described in US2022 / 0170155 and WO2021 / 035236, which are incorporated herein by reference in their entireties.

[0240] tridentate ligand A tridentate ligand is a ligand having three atoms capable of functioning as a receptor in a coordination complex. In certain embodiments, the tridentate ligand has three nitrogen atoms, three sulfur atoms, three phosphorus atoms, 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-triazacyclononane, bis(diphenylphosphinoethyl)phenylphosphine, N,N,N',N"N"-pentamethyldiethylenetriamine, tris(4S-isopropyl-2-oxazolinyl)phenylborate, tris(4,4-dimethyl-2-oxazolinyl)phenylborate, trispyrazolylborate, 1,4,7-trioxonane, diethylenetriamine, or iminodiacetate anion. Suitable low valent molybdenum precursors may contain one, two, or more tridentate ligands, which may be the same or different.

[0241] The low valent molybdenum precursor may have two to six ligands. Each occurrence of L may independently be a monodentate, ambidentate, bidentate, or tridentate ligand as described above. The low valent molybdenum precursor having two ligands may be of the formula MoL2. Precursors having two ligands include bis(ethylbenzene)molybdenum (C 16 H 20 Mo), but are not limited to these.

[0242] 2B shows exemplary structures of molybdenum precursors having three ligands (Formula XIV), four ligands (Formulas V and VI), or five ligands (Formulas IX and X) in certain embodiments. For Formulas XIV, VI, IX, and X, R 4 , R 6 , R 7 , and R 15 are each independently -CH3, -C2H5, -C3H7, -C4H9, -C5H 11 , -CF3, -C4F9, -C5F 11 , -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), -C(CF3)3, -Si(CH3)3, -Si(C2H5)3 or -CH2Si(CH3)3, -CH(Si(CH3)3)2, -C(Si(CH3)3)3, -P(CH3)3, -CH2P (CH3)3, -P(O)OH, -P(O)(OCH3)2, -P(O)(OCH2CH3)2, -CH(Si(CH3)3)(P(CH3)3), -SO2CF3, -SO2C3N2H3, -C(O)C3F7, -CHCHSO2C6H5, -SO2OCH3, or -SO2C6H4CH3. For Formula IX, G can be =O, =NR, =S, or =CR2, and each R is independently an aliphatic group, an aryl group, a haloalkyl group, or a haloaryl group. Suitable precursors having four ligands include, but are not limited to, Mo(NtBu)2(OBu)2 and (iPrCp)2MoH2. Suitable precursors having five ligands include, but are not limited to, MoO(OiPr)4.

[0243] For formula X, each R 8 are independently any of the monodentate, ambidentate, or bidentate ligands described above. 1 may be aliphatic, and R 2 may be any of the monodentate, ambidentate, bidentate, or tridentate ligands described above, and n may be 1, 2, 3, 4, or 5.

[0244] Low-valent molybdenum precursors may have six ligands. Precursors with six ligands include, but are not limited to, molybdenum hexafluoride (MoF6) and molybdenum hexacarbonyl (Mo(CO)6). In some embodiments, such precursors have the general formula Mo(X) p (R 10 ) q (XII), wherein each X independently comprises chloro, fluoro, bromo, or iodo; and each R 10 are 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)3, or -CNR 11 Contains R 11 includes aliphatic, aryl, or heterocyclyl, p is 1 to 4, q is 2 to 5, and p+q=6.

[0245] Alternatively, a low-valent molybdenum precursor having six ligands can be prepared according to the formula Mo(R 12 ) r (R 13 ) s (XIII), wherein each R 12are 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)3, or -CNR 14 Contains R 14 includes aliphatic, aryl, or heterocyclyl, and each R 13 independently include trimethylphosphine, triethylphosphine, tri-i-propylphosphine, triphenylphosphine, tris(trimethylsilyl)phosphine, tris(2-carboxyethyl)phosphine, tris(dimethylamino)phosphine, tris(o-tolyl)phosphine, tris(4-methoxyphenyl)phosphine, or tris(2-furyl)phosphine, where r is 1 to 6, s is 0 to 5, and r+s=6.

[0246] Figure 2C shows exemplary structures of low-valent molybdenum precursors with six ligands. Structures 1-9 have one or more CNR ligands, which may be isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, or isocyanohaloaryl groups. In some embodiments, R is an aliphatic group such as haloalkyl, or an aryl group such as haloaryl. In certain embodiments, R may be -CHCF, -CH(CF), -CH(CH)(CF), or -C(CH)(CF). In certain embodiments, R is a perfluoroalkyl-substituted moiety having 1 to 10 carbon atoms, such as perfluorinated methyl, ethyl, i-propyl, n-propyl, t-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl, or n-hexyl. Structures 10-18 have one or more PMe ligands.

[0247] Molybdenum complexes can be prepared using zerovalent starting materials such as molybdenum hexacarbonyl. Other synthetic routes include the reaction of MoCl3(THF)3 with an appropriate ligand followed by reduction, and the reaction of MoX5 (X = Cl, Br, I) with an appropriate ligand followed by reduction.

[0248] The starting materials can be treated with neutral ligands such as thioethers (dialkylsulfides) to induce redox-neutral ligand exchange. Zero-valent starting materials can also be treated with ligand precursors such as bis(diethylthiocarbamoyl)disulfide or bis(trifluoromethyl)-1,2-dithiete to induce oxidative addition to form the sulfur-containing complexes described herein.

[0249] The reaction may be carried out in a variety of aprotic solvents. For example, the reaction may be carried out in ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,2-dimethoxyethane, etc.; hydrocarbon solvents such as toluene, benzene, heptane, hexane, pentane, etc.; or halocarbon solvents such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc. The reaction may be carried out over a wide temperature range, depending on the boiling point of the solvent and the solubility of the product. In some embodiments, the starting materials, reaction intermediates, and desired products are not stable to moisture and oxygen. Therefore, the reaction process should be carried out under anhydrous and air-free conditions using a protective inert gas such as nitrogen or argon.

[0250] Dimolybdenum Complexes In another aspect, precursors for the deposition of molybdenum-containing films are di-molybdenum compounds containing direct molybdenum-molybdenum bonds (e.g., multiple molybdenum-molybdenum bonds, such as double bonds, or multiple bonds with bond orders of 2 to 5). Directly bonded dimolybdenum precursors have the structure Mo2L n(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 exemplary precursor is Mo2(O-isopropyl)6. Another exemplary precursor is shown in Figure 2D. In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by double bonds (e.g., Structure 19). In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by triple bonds (e.g., Structures 20-23). ​​For Structures 20 and 21, R may be an aliphatic group such as an alkyl group, a haloalkyl group, or a silyl group. For Structure 23, L may be any ligand described above, or may be either CO, CNR, or PMe3 (where R is aliphatic, aryl, or heterocyclyl), and X is halo. Such precursors are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal. This is because such compounds can be more easily reduced to metallic molybdenum than some of the monoatomic molybdenum compounds.

[0251] The di-molybdenum precursors described herein can be synthesized using dimolybdenum tetraacetate as the starting material by treatment with a ligand salt, such as lithium amidate. In one aspect, a container containing any of the precursors described herein in solid or liquid form is provided. In another aspect, a solution of any of these precursors is provided, and the solvent may include, for example, a high-boiling hydrocarbon solvent, such as a higher alkane. In some embodiments, the container holding the molybdenum precursor (in solid or liquid form, or in solution) is filled with an inert gas, such as nitrogen (N) or argon (Ar), to prevent contact with air and potential decomposition of the precursor due to contact with moisture and / or air. In some embodiments, the container is adapted for vaporization of the precursor within the container. For example, the container may include an inlet and an outlet, the inlet adapted to be connected to a source of carrier gas that can flow over or through the precursor, thereby assisting in vaporization of the precursor. The outlet is adapted to remove the carrier gas and precursor vapor from the container and is configured to be connected to a conduit that can be used to deliver the precursor vapor to a processing chamber. The inlet and outlet each have a closed position and an open position and may include, for example, a manual valve that can be switched from the closed position to the open position and vice versa. When the container is stored or transported, the inlet and outlet are closed. When the container is installed in a deposition apparatus and in use, the inlet and outlet valves may be open, allowing a carrier gas, carrying precursor vapor, to flow into the inlet and out the outlet.

[0252] In some embodiments, the vessel has a flow-over design in which the inlet and outlet are located above the surface of the precursor. For example, in a cylindrical vessel, the inlet and outlet may be located at a similar vertical height (e.g., the vertical distance between the inlet and outlet may be less than about 20% of the height of the cylinder). In other embodiments, the vessel has a bubbler design in which the inlet is located below the surface of the precursor and the outlet is located above the inlet (e.g., above the surface of the precursor). For example, in a cylindrical vessel, the inlet and outlet may be located vertically apart from each other (e.g., the vertical distance between the inlet and outlet may be about 30% or more, e.g., about 50% or more, or about 80% or more of the height of the cylinder).

[0253] Low valent dimolybdenum complexes may also contain two molybdenum atoms indirectly connected to each other by a linking moiety. Such precursors have the formula L n Mo(L') m MoL n (III), where each L is independently a monodentate, ambidentate, bidentate, 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 have the structure -(E) e -, each E independently represents C(R) n , NR, Si(R) n , S, O, or P(R) n wherein each R independently comprises hydrogen, aryl, amino, or aliphatic; n is 0, 1, or 2; and e is 1, 2, 3, 4, or 5.

[0254] In some embodiments, a low-valent dimolybdenum complex may contain two molybdenum atoms that are directly bonded to each other and indirectly connected to each other by a linking moiety as described above. Referring back to Figure 2D, exemplary structures 24 and 25 are shown having both types of connections. For structures 24 and 25, L may be any of the ligands described above, or preferably CO, CNR, or PMe3 (where R is aliphatic, aryl, or heterocyclyl), and X is halo.

[0255] The molybdenum-containing films provided herein, and particularly high-purity molybdenum metal, can be used in metallization of interconnects (e.g., for filling recessed features to form contacts), logic gate applications for FinFETs, as adhesion layers or diffusion barriers, and in 3D NAND manufacturing.Example applications include filling logic and memory contacts, filling DRAM embedded word lines, filling vertically integrated memory gates and word lines, and three-dimensional integration using through-silicon vias (TSVs).Molybdenum resistivity is more scalable than tungsten resistivity, and in some embodiments, molybdenum is a particularly advantageous metal for filling narrow recessed features, for example, features with a width of less than about 20 nm.

[0256] In one application, molybdenum metal is used to produce barrier-less contacts. In this application, molybdenum metal is deposited directly into recessed features (contact holes) having widths of about 5-100 nm (e.g., about 5-20 nm), where the recessed features are formed in a dielectric layer and include a low-k material, such as silicon oxide, silicon nitride, or silicon oxycarbide, on the sidewalls and exposed silicon or silicon germanium at the bottom. In an alternative embodiment, the contact holes prior to deposition may be lined with a barrier layer, such as WN, MoN, MoC, or TiN, onto which the molybdenum metal is deposited.

[0257] copper precursor Copper metal can be deposited using a variety of copper precursors, and the copper can be in the +1 or +2 oxidation state. The precursors can be cuprous (copper(I)) compounds such as acetylacetonates, ketominates, 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 in which the copper is coordinated to a multiple bond, such as a double or triple bond, or to the oxygen of, for example, a carbonyl group.

[0258] Examples of copper precursors include Cu(acac)2 (acac = acetylacetonate); Cu(thd)2 (thd = tetrahydrodionate); hexafluoroacetylacetonate-copper-trimethylsilane; cyclopentadienyl (Cp) compounds such as CpCu(CNMe), CpCu(CNCMe3), CpCuCO, CPCuPR3 (where R = Me, Et, or Ph), and CpCu(CSiMe3)2; MeCu(PPh3)3, CuMe, CuCCH (ethynylcopper), CuCMe3 (methylacetylide copper), (HC = CMeCC)Cu(3-methyl-3-butene). alkyl or aryl compounds such as (Me)3CCCCu(3,3-dimethyl-1-butynyl)copper, CuCCPh, CHCu(phenylcopper), (Me)3CCCCu(3,3-dimethyl-1-butynyl)copper, Me3SiCCCH2Cu; and other compounds such as CuCN, [Cu(OAc]n (OAc = acetate), Cu2Cl2(butadiene), CHCuO(2-methoxyphenylcopper), (MeCN)4CuX (X is a halide, alkyl, amine, or phenyl group), Me3SiOCu(PMe3)3, Cu(C4H4S), and Cu-carbene compounds such as those derived from imidazolium.

[0259] Cobalt precursor Cobalt metal can be deposited using a variety of cobalt precursors, with the cobalt being in the +1, +2, or +3 oxidation state. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., cobalt(III) bis(acetylacetonate)), cobalt amidinate (e.g., bis(Nt-butyl-N'-ethylpropanimidamidate)cobalt(II)), cobaltocene, and carbonyl-containing cobalt precursors (e.g., cobalt tricarbonyl nitrosyl and cyclopentadienyl cobalt dicarbonyl). An example of a halogen-containing cobalt precursor is CoCl(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine.

[0260] Ruthenium Precursors Ruthenium metal can be deposited using vaporizable ruthenium precursors such as, for example, bis(ethylcyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium, ruthenocene, and cyclopentadienylpropylcyclopentadienylruthenium(II).

[0261] Tungsten Precursor Tungsten can be deposited using a variety of volatile precursors. x A halogen-containing tungsten precursor is used, such as tungsten chloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In another example, a tungsten fluoride, such as tungsten hexafluoride, may be used.

[0262] Other precursors In some embodiments, other useful precursors include vanadium-containing precursors such as tetrakis(dimethylamino)vanadium, tris(dimethylamino)cyclopentadienylvanadium, and tetrakis(ethylmethylamino)vanadium; niobium-containing precursors such as (tert-butylimido)bis(diethylamino)niobium, (tert-butylimido)bis(dimethylamino)niobium, and (tert-butylimido)bis(ethylmethylamino)niobium; tantalum-containing precursors such as tert-butylimidotris(dimethylamido)tantalum and tantalum pentachloride; iron-containing precursors such as iron(III) tert-butoxide dimer, ferrocene, and iron pentocarbonyl; nickel-containing precursors such as allyl(cyclopentadienyl)nickel(II) and nickel(II) bis(acetylacetonate); zinc-containing precursors such as zinc acetate and diethylzinc; and chromium-containing precursors such as chromium carbonyl and bis(cyclopentadienyl)chromium(II).

[0263] 2A, an iodine-containing reagent is introduced into the process chamber and reacts with the metal-containing precursor in operation 220. The iodine-containing reagent may be: hydrogen iodide (HI); iodine (I2); alkyl iodides such as CHI, C2H5I, C3H7I, C4H9I, C2H12, C2H4I2, C3H6I2, or C4H8I2; iodosilanes such as SiH3I, SiH2I2, SiHI3, SiI4, or Si2I6; metal bromides; boron triiodide (BI3); metal iodides such as titanium tetraiodide (TiI4) or aluminum triiodide (AlI3); or alkyl iodosilanes such as Si(CH3)I3, Si(CH3)2I2, Si(CH3)3I, Si(CH3)HI2, Si(CH3)2HI, or Si(CH3)HI.

[0264] Suitable iodine-containing reagents include, but are not limited to, I2; HI; CH3I; CF3I, C2H5I; 1-iodopropane; 2-iodopropane; 1-iodobutane; 2-iodobutane; sec-butyl iodide; t-butyl iodide; iodocyclopentane; iodocyclohexane; diiodomethane; 1,2-diiodoethane; 1,1-diiodopropane; 1,2-diiodopropane; 1,3-diiodopropane; 2,2-diiodopropane; 1,1-diiodobutane; 1,2-diiodobutane; 1,3-diiodobutane; 2 ,2-Diiodobutane;2,3-Diiodobutane;1,2-Diiodo-2-methylpropane;2,3-Diiodo-2,3-dimethylbutane;1,1,2,2-Tetraiodoethane;2,2,3,3-Tetraiodobutane;1,1,1,2,2,2-Hexaiodoethane;1,2-Diiodocyclopentane;1,2-Diiodocyclohexane;Iodobenzene;Diiodobenzene;2-Iodopyridine;3-Iodopyridine;4-Iodopyridine;3-Iodo-1-nitrobenzene;3-Iodo-1-trifluoromethylbenzene;4-Iodoaniline ;4-Iodo-1-dimethylaminobenzene;4-Iodophenol;(Trimethylsilyl)methyl iodide;(Trimethylsilyl)methyl diiodide;(Trimethylsilyl)methyl triiodide;Bis(trimethylsilyl)methyl iodide;Bis(trimethylsilyl)methyl diiodide;Tris(trimethylsilyl)methyl iodide;1-(Trimethylsilyl)-1-iodoethane;1-(Trimethylsilyl)-2-iodoethane;1-(Trimethylsilyl)-1,2-diiodoethane;1,1-Bis(trimethylsilyl)-1,2-diiodoethane (trimethylsilyl)-1,2-diiodoethane;CHI3;CI4;1-Iodoethene;1-Iodopropane;2-Iodopropane;1-Iodo-1-butene;1-Iodo-2-butene;2-Iodo-1-butene;2-Iodo-2-butene;Iodoacetylene;Diiodoacetylene;3,3-Dimethyl-1-iodobut-1-yne;1,1-Diiodoethane;1,2-Diiodoethane;1,2-Diiodopropene;1,2-Diiodo-2-propene;1,2-Diiodobutene;1,2-Diiodo-2-butene;1,2-Diiodo-3-butene;3,4-Diiodocyclohexene;4,5-Diiodocyclohexadiene;1,2-Diiodoacetylene;1,1,2,2-Tetraiodoethene;SiI4;SiHI3;SiH2I2;SiH3I;Si(CH3)I3;Si(CH3)2I2Si(CH3)3I;Si(CH3)HI2;Si(CH3)2HI;Si(CH3)H2I;Si2I6;GeI4;GeHI3;GeH2I2;GeH3I;AlI3;BI3;TiI4;Sn I4; HfI4, N-iodosuccinimide; 1,3-diiodo-5,5-dimethylhydantoin; N-iodophthalimide; N-iodosaccharin; 1-chloro-2-iodoethane; IF5; iodoacetic acid; iodopropynyl butylcarbamate; benzyl iodide; iodoacetone; bromoiodomethane; chloroiodomethane; allyl iodide; 1-iodophenol; 2-iodophenol; 3-iodophenol, and combinations thereof.

[0265] Without wishing to be bound by theory, the iodine-containing reagent may act as a surface ligand exchange catalyst, reacting with the metal-containing precursor to form iodine-bonded metal species in situ within the process chamber.

[0266] Non-limiting examples of reactive species that constitute metal-iodine reactive sites or iodine bond-containing reactive species include radicals, metastables, ions, neutral species, plasma, photons, radiation, excited molecules, excited atoms, or others, as described herein. In one non-limiting embodiment, the metastables have energies of about 0.01-1 eV. In another non-limiting embodiment, the ions have energies of about 100-1000 eV. In yet another non-limiting embodiment, the reactive species have energies of about 0.01-1000 eV. References herein to radicals and metastables may, in some non-limiting instances, encompass any of the reactive species described herein. The iodine bond-containing metal species may be any reactive species, as defined above, that includes a metal and iodine. When the metal is molybdenum, the iodine bond-containing metal species may be MoI, such as MoI2 or MoI3. x, or reactive Mo-I* sites. Additionally, reactive species can include molybdenum halides such as MoI2 or MoI3.

[0267] In operation 230, the iodine bond-containing metal species is exposed to a reducing agent to form a metal-containing film. Suitable reducing agents include, but are not limited to, hydrogen (H); ammonia (NH); ammonia plasma; hydrazine (N2H4); t-butylhydrazine (CH4H4); 12 Alkylhydrazines such as N2; hydrogen atoms; hydrogen plasma; hydrogen radicals; other hydrogen species; alcohols; aldehydes; carboxylic acids; boranes; amines; silane (SiH4); disilane (Si2H6); trisilane (Si3H8); germane (GeH4); digermane (Ge2H6); borane (BH3); diborane (B2H6); and combinations thereof. In addition to the plasmas listed, other reducing agents may be provided by generating a plasma from one or more reducing agents.

[0268] Exposing the substrate to the reducing agent may include contacting the substrate with the reducing agent for a time period of about 0.1 seconds to about 180 seconds, about 0.5 seconds to about 60 seconds, or about 0.1 seconds to about 10 seconds. The flow rate of the reducing agent during exposure of the substrate may, in some embodiments, be less than 30 slm, or less than 15 slm, or less than 10 slm, or less than 5 slm, or less than 2 slm, or less than 0.1 slm. The flow rate of the reducing agent may range from about 0.1 to 30 slm, about 5 to 15 slm, or greater than 10 slm.

[0269] If the deposited film is thick enough, the method is complete and terminated, as shown in operation 240. As used herein, a "metal-containing film" refers to a film containing only a metal or a film containing a metal and additional components. Metal-containing films can be deposited for a variety of semiconductor applications; therefore, the desired thickness will vary depending on the particular application. In some embodiments, the metal-containing film may be deposited as a conformal layer on the substrate to a thickness of about 0.1 to 10 nm.

[0270] If a thicker film is desired, operation 250 is a process flow path indicating that operation 210 can be repeated n times, beginning again after operation 230. In process flow path 250, n is the number of cycles, which can be from 1 to 50 or from 20 to 40. The cycle of operations 210, 220, and 230 can be repeated as many times as necessary. As used herein, the term "cycle" refers to a particular set of consecutive operations.

[0271] Metal-containing films formed by method 200 may have fewer halogen-based or other impurities than metal-containing films made at higher temperatures by conventional processes.

[0272] In addition to the steps of method 200 described above, in some embodiments, purge 215 may be optionally performed after operation 210. Purge 225 may be optionally performed after operation 220 in some embodiments, or both purge 215 and purge 225 may be performed in some embodiments. Purging may involve flowing a purge gas or sweep gas, which may be the carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Examples of purge gases include argon (Ar), nitrogen (N), hydrogen (H), helium (He), oxygen (O), krypton (Kr), xenon (Xe), neon (Ne), and combinations thereof. In various embodiments, the purge gas is an inert gas. The purge gas may include one or more gases. In some embodiments, operations 215 and / or 225 may include one or more evacuation substages to evacuate the process chamber. Alternatively, it will be understood that purging may be omitted in some embodiments. Operations 215 and / or 225 may have any suitable duration, such as from about 0 seconds to about 60 seconds (e.g., about 0.01 seconds). In some embodiments, the duration of the purge may be shortened by increasing the flow rate of one or more purge gases. For example, the purge gas flow rate may be adjusted to modify the duration of the purge according to the thermodynamic properties of the various reactants and / or the geometric characteristics of the process chamber and / or process chamber piping. In one non-limiting example, the duration of the purge phase may be adjusted by adjusting the purge gas flow rate. This may shorten the deposition cycle time and increase substrate throughput. After purging, the organosilicon-containing precursor molecules remain adsorbed on the substrate surface.

[0273] The purge gas can be flowed into the chamber containing the substrate at a flow rate of about 1,000 sccm to about 40,000 sccm (e.g., about 100 to 2,000 sccm) for any useful period of time (e.g., about 0.1 to 10 seconds) and at any useful pressure (e.g., about 0.5 to 25 Torr).

[0274] FIG. 3 is a flowchart illustrating method 300, another continuous and optionally cyclical deposition process, beginning with the introduction of a metal-containing precursor into a process chamber in operation 310. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. Operation 310 is similar to operation 210 described above. In method 300, operation 320 is the simultaneous introduction of an iodine-containing reagent and a reducing agent, combining operations 220 and 230 described above for method 200. During operation 320, the iodine-bonded species described above are formed and reduced. Next, in operation 325, the process chamber is purged. In operation 330, it is determined whether the deposited film is of the desired thickness. If not, process flow path 340 indicates that the cycle may be repeated n times by returning to operation 310 and rerunning n times. Additionally, the process chamber may optionally be purged in operation 315 after operation 310.

[0275] FIG. 4 is a flowchart illustrating method 400, another continuous and optionally cyclical deposition process, beginning with the introduction of a metal-containing precursor into a process chamber in operation 410. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. The introduction of the metal-containing precursor into the process chamber in operation 410 is similar to operation 210 described above. In operation 420, the substrate is exposed to an iodine-containing reagent, similar to operation 220 described above. Iodine-bonded metal species are formed, and then, in operation 430, upon exposure to a reducing agent, the iodine-bonded metal species are reduced to form the metal-containing film. A determination 440 is made as to whether the deposited film is sufficiently thick, and if a thicker film is desired, the cycle of process steps 410, 420, and 430 may be repeated n times, as shown by process flow path 450.

[0276] Process flow path 460 shows that after operation 420, operation 410 may be repeated m times. In operation 460, m is the number of cycles and may be between 1 and 50 or between 20 and 40. The cycle of operations 410 and 420 may be repeated as many times as necessary. In certain embodiments, the method includes a dual cycle, in which different sets of steps are both repeated. A dual cycle may be described as a subcycle within a cycle, as shown by process flow path 450 and process flow path 460.

[0277] In addition to the steps of method 400 described above, in some embodiments, purge 415 may be optionally performed after operation 410. Purge 425 may be optionally performed after operation 420 in some embodiments, or in some embodiments, both purge 415 and purge 425 may be performed, as described above in connection with method 200.

[0278] 5 is a flowchart illustrating method 500, another continuous and optionally cyclical deposition process, beginning with pretreatment of a substrate in a process chamber in operation 510. Pretreatment 510 may be exposing the substrate to an iodine-containing reagent or passivating gas. Pretreatment may prevent metal nucleation in certain areas and facilitate initial deposition at the bottom of features.

[0279] Suitable passivating gases include, but are not limited to, hydrogen, nitrogen, water, ammonia, oxygen, nitrous oxide (N2O), nitrogen trifluoride (NF3), and combinations thereof.

[0280] Operation 520 is the introduction of a metal-containing precursor into the process chamber, as described above in connection with operation 210. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. An iodine-containing reagent is then introduced into the process chamber to react with the metal-containing precursor to form an iodine-bonded-containing species in operation 530, as described above in connection with operation 220. If an iodine-containing reagent is selected for the pretreatment of operation 510, the iodine-containing reagent selected for operation 530 can be the same iodine-containing reagent or a different iodine-containing reagent. In operation 540, the iodine-bonded-containing metal species is exposed to a reducing agent to form a metal-containing film, as described above for operation 230.

[0281] If the deposited film is sufficiently thick, as indicated by operation 550, the method is complete and terminated. If a thicker film is desired, process flow path 555 indicates that operation 510 can begin again after operation 540 and be repeated n times. For process flow path 555, n is the number of cycles and may be between 1 and 50 or between 20 and 40. The cycle of operations 510, 520, 530, and 540 can be repeated as many times as necessary to achieve the desired thickness. In addition to the steps of method 500 described above, in some embodiments, purge 515 may be optionally performed after operation 510. In some embodiments, purge 525 may be optionally performed after operation 520, and in some embodiments, purge 535 may be optionally performed after operation 530. In some embodiments, purges 515, 525, and 535 may all be performed during one cycle, as described above in connection with method 200.

[0282] How to introduce iodine-containing reagents as the first step FIG. 6 is a flow chart illustrating method 600, another continuous and optionally cyclic deposition process, beginning with operation 610, pre-treating a substrate in a process chamber by simultaneously introducing a passivating gas and an iodine-containing reagent.

[0283] Suitable passivating gases include, but are not limited to, hydrogen, nitrogen, water, ammonia, oxygen, nitrous oxide (N2O), nitrogen trifluoride (NF3), and combinations thereof.

[0284] Operation 620 is the introduction of a metal-containing precursor into the processing chamber, as described above in connection with operation 210. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor and the deposited metal-containing film is a molybdenum-containing film. In operation 630, a reducing agent is introduced into the process chamber to form the metal-containing film, as described for operation 230 above.

[0285] If the deposited film is sufficiently thick, as indicated by operation 640, the method is complete and terminated. If a thicker film is desired, process flow path 650 indicates that after operation 640, operation 610 can begin again and be repeated n times. For process flow path 650, n is the number of cycles and may be between 1 and 50 or between 20 and 40. The cycle of operations 610, 620, and 630 can be repeated as many times as necessary to achieve the desired thickness. In addition to the steps of method 600 described above, in some embodiments, a purge 615 may be optionally performed after operation 610. In some embodiments, a purge 625 may optionally be performed after operation 620, or in some embodiments, both purge 615 and purge 625 may be performed, as described above in connection with method 200.

[0286] Method for forming molybdenum-containing materials Molybdenum-containing materials can be deposited using the precursors described herein by a variety of deposition methods, such as CVD (including thermal CVD and PECVD), ALD (including thermal ALD and PEALD), and the like. An exemplary method 700 is illustrated by the process flow diagram shown in FIG. 7. The process begins in 701 by introducing a molybdenum precursor described herein into a process chamber containing a semiconductor substrate. The precursor can be introduced in vaporized form into a flow of an inert gas, such as argon, helium, or nitrogen (N). In operation 703 (which can occur before, after, or during the introduction of the molybdenum-containing precursor 701), a second reactant is introduced into the process chamber containing the substrate. In some embodiments, the introduction of the molybdenum precursor and the second reactant occur sequentially. The chemical nature of the second reactant depends on the chemistry of the desired molybdenum-containing film. For example, when depositing molybdenum metal, the second reactant is typically a reducing reactant (including a reactant that forms a reducing environment upon activation in a plasma). Examples of suitable reactants for forming molybdenum metal include hydrogen (H), ammonia (NH), hydrazine (NH), amines, diborane (BH), silane (SiH), disilane (SiH), alcohols, hydrogen sulfide (HS), or thiols. In some embodiments, H is the preferred reducing reactant for depositing molybdenum metal. In some embodiments, a molybdenum-containing precursor is reacted sequentially with various reactants. For example, in some embodiments, molybdenum metal is deposited by adsorbing a layer of a molybdenum-containing precursor on a substrate, reacting it with a second reactant, and then reacting it with a third reactant.

[0287] In one example, a molybdenum-containing precursor (first reactant) is first reacted with at least one of water, HS, and a thiol (second reactant). The substrate containing the reacted precursor is then treated with hydrogen (H) (third reactant). In some embodiments, the process chamber is purged and / or evacuated after the introduction of each reactant. In some embodiments, the first reactant (e.g., water, HS, or a thiol) is selected to promote the removal of ligands from the molybdenum precursor, and the third reactant (e.g., H) is selected to remove ligand residues (e.g., C-, N-, S-, O-containing impurities) from the surface of the substrate and / or to reduce molybdenum to the zero oxidation state to form high-purity molybdenum metal.

[0288] When depositing a molybdenum-containing film other than molybdenum metal, the second reactant can be selected to act as a source of elements required for the molybdenum-containing film, although in some embodiments, these elements may be derived solely from ligands. Process conditions (temperature, pressure, reactant flow rates, and optionally plasma power) can be adjusted to favor specific film chemistries. For example, in some embodiments, borane and silane reactants can be used to deposit molybdenum boride- or molybdenum silicide-containing materials, but under different conditions, these reactants alone or in combination with other reactants (e.g., H ) may result in molybdenum metal. When depositing molybdenum nitride, in some embodiments, a nitrogen-containing second reactant can be selected, and process conditions can be adjusted to include nitrogen in the film. For example, NH , NH , N , alkylamines, and alkylhydrazines may be used as second reactants to deposit molybdenum nitride. When depositing molybdenum carbide, a carbon-containing second reactant may be used, and process conditions can be adjusted to incorporate carbon into the film. For example, a hydrocarbon may be introduced as the second reactant to form molybdenum carbide. Molybdenum carbonitride films can be formed by introducing a nitrogen-containing reactant and / or a carbon-containing reactant. In some embodiments, nitrogen- and carbon-containing ligands in the molybdenum precursor itself can act as sources of nitrogen and / or carbon. Molybdenum oxide films can be formed by introducing an oxygen-containing second reactant, such as O2, O3, NO, CO2, etc. The second reactant may be introduced into the processing chamber in a mixture with an inert carrier gas, such as N2, argon, or helium. Molybdenum sulfide films can be deposited using a sulfur-containing reactant or by adjusting process conditions to incorporate sulfur from a sulfur-containing molybdenum precursor into the film. Sulfur-containing reactants include H2S, dialkyl sulfides, dialkyl disulfides, and thiols such as methanethiol or tert-butylthiol.

[0289] In some embodiments, the precursor and the second reactant can be mixed within the body of the processing chamber. In other embodiments, after the molybdenum precursor is introduced and adsorbed on the surface of the substrate, the processing chamber is purged and / or evacuated with an inert gas to remove unadsorbed precursor from the processing chamber. In some embodiments, the layer of precursor on the substrate is adsorption-limited. In other embodiments, a thicker layer of molybdenum precursor can be formed on the surface of the substrate prior to purging and / or evacuating the process chamber. Note that when the precursor and the second reactant are introduced sequentially, the order of introduction of the precursor and the second reactant can be reversed. In some embodiments, the second reactant can be introduced first and then allowed to adsorb on the surface of the substrate. The process chamber is then purged and / or evacuated to remove the second reactant from the volume of the process chamber, and the molybdenum precursor is then introduced.

[0290] Referring to operation 705, a molybdenum precursor is reacted with a second reactant to form a layer of molybdenum-containing material on the substrate. This reaction occurs on the surface of the substrate and / or within the body of the processing chamber, and is optionally plasma-assisted. For example, in a CVD process, the precursor may react with the second reactant within the body of the processing chamber. The reaction may be carried out thermally or with plasma activation. In an ALD process, the reaction occurs only on the surface and is limited by the amount of adsorbed material on the surface (by the amount of molybdenum precursor and / or the amount of adsorbed second reactant). In surface-limited reactions (such as ALD), plasma activation is also possible. For example, an adsorbed layer of a molybdenum precursor may be reacted with a plasma formed in a gas containing a hydrogen-containing second reactant (e.g., H2, NH3, CO, alcohol, etc.) to form a molybdenum metal layer. Typically, the plasma may be generated directly in the process chamber containing the substrate (direct plasma) or remotely in a separate compartment, with the resulting plasma-activated species being supplied to the process chamber (remote plasma). The temperature during the reaction process can be, for example, about 20-600°C. Low-temperature deposition at about 450°C or less, such as about 400°C or less (e.g., about 100-400°C), is performed in some embodiments and is particularly advantageous for depositing molybdenum metal. The pressure in the process chamber can range from about 0.1-100 Torr, such as about 0.5-5 Torr for PEALD and about 1-60 Torr for thermal ALD.

[0291] After the reaction is complete, the formed molybdenum-containing layer can optionally be annealed, as shown in operation 707. Annealing can be performed by increasing the temperature. For example, if the reaction is performed at a relatively low temperature, e.g., less than about 450°C (e.g., less than about 400°C), the temperature can be increased, e.g., by 50-200°C, during annealing. In some embodiments, annealing is performed at a temperature of about 300-500°C.

[0292] An example of a surface-based deposition process 800 for forming a molybdenum metal film on a substrate is illustrated by the process flow diagram shown in FIG. 8 . In operation 801, a layer of a molybdenum precursor and / or a reducing reactant is formed on the surface of the substrate. In some embodiments, the layer is an adsorption-limiting layer. Next, in operation 803, the process chamber is purged and / or evacuated. This step ensures that the molybdenum precursor and / or reducing reactant is present only on the surface of the substrate and not within the volume of the process chamber. Next, in operation 805, the molybdenum precursor is reacted with the reducing reactant on the surface of the substrate. For example, if only the molybdenum precursor is adsorbed on the surface of the substrate in operation 801, a reducing reagent may be introduced into the process chamber to react with the molybdenum precursor on the surface. If both a molybdenum precursor layer and a reducing reactant layer are formed on the surface of the substrate in operation 801, the process conditions can be adjusted (e.g., using a plasma treatment of the surface or an elevated temperature) to activate the reaction in operation 803. The process chamber is then purged and / or evacuated at 807, and operations 801-807 are repeated at 809 to form more molybdenum metal. In some embodiments, each cycle of operations 801-807 deposits an average of about 0.1-5.0 Å of molybdenum metal. In some embodiments, 2-100 cycles are performed. For example, 2-20 cycles can be performed. Molybdenum layers having thicknesses of about 5-5,000 Å (e.g., 5-500 Å) can be formed with a high degree of control over the layer thickness. Using this method, conformal layers of molybdenum metal with excellent step coverage can be formed.

[0293] Molybdenum-containing films can be deposited on a variety of surfaces, such as on metals (copper, nickel, cobalt, tungsten, etc.), dielectrics (e.g., silicon oxide-based dielectrics, silicon nitride, silicon carbide, metal oxides, metal nitrides, etc.), amorphous silicon, and crystalline silicon, etc. In some embodiments, a molybdenum-containing film (e.g., molybdenum metal) is deposited on a substrate containing an exposed layer of dielectric and an exposed layer of metal.

[0294] In some embodiments, the molybdenum-containing film is selectively deposited on a dielectric in the presence of exposed metal, and in other embodiments, on a metal in the presence of exposed dielectric. As used herein, "selective deposition" refers to deposition on a target surface at a higher rate than on non-target surfaces. In some embodiments, the selectivity (the ratio of the deposition rate on the target surface to the deposition rate on non-target surfaces) is greater than 2 (e.g., greater than 5). In some embodiments, the molybdenum-containing film is deposited on a dielectric (e.g., a silicon oxide-based dielectric) without substantially depositing on exposed metal surfaces.

[0295] The provided molybdenum-containing films can be deposited on a variety of surfaces, such as on metals (copper, nickel, cobalt, tungsten, etc.), dielectrics (silicon oxide-based dielectrics, silicon nitride, silicon carbide, metal oxides, metal nitrides, etc.), amorphous silicon, and crystalline silicon, etc. In some embodiments, the films are deposited as liners or diffusion barrier layers.

[0296] In one embodiment, the provided molybdenum-containing film is used as a MOSFET gate electrode material. In one example, the provided film is integrated into a pMOS device structure. The device (e.g., a transistor) includes a semiconductor layer, a source region, a drain region, and a gate dielectric layer formed on the semiconductor layer and defining a channel region in the semiconductor layer between the source and drain regions. The semiconductor layer includes a semiconductor material such as silicon (Si), germanium (Ge), or silicon germanium (SiGe). The gate dielectric layer, in one embodiment, includes a high-k dielectric having a dielectric constant greater than about 3.9. For example, the gate dielectric layer may include a high-k material such as HfO, HfSiO, or HfSiON. The gate dielectric layer is typically very thin, e.g., about 10-15 Å thick. Each layer is disposed on top of the gate dielectric layer and collectively forms a gate electrode. An optional capping layer may be formed directly on and in contact with the gate dielectric layer. The capping layer, in some embodiments, comprises TiN, TaN, and / or WN and has a thickness of about 10-20 Å.

[0297] The layer above the capping layer is referred to as the work function metal-containing layer. This layer includes a molybdenum-containing material provided herein, the material having a work function greater than about 4.9 eV (e.g., greater than about 5.0 eV, greater than about 5.1 eV, etc.). In some embodiments, the layer is a MoN layer having an effective work function greater than about 5.0. This layer is deposited by the ALD or CVD methods described herein, and in some embodiments, is further treated with a plasma treatment reactant to increase its work function.

[0298] For example, in some embodiments, the as-deposited molybdenum-containing material is treated using a plasma-activated nitrogen-containing reactant (e.g., N2) to increase the nitrogen content and increase the work function of the formed layer. The layer, in some embodiments, has a thickness of about 5-50 Å, or 5-15 Å. In one example, the work function metal-containing layer has a thickness of about 30 Å. In some embodiments, the metal-containing layer is deposited directly on a capping layer. If no capping layer is present, the layer may be deposited directly on the gate dielectric layer. Finally, the device may optionally include one or more conductive layers formed on the metal-containing layer. In some embodiments, the conductive layer includes one or more of TiAl, TiAlC, TiAlON, and / or a conductive metal fill such as Mo, Co, or W.

[0299] The provided molybdenum-containing layers may be used in planar pMOS devices, FinFET pMOS devices, or gate-all-around (GAA) pMOS devices. Films having a work function greater than 5.0 eV (e.g., a work function of about 5.0-5.5 eV) can be obtained.

[0300] Molybdenum-containing films can be deposited for a variety of applications in semiconductor processing. In some embodiments, a molybdenum-containing film (e.g., molybdenum metal) is deposited as a conformal layer to a thickness of about 0.1 to 10 nm on a substrate containing one or more recessed or raised features. In some embodiments, the recessed features are filled with a molybdenum-containing material (e.g., molybdenum metal).

[0301] The molybdenum-containing films provided herein, and particularly high-purity molybdenum metal, can be used in metallization of interconnects (e.g., for filling recessed features to form contacts), logic gate applications for FinFETs, as adhesion layers or diffusion barriers, and in 3D NAND manufacturing.Example applications include filling logic and memory contacts, filling DRAM embedded word lines, filling vertically integrated memory gates and word lines, and three-dimensional integration using through-silicon vias (TSVs).Molybdenum resistivity is more scalable than tungsten resistivity, and in some embodiments, molybdenum is a particularly advantageous metal for filling narrow recessed features, for example, features with a width of less than about 20 nm.

[0302] In one application, molybdenum metal is used to produce barrier-less contacts. In this application, molybdenum metal is deposited directly into recessed features (contact holes) having widths of about 5-100 nm (e.g., about 5-20 nm), where the recessed features are formed in a dielectric layer and include a low-k material, such as silicon oxide, silicon nitride, or silicon oxycarbide, on the sidewalls and exposed silicon or silicon germanium at the bottom. In an alternative embodiment, the contact holes prior to deposition may be lined with a barrier layer, such as WN, MoN, MoC, or TiN, onto which the molybdenum metal is deposited.

[0303] Device The deposition methods described herein can be performed in a variety of apparatuses. A suitable apparatus includes a processing chamber having one or more inlets for introducing reactants, a substrate holder within the process chamber configured to hold the substrate in place during deposition, and optionally a plasma generating mechanism configured to generate a plasma in the process gases. The apparatus may also include a controller having program instructions for performing any of the method steps described herein. The deposition methods described herein may be performed in corresponding ALD and CVD apparatuses.

[0304] For example, in some embodiments, an apparatus includes a controller having program instructions for introducing a molybdenum precursor, such as any of the precursors described herein, into a process chamber and reacting the molybdenum precursor with a second reactant to form a layer of molybdenum-containing material on the substrate. The controller may also include program instructions for performing any of the methods described herein.

[0305] An example of a deposition apparatus suitable for depositing molybdenum-containing films using provided methods is shown in FIG. 9 , which schematically illustrates an embodiment of a process station 900 that can be used to deposit materials using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which may be plasma-enhanced. For simplicity, the process station 900 is depicted as a stand-alone process station having a process chamber body 902 for maintaining a low-pressure environment. However, it will be understood that multiple process stations 900 may be included in a common process tool environment. Furthermore, it will be understood that in some embodiments, one or more hardware parameters of the process station 900, including those described in detail below, may be programmably adjusted by one or more computer controllers.

[0306] The process station 900 is in fluid communication with a reactant delivery system 901 for delivering process gases to a distribution showerhead 906. The reactant delivery system 901 includes a mixing vessel 904 for blending and / or conditioning the process gases for delivery to the showerhead 906. One or more mixing vessel inlet valves 920 may control the introduction of process gases into the mixing vessel 904. Similarly, a showerhead inlet valve 905 may control the introduction of process gases to the showerhead 906.

[0307] Some molybdenum-containing precursors may be stored in solid or liquid form before vaporization and subsequent delivery to the process chamber. For example, the embodiment of FIG. 9 includes a vaporization point 903 for vaporizing solid reactants fed to a mixing vessel 904. In some embodiments, the vaporization point 903 may be a heated vaporizer. In some embodiments, a flow of inert gas is passed over the heated solid molybdenum precursor or bubbled through the heated liquid molybdenum precursor at subatmospheric pressure to carry the precursor vapor to the process chamber. Precursor vapor generated from such a vaporizer may condense in the downstream delivery piping. Exposure of incompatible gases to the condensed reactant may generate small particles. These small particles can clog piping, interfere with valve operation, contaminate the substrate, and so on. Some methods for addressing this issue involve cleaning and / or evacuating the supply piping to remove residual reactants. However, cleaning the delivery piping may increase the cycle time of the process station and reduce the throughput of the process station. Thus, in some embodiments, the delivery piping downstream of vaporization point 903 may be heat traced. In some examples, mixing vessel 904 may also be heat traced. In one non-limiting example, the piping downstream of vaporization point 903 has an increasing temperature profile at mixing vessel 904 ranging from about 100°C to about 200°C.

[0308] The showerhead 906 distributes process gases toward the substrate 912. In the embodiment shown in FIG. 9 , the substrate 912 is shown positioned below the showerhead 906 and resting on a pedestal 908. The showerhead 906 may have any suitable shape and any suitable number and arrangement of ports for distributing process gases to the substrate 912. Although not explicitly shown, in some embodiments, the showerhead 906 is a dual-plenum showerhead including at least two types of conduits, a first type of conduit dedicated to the delivery of a molybdenum-containing precursor vapor and a second type of conduit dedicated to the delivery of a second (or other) reactant. In these embodiments, the molybdenum-containing precursor and the reactants do not mix in the conduits before entering the process chamber and do not share conduits if delivered sequentially to the chamber.

[0309] In some embodiments, a micro-volume 907 is located below the showerhead 906. Performing ALD and / or CVD processes within the micro-volume rather than the entire volume of the process station may enable reduced reactant exposure and clean-up times, reduced time for changing process conditions (e.g., pressure, temperature, etc.), or limited exposure of the process station robotics to process gases. Examples of micro-volume sizes include, but are not limited to, volumes between 0.1 liters and 2 liters. This micro-volume also impacts productivity throughput. While the deposition rate per cycle is reduced, cycle time is simultaneously reduced. In certain cases, the latter effect can be dramatic enough to increase the overall throughput of the module for a given target film thickness.

[0310] In some embodiments, the pedestal 908 may be raised or lowered to expose the substrate 912 to the micro-volume portion 907 and / or to change the volume of the micro-volume portion 907. For example, during a substrate transfer phase, the pedestal 908 may be lowered to place the substrate 912 on the pedestal 908. During a deposition process phase, the pedestal 908 may be raised to position the substrate 912 within the micro-volume portion 907. In some embodiments, during the deposition process, the micro-volume portion 907 may completely surround a portion of the pedestal 908 along with the substrate 912, forming a region of high flow impedance.

[0311] Optionally, the pedestal 908 may be lowered and / or raised during portions of the deposition process to adjust the process pressure, reactant concentration, etc., within the micro-volume 907. In one scenario in which the process chamber body 902 remains at a base pressure during the deposition process, the pedestal 908 may be lowered to allow the micro-volume 907 to be evacuated. Example ratios of the micro-volume to the process chamber volume include, but are not limited to, volume ratios of 1:700 to 1:10. It will be appreciated that the height of the pedestal may, in some embodiments, be programmably adjusted by a suitable computer controller.

[0312] While the micro-volume variations described herein refer to a height-adjustable pedestal, it will be understood that in some embodiments, the position of the showerhead 906 may be adjusted relative to the pedestal 908 to vary the volume of the micro-volume 907. Furthermore, it will be understood that the vertical position of the pedestal 908 and / or the showerhead 906 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 908 may include a rotation axis for rotating the orientation of the substrate 912. It will be understood that in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers.

[0313] Returning to the embodiment shown in FIG. 9 , the showerhead 906 and pedestal 908 are in electrical communication with an RF power source 914 and a matching network 916 to power the plasma. In other embodiments, a plasma generator-less apparatus is used to deposit molybdenum-containing films using the provided methods. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, radio frequency (RF) source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 914 and matching network 916 may be operated at any suitable power to form a plasma having a desired composition of radical species. Similarly, the RF power source 914 may provide RF power at any suitable frequency. In some embodiments, the RF power source 914 may be configured to independently control high-frequency RF power and low-frequency RF power. Examples of low-frequency RF frequencies include, but are not limited to, frequencies between 50 kHz and 700 kHz. Examples of high-frequency RF frequencies 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 adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be pulsed intermittently to reduce ion bombardment of the substrate surface compared to a continuously powered plasma.

[0314] 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 concentrations 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, OES sensors may be used in a feedback loop to programmatically control plasma power. It will be appreciated that in some embodiments, other monitors may be used to monitor the plasma and other process attributes. Such monitors include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0315] In some embodiments, the plasma may be provided through input / output control (IOC) sequence instructions. In one example, instructions for setting plasma conditions for a plasma process step may be included in a corresponding plasma activation recipe step of a deposition process recipe. In some cases, process recipe steps may be arranged sequentially so that all instructions for a deposition process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe step preceding a plasma process step. For example, a first recipe step may include instructions for setting flow rates of an inert gas and / or a reactant gas, instructions for setting a power setpoint for a plasma generator, and a time delay instruction for the first recipe step. A subsequent second recipe step may include instructions for enabling the plasma generator and a time delay instruction for the second recipe step. A third recipe step may include instructions for disabling the plasma generator and a time delay instruction for the third recipe step. It will be understood that these recipe steps may be further subdivided and / or repeated in any appropriate manner within the scope of the present disclosure.

[0316] In some embodiments, the pedestal 908 may be temperature controlled via a heater 910. Additionally, in some embodiments, pressure control of the deposition process station 900 may be provided by a butterfly valve 918. As shown in the embodiment of Figure 9, the butterfly valve 918 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the process station 900 may be adjusted by varying the flow rate of one or more gases introduced to the process station 900.

[0317] FIG. 10 is a schematic diagram of one embodiment of a multi-station processing tool 1000 having an inbound load lock 1002 and an outbound load lock 1004, one or both of which may include a remote plasma source. Such a tool may be used to process substrates using the methods provided herein. A robot 1006 is configured to move wafers at atmospheric pressure from a cassette loaded through a pod 1008 to the inbound load lock 1002 through an atmospheric port 1010. The wafer is placed on a pedestal 1012 in the inbound load lock 1002 by the robot 1006, the atmospheric port 1010 is closed, and the load lock is pumped down. If the inbound load lock 1002 includes a remote plasma source, the wafer may be exposed to a remote plasma process within the load lock prior to being introduced into the processing chamber 1014. Additionally, the wafer may also be heated within the inbound load lock 1002, for example, to remove moisture and adsorbed gases. The chamber transfer port 1016 to the processing chamber 1014 is then opened and another robot (not shown) places the wafer into the reactor on a pedestal in the first station shown in the reactor for processing. While the embodiment shown in Figure 10 includes a load lock, it will be understood that in some embodiments the wafer may be placed directly into a process station.

[0318] The illustrated processing chamber 1014 includes four processing stations, numbered 1 through 4 in the embodiment shown in FIG. 10. Each station has a heated pedestal (shown at 1018 for station 1) and a gas line inlet. It will be understood that each process station may have a different purpose or multiple purposes in some embodiments. While the illustrated processing chamber 1014 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.

[0319] FIG. 10 also illustrates one embodiment of a wafer handling system 1090 for transferring wafers within the processing chamber 1014. In some embodiments, the wafer handling system 1090 may transfer wafers between various process stations and / or between process stations and load locks. It will be understood that any suitable wafer handling system may be employed. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 10 also illustrates an embodiment of a system controller 1050 employed to control the process conditions and hardware states of the process tool 1000. The system controller 1050 may include one or more memory devices 1056, one or more mass storage devices 1054, and one or more processors 1052. The processor 1052 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0320] In some embodiments, the system controller 1050 controls all of the activity of the process tool 1000. The system controller 1050 executes system control software 1058 stored on the mass storage device 1054, loaded into the memory device 1056, and executed on the processor 1052. The system control software 1058 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequency, substrate, pedestal, chuck, and / or susceptor position, and other parameters of a particular process being performed by the process tool 1000. The system control software 1058 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components necessary to perform various process tool processes in accordance with the disclosed methods. The system control software 1058 may be coded in any suitable computer-readable programming language.

[0321] In some embodiments, the system controller software 1058 may include input / output control (IOC) sequence instructions for controlling the various parameters described above. For example, each stage of an ALD process may include one or more instructions for execution by the system controller 1050. Instructions for setting process conditions for an ALD process stage may be included in the corresponding ALD recipe step. In some embodiments, the ALD recipe steps may be arranged sequentially such that all instructions for an ALD process step are executed simultaneously with that process step.

[0322] Other computer software and / or programs stored on the mass storage device 1054 and / or memory device 1056 associated with the system controller 1050 may be employed in some embodiments. Examples of programs or portions of programs for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0323] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 1018 and control the spacing between the substrate and other parts of the process tool 1000 .

[0324] The process gas control program may include code for controlling gas composition and flow rates, and optionally for flowing gases into one or more process stations prior to deposition to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rates within any of the disclosed ranges. The pressure control program may include code for controlling the pressure in the process station by, for example, regulating a throttle valve in the exhaust system of the process station, gas flow to 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.

[0325] The heater control program may include code for controlling current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions for maintaining the temperature of the substrate within any of the disclosed ranges.

[0326] The plasma control program may include code for setting the RF power level and frequency applied to the process electrodes of 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.

[0327] In some embodiments, there may be a user interface associated with the system controller 1050. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0328] In some embodiments, the parameters adjusted by the system controller 1050 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power level, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

[0329] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 1050 from various process tool sensors. Signals for controlling the process may be output on analog and digital output connections of the process tool 1000. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0330] Any suitable chamber may be used to implement the disclosed embodiments. Two or more stations may perform the same function. Similarly, two or more stations may perform different functions. Each station may be designed / configured to perform a particular function / method as desired.

[0331] FIG. 11 is a block diagram of a processing system suitable for performing a thin film deposition process according to certain embodiments. The system 1100 includes a transfer module 1103. The transfer module 1103 provides a clean, pressurized environment and minimizes the risk of contamination of processed substrates as they are moved between various reactor modules. The transfer module 1103 is fitted with two multi-station reactors 1109 and 1110, each capable of performing atomic layer deposition (ALD) and / or chemical vapor deposition (CVD) according to certain embodiments. The reactors 1109 and 1110 may include multiple stations 1111, 1113, 1115, and 1117 that may perform operations sequentially or non-sequentially according to disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets, showerheads, or distribution plates.

[0332] The transfer module 1103 may also be equipped with one or more single- or multi-station modules 1107 capable of performing plasma or chemical (non-plasma) pre-cleaning or any other process described in connection with the disclosed methods. The modules 1107 may optionally be used for various processes, such as to prepare substrates for deposition processes. The modules 1107 may also be designed / configured to perform various other processes, such as etching or polishing. The system 1100 also includes one or more wafer source modules 1101 where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 1119 may first retrieve wafers from the source modules 1101 to a load lock 1121. A wafer transfer device (typically a robot arm unit) in the transfer module 1103 moves wafers from the load lock 1121 to between modules mounted on the transfer module 1103.

[0333] In various embodiments, a system controller 1129 is employed to control process conditions during deposition. The controller 1129 will typically include one or more memory devices and one or more processors. The processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0334] The controller 1129 may control all activity of the deposition apparatus. The system controller 1129 executes system control software that includes sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 1129 may also be employed in some embodiments.

[0335] Typically, a user interface is associated with the controller 1129. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0336] The system control logic may be configured in any suitable manner. Generally, logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry may be hard-coded or provided as software. The instructions may be provided by "programming." Such programming is understood to include any form of logic, including hard-coded logic in digital signal processors, application-specific integrated circuits, and other devices in which particular algorithms are implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general-purpose processor. The system control software may be coded in any suitable computer-readable programming language.

[0337] The computer program code for controlling the germanium-containing reducing agent pulses, hydrogen flow, tungsten-containing precursor pulses, and other processes in the process sequence can be written in any conventional computer-readable programming language, such as assembly language, C, C++, Pascal, Fortran, etc. The compiled object code or script is executed by the processor to perform the tasks specified in the program. Also, as suggested, the program code may be hard-coded.

[0338] The controller parameters relate to process conditions such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters may be provided to a user in the form of a recipe and entered using a user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 1129. Signals for controlling the process are output to analog and digital output connections of the deposition apparatus 1100.

[0339] The system software may be designed or configured in a variety of ways. For example, various chamber component subroutines or control objects may be written to control the operation of chamber components necessary to perform deposition processes (and, in some cases, other processes) in accordance with the disclosed embodiments. Examples of programs or portions of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0340] In some embodiments, the controller 1129 is part of a system that may be part of the examples described above. Such systems may include semiconductor processing equipment, such as one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling the operation of the system before, during, and after processing of the semiconductor wafer or substrate. This electronics may be referred to as a “controller,” which may control various components or subcomponents of the system(s). Depending on the processing requirements and / or type of system, the controller 1129 may be programmed to control any of the processes disclosed herein, such as delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out of the tool, and wafer transfer in and out of other transfer tools and / or load locks connected to or interfaced with the particular system.

[0341] Broadly speaking, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that, for example, receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various personalizations (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters, in some embodiments, may be part of a recipe defined by a process engineer to accomplish one or more processing steps in the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer types.

[0342] The controller, in some embodiments, may be part of, or coupled to, a computer integrated with, coupled to, or otherwise networked to the system, or a combination thereof. For example, the controller may be all or part of a host computer system in the “cloud” or at a fab that allows remote access to wafer processing. This computer may provide remote access to the system to monitor the current progress of manufacturing operations, review the history of past manufacturing operations, and review trends or performance criteria from multiple manufacturing operations to modify parameters of a current process, set processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows input or programming of parameters and / or settings, which are then communicated from the remote computer to the system.

[0343] In some examples, the controller receives instructions in the form of data defining parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed or the type of tool the controller is configured to interface with or control. Thus, as discussed above, the controller may be distributed, such as by including one or more separate controllers networked together and working toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes includes one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) combined to control the processes on the chamber.

[0344] Without limitation, exemplary systems may include a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing system associated with or that may be used in the fabrication and / or production of semiconductor wafers.

[0345] As described above, depending on the process step or steps being performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools installed throughout the factory, a main computer, other controllers, or tools used in material transport to and from containers of wafers to tool locations and / or load ports within a semiconductor manufacturing factory.

[0346] Further Examples The apparatus and processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the manufacture or production of semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, but not necessarily, such apparatus / processes are used or performed together in a common manufacturing facility. Lithographic patterning of a film typically includes some or all of the following steps, each enabled by several possible tools: (1) applying a photoresist onto a workpiece (i.e., substrate) using a spin-on or spray-on tool; (2) curing the photoresist using a hotplate, furnace, or UV curing tool; (3) exposing the photoresist to visible, ultraviolet, or X-ray light using a tool such as a wafer stepper; (4) patterning the resist by selectively growing the resist to remove it using a tool such as a wet bench; (5) transferring the resist pattern to an underlying film or workpiece using a dry etching tool or a plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0347] conclusion Although the foregoing embodiments have been described in some detail for 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 considered to be illustrative and not restrictive, and the present embodiments are not limited to the details set forth herein.

Claims

1. 1. A method for depositing a film on a semiconductor substrate, comprising: Providing a semiconductor substrate in a process chamber; forming an iodine bond-containing metal species in the process chamber; forming a metal-containing film on the semiconductor substrate by exposing the iodine bond-containing metal species to a reducing agent; The method wherein the reducing agent comprises a hydrogen-containing gas source.

2. 10. The method of claim 1, forming the iodine bond-containing metal species; (i) introducing a metal-containing precursor into the process chamber containing the semiconductor substrate; (ii) introducing an iodine-containing reagent to react with said metal-containing precursor; or forming the iodine bond-containing metal species; (i) introducing an iodine-containing reagent into the process chamber containing the semiconductor substrate; (ii) introducing a metal-containing precursor to react with said iodine-containing reagent.

3. 3. The method of claim 2, the metal-containing precursor comprises a molybdenum-containing precursor; The method, wherein the iodine-containing reagent comprises hydrogen iodide, iodine, an alkyl iodide, an iodosilane, an alkyliodosilane, a metal iodide, or a metal bromide.

4. 10. The method of claim 1, 10. The method of claim 1, wherein the hydrogen-containing gas source comprises hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and oxygen, hydrogen and nitrogen, ammonia, deuterated mono-substituted ammonia, deuterated di-substituted ammonia, deuterated tri-substituted ammonia, hydrazine, an alcohol, an aldehyde, or a combination thereof.

5. 1. A method for forming a molybdenum-containing layer on a substrate, comprising: Providing a substrate in a processing chamber; introducing a low-valent molybdenum precursor and at least one reactant into the processing chamber; the low valent molybdenum precursor is in an oxidation state of 0, 1, 2, or 3; The low valent molybdenum precursor is represented by formula (I), formula (II), or formula (III): MoL n (I)、 Mo 2 L n (II), or L n Mo (L') m Mol n (III) (In the formula, each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L' is a linking moiety; n is 2, 3, 4, 5, or 6; m is 1, 2, or 3. and and forming a molybdenum-containing layer on the substrate by reacting the low-valent molybdenum precursor with the at least one reactant.

6. 6. The method of claim 5, The low valent molybdenum precursor has the formula MoL 4 The structure of The low valent molybdenum precursor has formula (V): 【Chemical 1】 The structure of During the ceremony, Each R 1 independently comprises alkyl or haloalkyl; Each R 2 independently comprises carbonyl, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl, isocyanato, or isothiocyanato; The method wherein n is 0, 1, 2, or 3.

7. 6. The method of claim 5, The low valent molybdenum precursor has the formula MoL 4 The structure of The low valent molybdenum precursor has formula (VI): 【Chemistry 2】 The structure of During the ceremony, Each R 4 are independently aliphatic, alkylsilyl, or haloalkyl; or R 4 The method wherein the substituted moieties are optionally linked to form a ring.

8. 6. The method of claim 5, The low valent molybdenum precursor has the formula MoL 5 The structure of The low valent molybdenum precursor has formula (X) or formula (XI): 【Chemistry 3】 【Chemistry 4】 The structure of During the ceremony, Each R 7 is independently, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -CF 3 , -C(F)=CF 2 , -C(F)=C(F)CF 3 , -CF 2 C(F)=CF 2 , -C 4 F 9 , -C 5 F 11 , -CH 2 CF 3 , -CH(CF 3 ) 2 , -CH(CH 3 )(CF 3 ), -C(CH 3 ) 2 (CF 3 ), -C(CF 3 ) 3 , -Si(CH 3 ) 3 , -Si(C 2 H 5 ) 3 , -CH 2 Si(CH 3 ) 3 , -CH(Si(CH 3 ) 3 ) 2 , -C(Si(CH 3 ) 3 ) 3 , -P(CH 3 ) 3 , -CH 2 P(CH 3 ) 3 , -P(O)OH, -P(O)(OCH 3 ) 2 , -P(O)(OCH 2 CH 3 ) 2 , -CH(Si(CH 3 ) 3 )(P(CH 3 ) 3 ), -SO 2 CF 3 , -SO 2 C 3 N 2 H 3 , -C(O)C 3 F 7 , -CHCHSO 2 C 6 H 5 , -SO 2 OCH 3 , or -SO 2 C 6 H 4 CH 3 and Each R 8 are independently selected from allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, —NO, —CO, —P(CH 3 ) 3 , -P(CH 2 CH 3 ) 3 , or -CNR 9 and R 9 comprises an aliphatic, aryl, or heterocyclyl.

9. 6. The method of claim 5, The low valent molybdenum precursor has the formula MoL 3 The structure of The low valent molybdenum precursor has formula (XIV): 【Chemistry 5】 The structure of During the ceremony, Each R 15 independently comprises an aliphatic, alkylsilyl, or haloalkyl; or R 15 The method wherein the substituted moieties are optionally linked to form a ring.

10. A metal coordination complex represented by formula (VI), formula (IX), formula (X), formula (XI): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】 Or formula (XV): Mo 2 (OR 16 ) 6 The structure of During the ceremony, R 4 , R 6 , R 7 , and R 16 are each independently, -CH 3 , -C 2 H 5 , -C 3 H 7 , -C 4 H 9 , -C 5 H 11 , -CF 3 , -C(F)=CF 2 , -C(F)=C(F)CF 3 , -CF 2 C(F)=CF 2 , -C 4 F 9 , -C 5 F 11 , -CH 2 CF 3 , -CH(CF 3 ) 2 , -CH(CH 3 )(CF 3 ), -C(CH 3 ) 2 (CF 3 ), -C(CF 3 ) 3 , -Si(CH 3 ) 3 , -Si(C 2 H 5 ) 3 , -CH 2 Si(CH 3 ) 3 , -CH(Si(CH 3 ))[[ID=8​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 3 ) (P (CH 3 ) 3 ), -SO 2 CF 3 , -SO 2 C 3 N 2 H 3 , -C(O)C 3 F 7 , -CHCHSO 2 C 6 H 5 , -SO 2 OCH 3 , or -SO 2 C 6 H 4 CH 3 Including, G is =O, =NR, =S, or =CR 2 Including, each R independently comprises an aliphatic group, an aryl group, a haloalkyl group, or a haloaryl group; Each R 8 are independently selected from allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, —NO, —CO, —P(CH 3 ) 3 , -P(CH 2 CH 3 ) 3 , or -CNR 9 and R 9 is an aliphatic, aryl, or heterocyclyl-containing metal coordination complex.

11. 1. A method for depositing a film on a semiconductor substrate, comprising: Providing a semiconductor substrate in a process chamber; forming an iodine bond-containing metal species in the process chamber; forming a metal-containing film on the semiconductor substrate by exposing the iodine bond-containing metal species to a reducing agent; forming the iodine bond-containing metal species; (i) introducing a metal-containing precursor into the process chamber containing the semiconductor substrate; (ii) introducing an iodine-containing reagent to react with said metal-containing precursor; or forming the iodine bond-containing metal species; (i) introducing an iodine-containing reagent into the process chamber containing the semiconductor substrate; (ii) introducing a metal-containing precursor to react with the iodine-containing reagent; the metal-containing precursor comprises a low-valent molybdenum precursor; the low valent molybdenum precursor is in an oxidation state of 0, 1, 2, or 3; The low valent molybdenum precursor is represented by formula (I), formula (II), or formula (III): MoL n (I)、 Mo 2 L n (II), or L n Mo (L') m Mol n (III) The structure of During the ceremony, each L is independently a monodentate, ambidentate, bidentate, or tridentate ligand; L' is a linking moiety; n is 2, 3, 4, 5, or 6; The method wherein m is 1, 2, or 3.

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