Deposition of metal-containing films

Abstract

A method of providing a deposited metal-containing film by generating an iodine bond-containing metal species in situ with an iodine-containing reagent and a metal-containing precursor at a processing temperature of less than 400 DEG C and followed by reduction. In particular, the film may be a molybdenum-containing film. The method may also include the simultaneous introduction of the reagent with a precursor or optionally a pretreatment with a passivation gas. Also provided are methods of depositing molybdenum-containing films on semiconductors using the low-valent molybdenum-containing precursors. The low valent molybdenum precursor of one or two molybdenum atoms may have at least one ligand that is an isocyano haloalkyl group, an allyl group, an aryl group, a tertiary organic phosphino group, or an alkoxy group.

Description

Incorporation by reference

[0001] The PCT application form is filed simultaneously with this specification as part of this application. Each application identified in the simultaneously filed PCT application form for which this application claims the benefit or priority thereof is incorporated herein by reference in its entirety and for all purposes. Technical Field

[0002] The present disclosure relates to methods of manufacturing semiconductor devices. In particular, embodiments of the present disclosure relate to precursors for depositing molybdenum-containing films in semiconductor processing. Background Art

[0003] In the manufacture of integrated circuits (ICs), deposition and etching techniques are used to form patterns of materials, such as for forming metal lines embedded in dielectric layers. Some patterning schemes require conformal deposition of materials, where the deposited layer should follow the contours of the protrusions and / or recessed features on the substrate surface. Atomic layer deposition (ALD) is generally the preferred method for forming conformal films on substrates because ALD relies on the adsorption of one or more reactants (precursors) onto the substrate surface and the subsequent chemical conversion of the adsorbed layer into the desired material. Since ALD uses sequential reactions that occur on the substrate surface, these reactions are separated in time and are generally limited by the amount of adsorbed reactants, so the method can provide thin conformal layers with excellent step coverage.

[0004] Atomic layer deposition (ALD) is a known method for depositing thin films. It is a unique self-limiting and continuous thin film growth technique based on surface reactions that provide atomic layer control and deposit conformal thin films of the materials provided by the precursors onto substrates of different compositions. In ALD, the precursors are conventionally separated during the reaction. A first precursor passes over the substrate, creating a monolayer on the substrate. Any excess unreacted precursor is pumped out of the processing chamber. A second precursor then passes over the substrate and reacts with the first precursor to form a monolayer film on the substrate surface. This cycle is typically repeated at a processing temperature above 450 °C to form a film of the desired thickness.

[0005] Depositing metal-containing films at lower temperatures (below 400 °C) would be advantageous for certain applications. At such reduced temperatures, the likelihood of impurities appearing increases. Therefore, there is a need for ALD processes that can be carried out at lower temperatures and that can minimize impurities.

[0006] Chemical vapor deposition (CVD) is another deposition method widely used in semiconductor processing. In CVD, the reaction occurs in the volume of the processing chamber and is not limited by the amount of reactants adsorbed onto the substrate. Therefore, CVD-deposited films are generally less conformal than ALD-deposited films. CVD is typically used in applications where step coverage is less important.

[0007] ALD and CVD can use plasma to facilitate the reaction of deposition precursors to form the desired film. The methods that utilize plasma are referred to as plasma-enhanced ALD (PEALD) and plasma-enhanced CVD (PECVD). The methods that do not use plasma are referred to as thermal ALD and thermal CVD.

[0008] Although ALD and CVD are most commonly used for the deposition of silicon-containing films (e.g., silicon oxides, silicon nitrides, and silicon carbides), these methods are also applicable to the deposition of certain metals, especially tungsten and cobalt.

[0009] The background description provided here is for the purpose of generally presenting the background of the present disclosure. Aspects of the work of the currently named inventors that are within the scope described in this background art section and that are not, at the time of filing the application, determined to be prior art in the specification are neither expressly nor impliedly admitted to be prior art against the present disclosure. Summary of the Invention

[0010] There is provided a method for depositing a metal-containing film by in-situ generating a metal species having iodine bonds with an iodine-containing reagent and a metal precursor at a processing temperature below 400 °C and then performing reduction. In some instances, the method may further include simultaneously introducing the iodine-containing reagent and the metal precursor or optionally pre-treating with a passivation gas. In particular, the precursor may be a molybdenum-containing precursor, such as a low-valent molybdenum precursor, and the film may be a molybdenum-containing film. The method can advantageously produce a metal-containing film having fewer halogen-based impurities or other impurities. There is also provided a low-valent molybdenum precursor having one or two molybdenum atoms and having at least one ligand selected from the group consisting of isocyano haloalkyl, allyl, aryl, tertiary organophosphino, or alkoxy groups. Additionally, there is provided a method for depositing a molybdenum-containing film, such as metallic molybdenum, molybdenum nitride (MoN x )), molybdenum carbide (MoC x ), molybdenum boride (MoB x ), molybdenum silicide (MoSi x ), and combinations thereof, such as molybdenum carbonitride (MoC x N y ), molybdenum borocarbonide (MoB x C y ).

[0011] Thus, in a first aspect, the present invention encompasses a method for depositing a film on a semiconductor substrate. In some embodiments, the method includes providing a semiconductor substrate in a processing chamber; forming a metal species having iodine bonds in the processing chamber; and exposing the metal species having iodine bonds to a reducing agent, thereby forming a metal-containing film on the semiconductor substrate; wherein the reducing agent includes a hydrogen-containing gas source.

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

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

[0014] In some embodiments, the metal 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 precursor is a molybdenum-containing precursor.

[0016] In some embodiments, the molybdenum precursor has a structure of 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 ligand, an ambidentate ligand, a bidentate ligand, or a 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, halogen, hydroxyl, alkylsilyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynyloxy, 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(C 1-(C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclic group, alkyl heterocyclic group, heterocycloalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, =O, =S, ≡N, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, -C(O)NH(benzyl), amide group, azide group, isocyanato group, cyanothio group, isocyanothio group, cyano group, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl or cyclo group.

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

[0020] In some embodiments, the molybdenum oxohalide is Mo q O n Y m , where Y is a halogen; n is 1 or 2; q is 1, 2 or 4; m is 1, 2 or 11.

[0021] In some embodiments, the molybdenum oxohalide is MoOF4, Mo4O 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)6 or C 16 H 20 Mo.

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

[0025] In some embodiments, the low-valent molybdenum precursor has an oxidation state of zero, one, two or three.

[0026] In some embodiments, the iodine-containing reagent is hydrogen iodide, iodine, alkyl iodide, iodosilane, alkyl iodosilane, metal iodide or 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 alkyl iodosilane 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 metal species containing an iodine bond 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, monodeuterated ammonia, dideuterated ammonia, trideuterated ammonia, hydrazine, alcohol, aldehyde, or a combination thereof.

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

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

[0037] In some embodiments, forming the metal species containing an iodine bond and exposing the metal species containing an iodine bond to the reducing agent are carried out simultaneously.

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

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

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

[0041] In some embodiments, the method further comprises (iii) pre - treating with an iodine - containing reagent, a passivation gas, or both an iodine - containing reagent and a passivation gas before (i).

[0042] In some embodiments, the method further comprises pre - treating with a passivation gas simultaneously during (i).

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

[0044] In some embodiments, the method further comprises cyclically repeating (i), (ii), and exposing a metal species having an iodine bond to a reducing agent to form a metal - containing film.

[0045] In some embodiments, the method further comprises cyclically repeating (i) and simultaneously forming a metal species having an iodine bond and exposing the metal species having an iodine bond to a reducing agent to form a metal - containing film.

[0046] In some embodiments, the method further comprises cyclically repeating (i) and (ii) to form a metal - containing film.

[0047] In some embodiments, the method further comprises cyclically repeating (i) and (ii) and repeating (i), (ii), and exposing a metal species having an iodine bond to a reducing agent to form a metal - containing film.

[0048] In some embodiments, the method further comprises cyclically repeating (i), (ii), and exposing a metal species having an iodine bond to a reducing agent to form a metal - containing film.

[0049] In some embodiments, the method further comprises cyclically repeating (i), (ii), (iii), and exposing a metal species having an iodine bond to a reducing agent to form a metal - containing film.

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

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

[0052] In some embodiments, the temperature of the processing chamber is maintained at less than about 400 °C.

[0053] In some embodiments, the temperature of the processing chamber is maintained at about 200 °C to about 300 °C, and the processing chamber has a pressure of less than about 500 Torr.

[0054] In some embodiments, at least one of the metal species forming an iodine-containing bond and the metal-containing film is formed by atomic layer deposition, purge-free atomic layer deposition, pulsed chemical vapor deposition, or plasma-enhanced atomic layer deposition.

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

[0056] In a third aspect, the present invention encompasses a method for forming a molybdenum-containing layer on a substrate. In some embodiments, the method includes providing a substrate within a processing chamber; introducing a low-valence molybdenum precursor and at least one reactant into the processing chamber, wherein the low-valence molybdenum precursor has an oxidation state of zero, one, two, or three, and wherein the low-valence molybdenum precursor has a structure of 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 ligand, an ambidentate ligand, a bidentate ligand, or a tridentate ligand, L' is a linking moiety, n is 2, 3, 4, 5, or 6; and m is 1, 2, or 3; and reacting the low-valence molybdenum precursor with the at least one reactant to form a molybdenum-containing layer on the substrate.

[0057] In some embodiments, the monodentate ligand includes hydrogen, halogen, 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(C 1-(C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclic group, alkyl heterocyclic group, heterocycloalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, =O, =S, ≡N, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, -C(O)NH(benzyl), amido, azide, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl or cyclo group.

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

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

[0060] In some embodiments, the monodentate ligand is at least one allyl, allene, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuryl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl or pyrimidinyl.

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

[0062] In some embodiments, the bidentate ligand is -O(C(R) n ) m O-, -O(C(R) n ) mNR−, −C(R)2P(R)2C(R)2P(R)2−C(R)2− or −C(R)2P(R)2N(R)P(R)2−C(R)2−; where each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or the R groups may 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 the 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 structure of formula (V):

[0066] where each R 1 independently comprises alkyl or haloalkyl; each R 2 independently comprises 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 , where R 3 comprises aliphatic, aryl or heterocyclic.

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

[0069] In some embodiments, R 3 is pentafluoroethyl, heptafluoropropyl, 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 nonafluorobutyl.

[0070] In some embodiments, the low-valent molybdenum precursor has the structure of formula (VI):

[0071] where each R 4 is independently aliphatic, alkylsilyl or haloalkyl; or the R 4 substituents may be joined to form a ring.

[0072] In some embodiments, each R4 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 a structure of formula (VII): where each E independently comprises NR, C(R) n , Si(R) n , S, O or P(R) n , where each R independently comprises hydrogen, aryl, amino or aliphatic; each R 5independently includes halogen, hydroxyl, aliphatic, alkylsilyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynyloxy, 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, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclic group, alkyl heterocyclic group, heterocycloalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, =O, =S, -CO, aralkenyl, aralkyl, sulfonyl, sulfonamido, carbamate, aryloxyalkyl, carboxyl, -C(O)NH(benzyl), amido, azide, isocyanate, isocyanoalkyl, isocyano haloalkyl, isocyanoaryl, cyanosulfanyl, isocyanosulfanyl, cyano or cyclo group; 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 a structure of formula (VIII): where each E independently includes NR, C(R) n , Si(R) n , S, O or P(R) n ; where each R independently includes 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 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 a structure of formula (IV): -(E) e -(IV), where each E is independently NR, C(R) n , Si(R)n 、 S, O or P(R) n ; 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-; wherein each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or the R groups may 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 a structure of formula (X) or formula (XI): wherein each R 7 is 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; and each R 8 is independently allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR9 , wherein R 9 is an aliphatic, aryl or heterocyclic group.

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

[0082] In some embodiments, R 9 is pentafluoroethyl, heptafluoropropyl, 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 nonafluorobutyl.

[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 a structure of formula (IV): -(E) e -(IV), wherein each E is independently NR, C(R) n , Si(R) n , S, O or P(R) n ; 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-; wherein each R is independently H, aliphatic, haloalkyl, alkylsilyl, alkylamino, amino or alkoxy, or the R groups may be linked 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 a structure of formula (XII): Mo(X) p (R10) q (XII), wherein each X is independently chlorine, fluorine, bromine or iodine; each R 10are independently allyl, propadienyl, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 11 , where R 11 is an aliphatic, aromatic or heterocyclic group; p is 1, 2, 3 or 4; q is 2, 3, 4 or 5; p+q=6.

[0088] In some embodiments, R 11 It is a halogenated alkyl group or a halogenated aryl group.

[0089] In some embodiments, R 11 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 structure of Formula (XIII): Mo(R 12 ) r (R 13 ) s (XIII), where each R 12 are independently allyl, propadienyl, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)2, -P(CH2CH3)2, or -CNR 14 , where R 14 is an aliphatic, aromatic or heterocyclic group; each R 13 are independently trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine, tri(trimethylsilyl)phosphine, tri(2-carboxyethyl)phosphine, tri(dimethylamino)phosphine, tri(o-tolyl)phosphine, tri(4-methoxyphenyl)phosphine or tri(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 It is a halogenated alkyl group or a halogenated aryl group.

[0092] In some embodiments, R 14is pentafluoroethyl, heptafluoropropyl, 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 nonafluorobutyl.

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

[0094] In some embodiments, each L is independently allyl, allene, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuryl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, or pyrimidinyl.

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

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

[0097] In some embodiments, the low-valent molybdenum precursor has a structure of formula (XIV): where each R 15 is independently aliphatic, alkylsilyl or haloalkyl; or R 15 substituents may be linked to form a ring.

[0098] In some embodiments, each R 15 is 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): Mo2(OR 16 )6 (XV), where each R 16 is 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, the at least one reactant is hydrogen, ammonia, diborane, water, hydrogen sulfide, thiol, alcohol, amine, hydrazine, silane, or disilane.

[0104] In a fourth aspect, the present invention encompasses metal coordination complexes. In some embodiments, the complex has the structure of formula (V): where each R 1 is independently alkyl or haloalkyl; 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 invention encompasses metal coordination complexes. In some embodiments, the complex has the structure of formula (VI), formula (IX), formula (X), formula (XI), or formula (XV): Mo2(OR 16 )6 (XV), where 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, where each R is independently aliphatic, aryl, haloalkyl or haloaryl; and each R 8 is independently allyl, allene, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuryl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 9 , where R 9 is aliphatic, aryl or heterocyclic.

[0106] In a sixth aspect, the present invention encompasses metal coordination complexes. In some embodiments, the complex has a structure of formula (XII) or formula (XIII): Mo(X) p (R 10 ) q (XII) or Mo(R 12 )r(R 13 ) s (XIII), where each X is independently chlorine, fluorine, bromine or iodine; where R 10 and R 12Each independently is allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 14 , where R 14 is aliphatic, aryl or heterocyclic; each R 13 is independently trimethylphosphine, triethylphosphine, triisopropylphosphine, triphenylphosphine, tris(trimethylsilyl)phosphine, tris(2-carboxyethyl)phosphine, tris(dimethylamino)phosphine, tris(o-tolyl)phosphine, tris(4-methoxyphenyl)phosphine or tris(2-furyl)phosphine; p is 1, 2, 3 or 4; q is 2, 3, 4 or 5; p + q = 6; r is 1, 2, 3, 4, 5 or 6; s is 0, 1, 2, 3, 4 or 5; r + s = 6; provided that at least one R 10 of formula (XII) is -CNR 14 ; and provided that at least one R 12 of formula (XIII) is -CNR 14 .

[0107] In a seventh aspect, the present invention encompasses an apparatus for processing a substrate. In some embodiments, the apparatus includes a processing chamber having a substrate holder and one or more inlets for introducing reactants into the processing chamber; and a device controller including program instructions for: causing a low-valent molybdenum precursor to be introduced into the processing chamber; where the low-valent molybdenum precursor has an oxidation state of zero, one, two or three, and where the low-valent molybdenum precursor has a structure of 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 ligand, a multidentate ligand, a bidentate ligand or a tridentate ligand, L' is a connecting moiety, n is 2, 3, 4, 5 or 6; m is 1, 2 or 3; and causing the low-valent molybdenum precursor to react and form a molybdenum-containing layer on the substrate.

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

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

[0110] The molybdenum precursors described herein can be used in ALD and CVD to deposit molybdenum-containing films in various applications. In some embodiments, the precursors are used to form conformal films. In other embodiments, the precursors are used to fill recessed features with a molybdenum-containing material (e.g., with 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 invention encompasses a method of depositing a film on a semiconductor substrate. In some embodiments, the method includes providing a semiconductor substrate in a processing chamber; forming a metal species having an iodine bond in the processing chamber; exposing the metal species having an iodine bond to a reducing agent, thereby forming a metal-containing film on the semiconductor substrate; wherein forming the metal species having an iodine bond includes (i) introducing a metal precursor into a processing chamber containing the semiconductor substrate; and (ii) introducing an iodine-containing reagent to react with the metal precursor, or wherein forming the metal species having an iodine bond includes (i) introducing an iodine-containing reagent into a processing chamber containing the semiconductor substrate; and (ii) introducing a metal precursor to react with the iodine-containing reagent; wherein the metal precursor is a low-valent molybdenum precursor having an oxidation state of zero, one, two, or three, and wherein the low-valent molybdenum precursor has a structure of 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 ligand, a multidentate ligand, a bidentate ligand, or a 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 aspects of the embodiments of the subject matter described in this specification are set forth in the accompanying drawings and the description below. BRIEF DESCRIPTION OF THE DRAWINGS

[0113] Figure 1A-1C A cross-sectional view of a substrate during deposition of a metal-containing film according to certain disclosed embodiments is shown.

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

[0115] Figure 2B Examples of general formula structures of molybdenum precursors according to certain disclosed embodiments are provided.

[0116] Figure 2C Examples of low-valent molybdenum precursors of formula Mo(L)6 according to certain disclosed embodiments are provided.

[0117] Figure 2DProvide examples of low-cost dimolybdenum precursors according to certain disclosed embodiments.

[0118] Figure 3 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a metal-containing film by exposing to a metal precursor and simultaneously exposing to an iodine-containing reagent and a reducing agent according to certain disclosed embodiments.

[0119] Figure 4 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a metal-containing film by cyclic deposition process according to certain disclosed embodiments.

[0120] Figure 5 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a metal-containing film by cyclic deposition process according to certain disclosed embodiments, the cyclic deposition process including pretreatment with an iodine-containing reagent or a passivation gas.

[0121] Figure 6 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a metal-containing film by cyclic deposition process according to certain disclosed embodiments, the cyclic deposition process including pretreatment with an iodine-containing reagent and a passivation gas simultaneously.

[0122] Figure 7 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a molybdenum-containing film according to certain disclosed embodiments.

[0123] Figure 8 FIG. [not clear what number should be here, seems like a missing number in the original] is a process flow diagram of a method for forming a molybdenum metal film according to certain disclosed embodiments.

[0124] Figure 9 FIG. [not clear what number should be here, seems like a missing number in the original] is a schematic diagram of an apparatus suitable for depositing a molybdenum-containing film according to certain disclosed embodiments.

[0125] Figure 10 FIG. [not clear what number should be here, seems like a missing number in the original] shows a schematic diagram of a multi-station processing system according to certain disclosed embodiments.

[0126] Figure 11 FIG. [not clear what number should be here, seems like a missing number in the original] shows a schematic diagram of a multi-station processing system according to certain disclosed embodiments. DETAILED DESCRIPTION

[0127] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known processing operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that it is not intended to limit the disclosed embodiments.

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

[0129] The methods can be used to deposit a variety of molybdenum-containing materials, including but not limited to molybdenum metal, molybdenum nitride (MoN x ), molybdenum carbide (MoC x ), molybdenum boride (MoB x ), molybdenum silicide (MoSi x ), molybdenum boron carbide (MoB x C y ), and molybdenum carbonitride (MoC x N y ), where x and y indicate that the stoichiometry of these compounds may vary. The provided precursors are particularly suitable for depositing molybdenum metal, such as high-purity molybdenum metal with a low incorporation of other elements. Definitions

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

[0131] Molybdenum nitride (MoN x ), molybdenum carbide (MoC x ), molybdenum boride (MoB x ), molybdenum silicide (MoSi x ), molybdenum boron carbide (MoB x C y ) and molybdenum carbonitride (MoC x N y ) refer to materials consisting essentially of molybdenum with nitrogen (MoN x ), molybdenum with carbon (MoC x ), molybdenum with boron (MoB x ), molybdenum with silicon (MoSi x ), molybdenum, boron and carbon (MoB x C y ), and molybdenum, carbon and nitrogen (MoC x N yThe materials are composed of, where x and y represent that the stoichiometry of these compounds may vary. Other elements may be present in these compounds in small amounts, for example, in amounts less than about 10% by atom, with hydrogen excluded from the calculation.

[0132] As used herein, the term "semiconductor substrate" refers to a substrate at any stage of semiconductor device manufacturing that contains semiconductor material located at any position within its structure. It is understood that the semiconductor material in the semiconductor substrate does not need to be exposed. Examples of semiconductor substrates are semiconductor wafers having multiple other material (e.g., dielectric) layers covering the semiconductor material. The detailed description below assumes that the disclosed implementations are implemented on semiconductor wafers (e.g., on 200 mm, 300 mm, or 450 mm semiconductor wafers). However, the disclosed implementations are not limited thereto. The workpiece can be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpiece types that can utilize the disclosed implementations include various articles, such as printed circuit boards, etc.

[0133] "Aliphatic" means having at least one carbon atom to 50 carbon atoms (C 1-50 )(e.g., one to 25 carbon atoms (C 1-25 )) or one to ten carbon atoms (C 1-10 )) hydrocarbon moiety, and it includes saturated groups such as alkanes (or alkyls) and unsaturated groups such as alkenes (or alkenyls), alkynes (or alkynyls), and also includes its cyclic forms, and further includes straight-chain and branched arrangements, as well as all stereoisomers and positional isomers. Such hydrocarbons can be unsubstituted or substituted with one or more groups (e.g., halogens or the groups described herein for alkyls).

[0134] "Alkenyl" means an optionally substituted C 2-24 alkyl having one or more double bonds. Alkenyl can be cyclic (e.g., C 3-24 cycloalkenyl) or acyclic. Alkenyl can also be substituted or unsubstituted. For example, alkenyl can be substituted with one or more substituents as described herein for alkyls. Non-limiting unsubstituted alkenyls include C 2-8 alkenyl, C 2-6 alkenyl, C 2-5 alkenyl, C 2-4 alkenyl or C 2-3Alkenyl. Exemplary and non-limiting alkenyls include vinyl (vinyl or ethenyl, -CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), 2-butenylene (e.g., =CH-CH=CHCH3) and the like.

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

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

[0137] "Alkyl" and the prefix "alk" mean a branched or unbranched saturated hydrocarbon group having 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), sec-butyl (s-Bu or sBu), tert-butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl can be cyclic (e.g., C 3-24cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include a haloalkyl group, where the alkyl group is substituted with one or more halogen groups, such as those described herein. In another example, the alkyl group can be substituted with one, two, three, or four (in the example of an alkyl group having two or more carbons) substituents, the 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 alkyl); (2) amino (e.g., -NR N1 R N2 , where each R N1 and R N2 is independently H or an optionally substituted alkyl group, or R N1 and R N2 together with the nitrogen atom to which they are attached form a heterocyclic group); (3) aryl; (4) aralkoxy (e.g., -O-Lk-Ar, where Lk is a divalent form of an optionally substituted alkyl group and Ar is an optionally substituted aryl group); (5) aroyl (e.g., -C(O)-Ar, where Ar is an optionally substituted aryl group); (6) cyano (e.g., -CN); (7) carboxaldehyde group (e.g., -C(O)H); (8) carboxyl group (e.g., -CO2H); (9) C 3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C 3-8 hydrocarbyl group); (10) halogen (e.g., F, Cl, Br, or I); (11) heterocyclic group (e.g., a 3-, 4-, 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., nitrogen, oxygen, phosphorus, sulfur, or halogen), unless otherwise specified); (12) heterocyclic oxy group (e.g., -O-Het, where Het is a heterocyclic group as described herein); (13) heterocyclic acyl group (e.g., -C(O)-Het, where Het is a heterocyclic group as described herein); (14) hydroxyl group (e.g., -OH); (15) N-protected amino; (16) nitro group (e.g., -NO2); (17) oxo group (e.g., =O); (18) -CO2R A , where 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 group); (19) -C(O)NR B R C , where R B and R CEach 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 and Ar is an optionally substituted aryl); and (20) -NR G R H wherein 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., an optionally substituted alkyl having one or more double bonds), (e) C 2-6 alkynyl (e.g., an 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 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 and Cy is an optionally substituted cycloalkyl as described herein), provided that in one embodiment, no two groups are bonded to the nitrogen atom through a carbonyl group. The alkyl can be a primary, secondary, or tertiary alkyl substituted with one or more substituents (e.g., one or more halogens or alkoxy groups). In some embodiments, the unsubstituted alkyl 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 alkyl.

[0138] "Alkylene" means a divalent form of an alkyl as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene is C 1-3 C 1-6 C1-12 , 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 An alkylene group. The alkylene group may be branched or unbranched. The alkylene group may also be substituted or unsubstituted. For example, the alkylene group may be substituted with one or more substituents, as described herein for alkyl groups.

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

[0140] As used herein, the term "alkylsilyl" refers to an SiR3 group, where at least one R is an alkyl group and each R is independently selected from H and alkyl groups. Alkylsilyls include mono-, di-, and tri-alkylsilyls. Examples of alkylsilyls include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, and ethylsilyl.

[0141] "Alkynyl" means an optionally substituted C 2-24 alkyl group having one or more triple bonds. The alkynyl group may be cyclic or acyclic, such as ethynyl, 1-propynyl, and the like. The alkynyl group may also be substituted or unsubstituted. For example, the alkynyl group may be substituted with one or more substituents, as described herein for alkyl groups. Non-limiting unsubstituted alkynyls include C 2-8 alkynyl, C 2-6 alkynyl, C 2-5 alkynyl, C 2-4 alkynyl, or C 2-3 alkynyl. Exemplary non-limiting alkynyls include ethynyl (-C≡CH), 1-propynyl (-C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), and the like.

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

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

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

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

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

[0147] "Aryl" means a group containing any carbon-based aromatic group, including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl and the like, including fused benzo-C 4-8A cycloalkyl group (e.g., as defined herein), such as indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group and the aromatic group has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term "non-heteroaryl" (which is also included within the term "aryl") is defined as a group containing an aromatic group without heteroatoms. The aryl may be substituted or unsubstituted. The aryl may be substituted with one, two, three, four, or five substituents, such as any of those described herein for alkyl groups.

[0148] "Azido" means -N3.

[0149] "Branched alkenyl" means an isomer of a straight-chain alkenyl compound; a group having an alkyl group bonded to the main carbon chain.

[0150] "Cyano" means -CN.

[0151] "Carbonyl" means a -C(O)- group, which may also be represented as >C=O.

[0152] "Cycloalkyl" means a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group having three to eight carbons (unless otherwise specified), and examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. The cycloalkyl may also be substituted or unsubstituted. For example, the cycloalkyl may be substituted with one or more groups (including those described herein for alkyl groups).

[0153] "Deposition" or "vapor deposition" means a method of forming a metal layer on one or more surfaces of a substrate from a vaporized precursor composition comprising one or more metal-containing compounds. The metal-containing compounds are vaporized and directed to one or more surfaces of and / or in contact with a substrate (i.e., a semiconductor substrate or semiconductor component) placed in a deposition chamber. Typically, the substrate is heated. These metal-containing compounds form a non-volatile, thin, and uniform metal-containing layer on the surface of the substrate. One operation of this method is one cycle, and the process may be repeated for a number of cycles required to obtain the desired metal thickness.

[0154] "Dicarbonyl" means any moiety or compound comprising two carbonyls as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., R C1 -C(O)-C(O)RC2 , wherein R C1 and R C2 are each independently an optionally substituted alkyl, halogen, optionally substituted alkoxy, hydroxy, or leaving group); 1,3-dicarbonyl (e.g., R C1 -C(O)-C(R 1a R 2a )-C(O)R C2 , wherein R C1 and R C2 are each independently an optionally substituted alkyl, halogen, optionally substituted alkoxy, hydroxy, or leaving group, and wherein R 1a and R 2a are each independently H or an optional substituent 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 , wherein R C1 and R C2 are each independently an optionally substituted alkyl, halogen, optionally substituted alkoxy, hydroxy, or leaving group, and wherein R 1a , R 2a , R 3a and R 4a are each independently H or an optional substituent provided for alkyl as defined herein).

[0155] As used herein, "fluoroalkyl" refers to an alkyl containing one or more fluorine substitutions. In some embodiments, fluoroalkyl non-exclusively includes fluorine substituents such as CF3, C2F5, C3F7. Fluoroalkyl can be straight-chain, branched-chain, and cyclic.

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

[0157] "halo-containing substituent" means a group containing a halogen, such as a haloaliphatic or haloalkyl group.

[0158] "haloaliphatic" means an aliphatic group as defined herein substituted with one or more halogens.

[0159] "haloalkenyl" means an alkenyl as defined herein substituted with one or more halogens.

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

[0161] "Haloalkyl" means an alkyl group as defined herein that is substituted with one or more halogen atoms. 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 haloalkyl. Other non-limiting haloalkyl groups include -CX y H 3-y , where y is 1, 2, or 3, and where each X is independently a halogen (F, Cl, Br, or I); -CX z H 2-z CX y H 3-y , where z is 0, 1, or 2, where y is 0, 1, 2, or 3, and where each X is independently a halogen (F, Cl, Br, or I), where at least one of z or y is 0; -CH2CX y H 3-y , where y is 1, 2, or 3, and where each X is independently a halogen (F, Cl, Br, or I); -CX z1 H 2-z1 CX z2 H 2-z2 CX y H 3-y , where z1 and z2 are each independently 0, 1, or 2, where y is 0, 1, 2, or 3, and where each X is independently a halogen (F, Cl, Br, or I), where at least one of z1, z2, or y is not 0; and -CX z H 1-z [CX y1 H 3-y1 [CX y2 H 3-y2 , where z is 0 or 1, where y1 and y2 are each independently 0, 1, 2, or 3, and where each X is independently a halogen (F, Cl, Br, or I), where 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 halogen atoms.

[0163] "Heterocyclyl" means a 3-, 4-, 5-, 6- or 7-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 halogen), unless otherwise specified. The 3-membered ring has zero to one double bond, the 4- and 5-membered rings have zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic and tetracyclic groups, wherein any of the above heterocyclic rings is fused to one, two or three rings independently selected from the group consisting of an aromatic ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocycles include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl,benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimylbipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyldioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H-indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl,naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl,pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl, piperidyl, tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiadiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl,Thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl and the like, and modified forms thereof (e.g., including one or more oxo and / or amino), and salts thereof. The heterocyclic group may be substituted or unsubstituted. For example, the heterocyclic group may be substituted with one or more substituents as described herein for aryl.

[0164] "Hydroxyl" means -OH.

[0165] "Imino" means -NR-, where R may be H or optionally substituted alkyl.

[0166] "Isocyanato" means -NCO.

[0167] "Isocyano" means and includes nitriles of the formula RN≡C—, where R is an aliphatic, aryl or heteroaryl group.

[0168] “Isothiocyanato” means —N═C═S.

[0169] “Low valent” means a lower oxidation state when the metal has multiple oxidation states.

[0170] “Oxo” means ═O group.

[0171] “Oxy” means —O—.

[0172] “Silyl” means —SiR 1 R 2 R 3 or —SiR 1 R 2 — group. 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. In certain embodiments, R 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 , where each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In 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 , where R 1 、R 2 and R 3Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In certain embodiments, R 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 siloxy is -O-Si(R) a (OR) b (NR2) c , where each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0174] The use of the above terms is intended to cover both substituted and unsubstituted moieties. Substitution can be by one or more groups such as alcohol, ether, ester, amide, sulfone, sulfide, hydroxyl, nitro, cyano, carboxyl, amine, heteroatom, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogen, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxyl, carbonalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclic, alkylheterocyclic, heterocyclicalkyl, oxo, arylsulfonyl, and aralkylaminocarbonyl, or any substituent of the foregoing paragraphs or any substituent of these substituents directly linked or linked through a suitable linker. The linker is typically a short chain of 1-3 atoms and comprises any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)-, or -S(O)O-. The ring can be substituted multiple times.

[0175] The term "lower" modifying "alkyl", "alkenyl", "alkynyl", "alkoxy", or "alkoxycarbonyl" refers to a C1-C6 unit for a particular functional group. For example, "lower alkyl" refers to a C1-C6 alkyl.

[0176] "Substituted" means having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents are alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxy, thioether, alkcarbonyl, alkylcarbonyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkthiocarbonyl, phosphate, phosphonate, phosphinate, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxyl, dithiocarboxyl, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azide, heterocyclic group, ether, ester, silicon-containing moiety, thioester or combinations thereof. The substituent itself may be substituted. For example, an amino substituent itself may be mono-substituted or independently di-substituted with additional substituents as defined above, such as alkyl, alkenyl, alkynyl and cycloalkyl (non-aromatic ring).

[0177] "Thiocyanato" means -SCN.

[0178] "Thioether" means including monodentate and polydentate (e.g., bidentate or tridentate) thioethers, and ligands containing a thioether and a thiol group (or other) moiety.

[0179] "Unsubstituted" means that any open valence of an atom is occupied by hydrogen. Additionally, if the occupant of an open valence on an atom is not specified, it is hydrogen.

[0180] As used herein, the term "about" should be understood to account for minor increases and / or decreases beyond the stated value, the variations of which do not significantly affect the desired function of the parameter beyond the stated value. In some cases, "about" encompasses a difference of + / - 10% from any stated value. As used herein, this term modifies any stated value, a range of values, or the endpoints of one or more ranges.

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

[0182] The implementations disclosed below describe materials being deposited on substrates such as wafers, substrates, or other workpieces. The workpieces can have various shapes, sizes, and materials. In this application, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate", and "partially fabricated integrated circuit" are used interchangeably. One of ordinary skill in the art should understand that the term "partially fabricated integrated circuit" can refer to a silicon wafer during any of the many stages of integrated circuit fabrication thereon. Wafers or substrates used in the semiconductor device industry typically have a diameter of 200 mm or 300 mm or 450 mm. Unless otherwise specified, the processing details described herein (e.g., flow rates, power levels, etc.) relate to processing a 300 mm diameter substrate or a processing chamber configured to process a 300 mm diameter substrate and can be scaled appropriately for other sized substrates or chambers. In addition to semiconductor wafers, other workpieces that can be used in the implementations disclosed herein include various articles such as printed circuit boards and the like. These processes and apparatuses can be used in the manufacture of semiconductor devices, displays, LEDs, and solar photovoltaic panels and the like.

[0183] "Unsaturated" means a moiety containing a carbon-carbon double bond or a carbon-carbon triple bond.

[0184] "Unsaturated substituent" means an aliphatic chain, cyclic, aryl, or heteroaryl group containing a double or triple bond.

[0185] The term "independently selected" (when referring to 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 the selection of R substituents at one atom having multiple R substituents is also independent. Introduction & Background

[0186] Atomic layer deposition (ALD) is a technique that uses sequential self-limiting reactions to deposit thin layers of materials. ALD processing deposits films in a layer-by-layer manner in cycles using surface-mediated deposition reactions. As an example, an ALD cycle can include the following operations: (i) delivering / adsorbing a precursor, (ii) purging the precursor from the chamber, (iii) delivering a second reactant and optionally igniting a plasma, and (iv) purging the by-products from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of the substrate affects film composition and properties such as non-uniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc.

[0187] Unlike chemical vapor deposition (CVD) techniques, ALD processing utilizes surface-mediated deposition reactions to deposit films in a layer-by-layer manner. In one example of ALD processing, a substrate surface including a large number of surface active sites is exposed to a gas-phase distribution of a first precursor, such as a silicon-containing precursor, which is provided in a certain dose to a chamber containing the substrate. Molecules of the first precursor (including chemisorbed substances and / or physically adsorbed molecules of the first precursor) are adsorbed onto the substrate surface. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorbed layer may include the compound and derivatives of the compound. After the injection of the first precursor, the chamber is then evacuated to remove most or all of the first precursor remaining in the gas phase, such that mostly or only the adsorbed substances remain. In some implementations, the chamber may not be completely evacuated. For example, the reactor may be evacuated such that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant (such as an oxygen-containing gas) is introduced into the chamber such that a portion of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a temporary application of an activation source. The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments, the chamber may not be completely evacuated. Additional ALD cycles can be utilized to build up the film thickness.

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

[0189] Figure 1A A diagram of cross-section 100 of a substrate during a deposition process is provided. The diagram shows a substrate 101 having a recessed feature 103. The recessed feature may have sidewalls and a bottom. Generally, the substrate 101 may include various materials, including dielectrics, metals, and metal nitrides. A conformal layer of a metal-containing film 105 is deposited on the substrate 101 using the methods and precursors described below. The resulting structure is shown in Figure 1B In some applications, the process continues and the recessed feature 103 is filled with the metal-containing material 105, as shown in Figure 1C In some embodiments, a series of ALD or pulsed chemical vapor deposition cycles are utilized, using conformal film deposition as shown multiple times in Figure 1A-1C to deposit the metal-containing film into the recessed feature. In other embodiments, bottom-up film growth can be utilized to fill the recessed feature. A method with the first step of introducing a metal-containing precursor

[0190] Figure 2AFlowchart 200 showing a sequential and optional cycle method for depositing a metal-containing film, which begins at operation 210 where a metal-containing precursor is introduced into the processing chamber. 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 can flow to the chamber containing the substrate at a flow rate between about 100 sccm and about 5000 sccm (e.g., about 100 sccm to 2000 sccm). The precursor can flow for any available time period (e.g., about 0.1 to 10 seconds) and at any available pressure (e.g., about 1 to 500 torr). In some embodiments, the temperature of the processing chamber can be maintained at a temperature of 100 °C to 500 °C, or in other embodiments at about 400 °C or lower. In certain embodiments, the temperature can be very low, from about 200 °C to 300 °C.

[0191] During operation 210, a push gas can be made to flow. The push gas can be any inert gas, such as nitrogen (N2), argon (Ar), or any other gas listed herein. The push gas can be provided to assist in pressure and / or temperature control of the processing chamber, evaporation of liquid reactants, faster delivery of reactants, and / or as a sweep gas for removing process gases from the processing chamber and / or processing chamber piping. In some embodiments, the push gas flows to the chamber containing the substrate at a flow rate between about 100 sccm and about 5000 sccm (e.g., about 500 to 2000 sccm). The flow of the push gas and the metal-containing precursor can allow dilution of the precursor and pressure stability during operation.

[0192] In some embodiments, the metal-containing precursor can 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 discussed in the following paragraphs, starting with the molybdenum-containing precursor.

[0193] Molybdenum metal films have not been widely used in semiconductor processing, at least in part because molybdenum has a high affinity for carbon, nitrogen, and oxygen, making it difficult to obtain molybdenum metal with low impurity incorporation and therefore low resistivity. Many common molybdenum deposition precursors exhibit low thermal stability, which results in insufficient step coverage in high aspect ratio features. Existing organometallic molybdenum precursors with molybdenum-carbon bonds may provide high incorporation of carbon into the deposited molybdenum, resulting in high resistivity. For example, the use of carbonyl molybdenum compounds, such as Mo(CO)6, may result in a large amount of carbon (e.g., at least 5 atomic %) being incorporated into the growing molybdenum metal film because molybdenum acts as a catalyst for the dissociation of CO. Although molybdenum halides do not have this problem, existing halide-based molybdenum-containing deposition precursors have several other undesirable properties. For example, when 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), the use of molybdenum hexafluoride (MoF6) requires a fluorine barrier layer and an etch stop layer. Molybdenum pentachloride (MoCl5) is another conventional precursor that has several disadvantages: it has a high melting point and may cause etching of the growing molybdenum film. The volatility is increased by modifying the isoligand halide precursors by replacing the halide ligands with pendant oxygen ligands (such as molybdenum oxychlorides MoOCl4 and MoO2Cl2), but these precursors are difficult to reduce to pure molybdenum metal due to the strong molybdenum-oxygen double bond. In addition, MoCl5, MoOCl4 and MoO2Cl2 are all high melting point corrosive solids, which are not ideal in large-scale production.

[0194] The molybdenum precursors and deposition methods provided herein can overcome one or more of these disadvantages. In some embodiments, a high purity molybdenum metal film is deposited using the provided precursors and methods, wherein the deposited high purity molybdenum metal film consists essentially of molybdenum and has less than about 5% atoms of other elements, such as less than about 3% atoms of other elements, or less than about 1% atoms of other elements (excluding hydrogen in the calculation). In some embodiments, a method for depositing a high purity molybdenum metal film is provided. A platinum metal film having a thick film resistivity of less than about 50 μΩ·cm, for example, a resistivity of less than about 30 μΩ·cm. In some embodiments, particularly when a fluorine-free precursor is used, the platinum metal can be deposited directly onto a substrate containing exposed fluorine-sensitive materials without the need for an etch stop layer to protect them. For example, platinum metal or other molybdenum-containing films can be deposited onto a substrate containing exposed silicon oxide-based dielectrics, silicon-containing dielectrics (e.g., silicon nitrides and silicon carbides), or amorphous or crystalline silicon or silicon germanium. As used herein, a silicon oxide-based dielectric refers to a dielectric containing silicon-oxygen bonds, and includes thermally grown silicon oxides, silicates, silane (and related) deposited oxides, tetraethyl orthosilicate (TEOS) deposited oxides, and the like.

[0195] The precursors provided herein are readily evaporable and stable at the target temperature and pressure. For example, in some embodiments, the precursor is used in a deposition reaction at a temperature below about 450 °C (e.g., below about 400 °C).

[0196] To maintain suitable volatility, in many of the embodiments discussed herein, the precursor has a molecular weight of less than about 450 g / mol (e.g., 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. Further, the use of these compounds can be associated with reduced etching of the substrate material. These advantages are described for illustrative purposes and do not limit the use of these compounds to molybdenum metal deposition or deposition on an etch-sensitive substrate.

[0198] Generally, the molybdenum precursor can have two (MoL2) to six (MoL6) ligands and can include molybdenum in a wide range of oxidation states from 0 to +6. The molybdenum precursor can also be a dimolybdenum compound having 1) two molybdenum atoms bonded to each other in a single-bond or multiple-bond fashion; or 2) two molybdenum atoms connected by a linking group (e.g., a bidentate ligand).

[0199] Suitable molybdenum-containing precursors include molybdenum halides and oxohalides, such as fluorides, chlorides, bromides, oxyfluorides, oxochlorides, and oxobromides, where molybdenum can be in any oxidation state from +2 to +6.

[0200] The molybdenum chloride precursor is shown by the formula MoCl x where x is 2, 3, 4, 5, or 6, and includes molybdenum dichloride (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoC6 is used. Although the description mainly refers to the MoCl x precursor, in other embodiments, other molybdenum halide precursors can be used. The molybdenum halide precursor is shown 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. Examples of the MoX z precursor include molybdenum fluoride (MoF6). In some embodiments, a fluorine-free MoX z precursor is used to prevent fluorine etching or incorporation. In some embodiments, a bromine-free and / or iodine-free MoX z precursor is used to prevent etching or incorporation of bromine or iodine.

[0201] The molybdenum oxohalide precursor is shown by the formula MoO y X zis shown, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and y and z are numbers greater than 0 such that MoO y X z forms a stable compound. Examples of molybdenum oxohalides include molybdenum dioxydichloride (MoO2Cl2), molybdenum oxotetrachloride (MoOCl4), molybdenum oxotetrafluoride (MoOF4), molybdenum dioxydibromide (MoO2Br2), and molybdenum iodides MoO2I and Mo4O 11 I.

[0202] In some embodiments discussed herein, the precursor has a molecular weight of less than about 450 g / mol (e.g., 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, but are not limited to, MoCl5, Mo2Cl 10 , MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6. Low-valent molybdenum complexes

[0204] Low-valent molybdenum complexes or compounds are those having molybdenum in a low oxidation state of 0, +1, +2, or +3. In certain embodiments, low-valent molybdenum complexes may be effective precursors because it is easier to reduce Mo(I) to Mo(0) or Mo(II) / (III) to Mo(0) compared to reducing more commonly used Mo(IV) / (V) halide precursors.

[0205] Low-valent molybdenum precursors can provide a less circuitous surface redox process to obtain a fully reduced molybdenum metal film with minimal impurities. Without wishing to be bound by a particular theory, this may be a result of the ease of reduction of low-valent molybdenum precursors.

[0206] Zero-valent molybdenum complexes

[0207] Mo(0) precursors are advantageous because no reduction step is required and they are energetically easy to use because their use provides a lower energy barrier for Mo film formation upon exposure to a reducing agent. They are particularly suitable for multi-step ALD processes that involve surface ligand exchange and transformation (reduction). Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex present in the zero oxidation state.

[0208] The general formula structure of a low-valent molybdenum precursor having one molybdenum is MoL n (Formula I), and the general formula structure of a low-valent molybdenum precursor having two molybdenum atoms is Mo2Ln (Formula II) or L n Mo(L') m MoL n (Formula III). For any one of Formulas I - III, each L is independently a monodentate ligand, an ambidentate ligand, a bidentate ligand or a 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. Monodentate ligand

[0209] Suitable ligands for low-valent molybdenum complexes include monodentate ligands, also known as unidentate ligands. A monodentate ligand is a ligand that binds or coordinates to a metal center through only one ligand site of the metal or through only one site of the ligand. They can include a variety of substituents, such as hydrogen, halogen, hydroxy, alkylsilyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenyloxy, alkynyloxy, 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(C 1- C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclic group, alkylheterocyclic group, heterocycloalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, =O, =S, ≡N, ≡CR, =CR2, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, -C(O)NH(benzyl), amido, azide, isocyanato, thiocyanato, isothiocyanato, cyano, isocyano or cyclo group, where each R is independently aliphatic, such as haloalkyl or aryl, such as haloaryl.

[0210] In some embodiments, the low-valent molybdenum precursor includes at least one OR, P(R)3, CNR, allyl, or aryl group, where each R is independently an aliphatic, aryl, haloalkyl, or haloaryl group.

[0211] In some embodiments, the monodentate ligand may contain an oxygen atom. In certain embodiments, one or more ligands may be an optionally substituted alkoxy group. Non-limiting ligands include, for example, methoxy, ethoxy, isopropoxy (i-PrO), and tert-butoxy (t-BuO). Non-limiting molybdenum-containing precursors include, for example, Mo(CH2F)(t-BuO)3, Mo(CF3)(t-BuO)3, Mo(CH2I)(t-BuO)3, Mo(Cl3)(t-BuO)3, Mo(CH2CH2F)(t-BuO)3, Mo(CH2CH2I)(t-BuO)3, Mo(CH2F)2(t-BuO)2, Mo(CF3)2(t-BuO)2, Mo(CH2I)2(t-BuO)2, Mo(Cl3)2(t-BuO)2, Mo(CH2CH2F)2(t-BuO)2, Mo(CH2CH2I)2(t-BuO)2, Mo(t-BuO)2, Mo(CH3)(t-BuO)3, Mo(CH2CH3)(t-BuO)3, Mo(CH=CH2)(t-BuO)3, Mo(CH=CHCH3)(t-BuO)3, Mo(CH2-CH=CH2)(t-BuO)3, Mo(C=CH)(t-BuO)3, Mo(C=CCH3)(t-BuO)3, Mo(CH2C=CH)(t-BuO)3, or Mo(acac)2.

[0212] In certain embodiments, the oxygen-containing monodentate ligand can be -OC(CH3)(CF3)2, -OC(CH3)2(CF3), -OC(CH3)3, -OSiR3 (such as -OSiPh3), CO (carbonyl ligand), or -OAr (where the Ar group includes, but is not limited to, phenyl, mesityl, 2,6-iPr2C6H3, hexaisopropyltriphenyl, and 2,3,5,6-Ph4C6H). In certain embodiments, the oxygen-containing ligand is an ether, epoxide, or ketone. In some cases, the oxygen-containing ligand can be a siloxy group.

[0213] In certain embodiments, the ligand is a phosphorus-containing ligand. Suitable complexes can have the formula R3P, where R is a halogen, 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 tris(benzenesulfonic acid)phosphine (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. In some embodiments, R is an aliphatic group such as haloalkyl, or an aryl group such as haloaryl. In certain embodiments, R can be -CH2CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -CH(CF3)2, -CH(CH3)(CF3), or -C(CH3)2(CF3). In certain embodiments, R is a perfluoroalkyl substituent having one to ten carbon atoms, such as perfluorinated methyl, ethyl, isopropyl, n-propyl, tert-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl, or n-hexyl groups.

[0215] In some embodiments, the monodentate ligand is a ligand having sp 2 hybridization characteristics, such as allyl, alleny, vinyl, indenyl, or cyclopentadienyl groups. Two identical such substituents or two different such substituents can be utilized to form a precursor having a sandwich structure. In some embodiments, one such substituent is utilized to form a half-sandwich structure. In certain embodiments, the ligand can be mesityl, tolyl, xylyl, benzyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, or pyrimidinyl.

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

[0217] In some embodiments, the molybdenum-containing precursor has at least one optionally substituted haloalkyl. Non-limiting haloaliphatic group ligands include -CX y H 3-y, where y is 1, 2 or 3, and each X is independently a halogen (F, Cl, Br or I); -CX z H 2-z CX y H 3-y , where z is 0, 1 or 2, y is 0, 1, 2 or 3, each X is independently a halogen (F, Cl, Br or I), and at least one of z or y is not 0; or -CH2CX y H 3-y , where y is 1, 2 or 3, and each X is independently a halogen (F, Cl, Br or I). Other non-limiting haloalkyls include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI) and the like. In certain embodiments, C 1-2 haloalkyl includes ethyl substituted with β-halogen. Other other haloaliphatic groups include C 1-4 haloalkyl, C 2-4 haloalkenyl and C 2-4 haloalkynyl.

[0218] In other embodiments, the ligand is an optionally substituted alkyl, an optionally substituted alkenyl or an optionally substituted alkynyl. Non-limiting groups include -C n H 2n+1 , where n is 1 or 2; -C n H 2n-1 , where n is 2, 3 or 4; or -C n H 2n-3, where n is 2, 3 or 4. Other non-limiting groups include methyl (-CH3), ethyl (-CH2CH3), vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g., -CH2CH2CH=CH2), ethynyl (-C≡CH), 1-propynyl (-C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (-C≡CCH2CH3), 2-butynyl (-CH2C≡CCH3), 3-butynyl (-CH2CH2C≡CH), 2-methyl-1-propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2), 1-methylallyl (CH(CH3)CH=CH2 and the like.

[0219] In some embodiments, the monodentate ligand can be -CH2P(CH3)3, -CH(Si(CH3)3)(P(CH3)3), -C(O)C3F7 or -CHCHSO2C6H5.

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

[0221] In some embodiments, the monodentate ligand contains a nitrogen atom. In certain embodiments, one or more monodentate ligands can be an optionally substituted amino group or an optionally substituted bis(trialkylsilyl)amino group. Non-limiting ligands can 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 group is -NR 1 R 2 , where each R 1 and R 2 is independently H or alkyl; or where R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclic group as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino group is -N(SiR 1 R 2 R 3 )2, where each R1 , R 2 and R 3 are independently alkyl. In other alternative embodiments, the optionally substituted trialkylsilyl is -SiR 1 R 2 R 3 , where each R 1 , R 2 and R 3 are independently alkyl.

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

[0224] In some embodiments, the monodentate ligand is an optionally substituted alkyl. Non-limiting alkyls include, for example, C n H 2n+1 , where n is 1, 2, 3 or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. 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 haloalkyls include, for example, C n H 2n+1-z X z , where n is 1, 2, 3 or greater; where z is 1 to 2n + 1 (e.g., 1 to 3, 1 to 5 or 1 to 7); and where each X is independently a halogen (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 alkenyls include, for example, C n H 2n-1 , where n is 2, 3, 4 or greater, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl or 3-butenyl. Non-limiting alkynyls include, for example, C n H 2n-3 , where n is 2, 3, 4 or greater, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl or 3-butynyl.

[0227] In certain embodiments, an alkynyl group is also a suitable monodentate ligand. In some embodiments, the carbon-carbon triple bond is not directly bonded to molybdenum, e.g., in the formula R 1 CCCH2MoL3, where R 1 is 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, tert-butoxy, sec-butoxy, or n-butoxy).

[0228] An alkyne compound having a carbon-carbon triple bond directly bonded to a molybdenum atom will hydrolyze in the presence of water, similar to amino and alkoxy groups, but much more slowly than amino and alkoxy groups. Thus, according to certain embodiments, compounds such as (R 1 C≡C)3MoR 2 and (R 1 C≡C)4Mo (where R 1 is a simple alkane such as methyl or ethyl and R2 is a C1-C2 hydrocarbon) are precursors having monodentate ligands. In the compound (R 1 C≡C)3MoR 2 , the molybdenum center has three alkynes whose carbon-carbon triple bonds are bonded to the molybdenum center. Tetra-alkynes are those such as shown for (R 1 C≡C)4Mo.

[0229] In some embodiments, the monodentate ligand is a halogen. In particular, the metal-containing precursor can be a metal halide or an organometallic halide. Non-limiting metal halides and organometallic halides include FCH2MoX3, CF3MoX3, ICH2MoX3, CI3MoX3, CH2FCH2MoX3, CH2ICH2MoX3, MoX2, or MoX4, where each X is independently a halogen. In other embodiments, the metal-containing precursor is RMoX3, where R is a C 1-4 haloalkyl, C 2-4 haloalkenyl, or C 2-4 haloalkynyl; and where each X is independently a halogen. In still other additional embodiments, the metal-containing precursor is RMoX3, where R is a C 1-2 alkyl, C 2-4 alkenyl, or C 2-4 alkynyl; and where each X is independently a halogen.

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

[0231] In some embodiments, the monodentate ligand may include a silicon atom. In some embodiments, the monodentate ligand may be -Si(CH3)3, -Si(C2H5)3, -CH2Si(CH3)3, -CH(Si(CH3)3)2, or -C(Si(CH3)3)3. In certain embodiments, one or more ligands may be an optionally substituted trialkylsilyl or an optionally substituted bis(trialkylsilyl)amino group. Non-limiting ligands may include, for example, -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2.

[0232] For any formula herein, each monodentate ligand may independently be hydrogen, halogen, azide, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted amino group, an optionally substituted bis(trialkylsilyl)amino group, an optionally substituted trialkylsilyl group, or an optionally substituted alkoxy group (e.g., -OR 1 , where R 1 may be an alkyl group).

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

[0234] A monodentate ligand may be an ambidentate ligand having two potential donor atoms but is attached to the metal through only one of the two. In certain embodiments, the ambidentate ligand is NO2-, which may be bonded to the metal through the nitrogen atom or the oxygen atom. Bidentate ligand

[0235] Suitable ligands for low-valent molybdenum complexes include bidentate ligands. A bidentate ligand (also known as a chelating ligand) is a ligand that binds or coordinates to a metal center through two ligand sites of the metal or through two sites of the ligand. A bidentate ligand is a Lewis base that donates two pairs of electrons to a metal atom. A bidentate ligand may be neutral or anionic. In addition, a bidentate ligand may have two identical coordinating atoms or may be an asymmetric bidentate ligand in which the two coordinating atoms are not the same. In some embodiments, the bidentate ligand may be ethylenediamine (en), bipyridine (bpy), 1,2-bis(dimethylphosphino)ethane (dmpe), phenanthroline (phen), 1,2-bis(diphenylphosphino)ethane (dppe), acetate (OAc), oxalate (ox), or acetylacetonate (acac). Precursors having bidentate ligands include, but are not limited to, molybdenum dioxide bis(acetylacetonate) (MoO2(acac)2).

[0236] Exemplary structures containing bidentate ligands include, but are not limited to

[0237] The bidentate ligand can be the linking moiety L' of the structure -(E) e - wherein each E independently comprises NR, C(R) n , Si(R) n , S, O or P(R) n ; 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 can contain one, two or three bidentate ligands, each of which can be the same or different.

[0239] The bidentate ligand can be amidinate, amidate, iminopyrrolidinate, diazadiene, beta-iminoamide, alpha-iminoalkoxide, beta-diketiminate, beta-ketoiminate, beta-diketonate, pyrazolate, beta-aminoalkoxide, guanidinidate, dithiolene and alpha-iminothiolene, alpha-dithiolate or bata-dithiolate. Examples of other suitable materials include the bidentate ligands described in US2022 / 0170155 and WO2021 / 035236, the entire contents of which are incorporated herein by reference. Tridentate ligand

[0240] A tridentate ligand is a ligand having three atoms that can act as acceptors in a coordination complex. In certain embodiments, the tridentate ligand has three nitrogen, three sulfur, three phosphorus, or three oxygen atoms available for chelation. Tridentate ligands include cis,cis-1,3,5-triaminocyclohexane, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7-trithia-cyclononane, bis(diphenylphosphinoethyl)phenylphosphine, N,N,N',N'',N''-pentamethyldiethylenetriamine, tris(4S-isopropyl-2-oxazolinyl)phenyl borate, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate, tripyrazolyl borate, 1,4,7-trioxonane, diethylenetriamine, or iminodiacetate anion. Suitable low-valent molybdenum precursors can contain one, two, or more tridentate ligands, which can be the same or different.

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

[0242] Figure 2B Exemplary structures of molybdenum precursors having three ligands (Formula XIV), four ligands (Formula V and Formula VI), or five ligands (Formula IX and Formula X) in certain embodiments are shown. 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, where each R is independently aliphatic, aryl, haloalkyl or haloaryl. 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 is independently any one of the above monodentate ligands, polydentate ligands or bidentate ligands. For Formula V, R 1 can be an aliphatic group, R 2 can be any one of the above monodentate ligands, polydentate ligands, bidentate ligands or tridentate ligands, and n can be 1, 2, 3, 4 or 5.

[0244] The low-valent molybdenum precursors can also have six ligands. Precursors having six ligands include, but are not limited to, molybdenum hexafluoride (MoF6) and molybdenum hexacarbonyl (Mo(CO)6). In some embodiments, such precursors can have the general formula Mo(X) p (R 10 ) q (XII), where each X independently includes chlorine, fluorine, bromine or iodine; each R 10 independently includes allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuryl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 11 , where R 11 includes aliphatic, aryl or heterocyclic groups; p is from 1 to 4; q is from 2 to 5; p + q = 6.

[0245] The low-valent molybdenum precursors having six ligands can also have the formula (XIII): Mo(R 12 )r (R 13 ) s (XIII), wherein each R 12 independently comprises allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 14 , wherein R 14 comprises aliphatic, aryl or heterocyclic group; each R 13 independently comprises trimethylphosphine, triethylphosphine, triisopropylphosphine, 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 from 1 to 6; s is from 0 to 5; and r + s = 6.

[0246] Figure 2C Exemplary structures of low-valent molybdenum precursors with six ligands are shown. Structures 1-9 have one or more CNR ligands, which can be isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl or isocyanohaloaryl. In some embodiments, R is an aliphatic group (e.g., haloalkyl), or an aryl group (e.g., haloaryl). In certain embodiments, R can be -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3) or -C(CH3)2(CF3). In certain embodiments, R is a perfluoroalkyl substituent of one to ten carbon atoms, such as perfluorinated methyl, ethyl, isopropyl, n-propyl, tert-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl or n-hexyl. Structures 10-18 have one or more PMe3 ligands.

[0247] The molybdenum complex can be prepared using a zero-valent starting material such as molybdenum hexacarbonyl. Other synthetic routes include reacting MoCl3(THF)3 with appropriate ligands followed by reduction; and reacting MoX5 (X = Cl, Br, I) with appropriate ligands followed by reduction.

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

[0249] The reaction can be carried out in various aprotic solvents. For example, the reaction can be carried out in ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, 1,2-dimethoxyethane, in hydrocarbon solvents such as toluene, benzene, heptane, hexane, pentane, or in halocarbon solvents such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc. The reaction can 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 unstable 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). Dimolybdenum complex

[0250] On the other hand, the precursor for depositing a molybdenum-containing film is a dimolybdenum compound containing a direct molybdenum-molybdenum bond (e.g., a multiple molybdenum-molybdenum bond such as a double bond, or any multiple bond with a bond order of 2-5). The directly bonded dimolybdenum precursor can have the structure Mo2L n (II), where each occurrence of L is independently a monodentate ligand, a multidentate ligand, a bidentate ligand, or a tridentate ligand as described above, and n is from 2 to 6. One example precursor is Mo2(O-isopropyl)6. Other exemplary precursors are shown in Figure 2D . In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a double bond (e.g., structure 19). In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a triple bond (e.g., structures 20-23). For structures 20 and 21, R can be an aliphatic group such as an alkyl, haloalkyl, or silyl group. For structure 23, L can be any of the ligands described above, or can be any one of CO, CNR, or PMe3 (where R is an aliphatic, aryl, or heterocyclic group) and X is a halogen. Such precursors are particularly useful for the deposition of molybdenum metal and high-purity molybdenum metal because they are more likely to reduce such compounds to metallic molybdenum compared to some mononuclear molybdenum compounds.

[0251] The dimolybdenum precursors described herein can be synthesized by treating molybdenum tetraacetate as a starting material with a ligand salt (such as lithium amidate). In one aspect, a container is provided that houses any of the precursors described herein in solid or liquid form. In another aspect, a solution of any of these precursors is provided, where the solvent can include, for example, a high-boiling hydrocarbon solvent, such as a higher alkane. In some embodiments, the container housing the molybdenum precursor (in solid or liquid form or in solution) is filled with an inert gas, such as nitrogen (N2) or argon (Ar), to prevent the precursor from coming into contact with air and potentially decomposing due to contact with moisture and / or air. In some embodiments, the container is adapted to evaporate the precursor inside the container. For example, the container can include an inlet and an outlet, where the inlet is adapted to be connected to a carrier gas source, and the carrier gas can flow over or through the precursor, thus facilitating evaporation of the precursor. The outlet is adapted to remove the carrier gas and the precursor vapor from the container and is configured to be connected to a conduit that can be used to transport the precursor vapor to a processing chamber. The inlet and the outlet each have a closed position and an open position and can include, for example, manual valves that can be used to switch from the closed position to the open position and back. When the container is being stored or transported, the inlet and the outlet are closed. When the container is installed on a deposition device for use, the inlet valve and the outlet valve can be opened, and the carrier gas can flow into the inlet and carry the precursor vapor out of the outlet.

[0252] In some embodiments, the container has an overflow design, where the inlet and the outlet are disposed above the surface of the precursor. For example, in a cylindrical container, the inlet and the outlet can be disposed at a similar vertical height (e.g., the vertical distance between the inlet and the outlet can be less than about 20% of the height of the cylinder). In other embodiments, the container has a bubbler design, where the inlet is disposed below the surface of the precursor and the outlet is disposed above the inlet (e.g., above the surface of the precursor). For example, in a cylindrical container, the inlet and the outlet can be disposed to be vertically separated from each other (e.g., the vertical distance between the inlet and the outlet can be greater than about 30% of the height of the cylinder, such as greater than about 50%, greater than about 80%.

[0253] The low-valent dimolybdenum complex can also contain two molybdenum atoms indirectly interconnected through a linking moiety. Such precursors can have the formula L n Mo(L') m MoL n (III), where each L is independently a monodentate ligand, a multidentate ligand, a bidentate ligand, or a tridentate ligand as described above; L' is a linking moiety; n is from 2 to 6; and m is from 1 to 3. The linking moiety L' can have the structure -(E) e -, where each E independently includes C(R) n 、NR、Si(R) n 、S、O or P(R) n; each R independently 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, the low-valent dimolybdenum complex may contain two molybdenum atoms that are directly bonded to each other and also indirectly interconnected through a linking moiety as described above. Return Figure 2D , showing exemplary structures 24 and 25 having two types of linkages. For structures 24 and 25, L can be any of the ligands described above, or preferably CO, CNR or PMe3 (where R is aliphatic, aryl or heterocyclic) and X is a halogen.

[0255] The molybdenum-containing films provided herein, particularly high-purity molybdenum metal, can be used for interconnect metallization (e.g., for filling recessed features to form contacts), in logic gate applications in FinFETs, as an adhesion layer or a diffusion barrier layer, and in 3D NAND fabrication. Examples of applications include logic and memory contact filling, DRAM buried word line filling, vertical integrated memory gate and word line filling, and 3D integration using through-silicon vias (TSVs). Molybdenum has a better resistivity than tungsten, and in some embodiments, molybdenum is a particularly advantageous metal for filling narrow recessed features (e.g., features having a width less than about 20 nm).

[0256] In one application, molybdenum metal is used to fabricate barrierless contacts. In this application, molybdenum metal is directly deposited into recessed features (contact holes) having a width of about 5 - 100 nm (e.g., about 5 - 20 nm), where the recessed features are formed in a dielectric layer and include exposed dielectric (e.g., silicon oxide, silicon nitride or a low-k material such as silicon carbon oxide) at the sidewalls, and 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, on which the molybdenum metal is deposited. Copper precursor

[0257] A variety of copper precursors can be used to deposit copper metal, where copper can be in the +1 or +2 oxidation state. The precursors can be cuprous (copper(I)) compounds, such as acetylacetonate, ketoiminate, diiminate, cyclopentadienyl compounds, amidinate, guanidinate or amide; or copper(II) compounds (such as acetylacetonate, ketoiminate or aminoalkoxide). In some embodiments, the precursor is a coordination complex where copper is coordinated to a multiple bond, such as a double bond or a triple bond; or coordinated to an oxygen such as a carbonyl.

[0258] Examples of copper precursors include Cu(acac)2, where acac = acetylacetone; Cu(thd)2, where thd = tetrahydrodionato; hexafluoroacetylacetonate-copper-trimethylsilane; cyclopentadienyl (Cp) compounds such as CpCu(CNMe), CpCu(CNCMe3), CpCuCO, CPCuPR3 (where R = Me, Et or Ph), and CpCu(CSiMe3)2; alkyl or aryl compounds such as MeCu(PPh3)3, CuMe, CuCCH (copper acetylide), CuCMe3 (copper methylacetylide), (H2C=CMeCC)Cu (3-methyl-3-butene-1-ynyl copper), CuCCPh, C6H5Cu (phenyl copper), (Me)3CCCCu (3,3-dimethyl-1-butynyl) copper, Me3SiCCCH2Cu; and other compounds such as CuCN, [Cu(OAc]n (where OAc = acetate), Cu2Cl2(butadiene), C7H7CuO (2-methoxyphenyl copper), (MeCN)4CuX (where X is a halogen, alkyl, amine or phenyl), Me3SiOCu(PMe3)3, Cu(C4H4S), and Cu-carbene compounds such as those derived from imidazolium. Cobalt precursors

[0259] Cobalt metal can be deposited using a variety of cobalt precursors, where cobalt can be in the +1, +2 or +3 oxidation state. Examples of cobalt precursors include cobalt acetate, cobalt acetylacetonate (e.g., bis(acetylacetonato)cobalt(III)), cobalt amidinates (e.g., bis(N-t-butyl-N’-ethylpropanimidamidato)cobalt(II)), cobaltocene, and carbonyl-containing cobalt precursors (e.g., cobalt tricarbonyl nitrosyl and cyclopentadienylcobalt dicarbonyl). An example of a halogen-containing cobalt precursor is CoCl2(TMEDA), where TMEDA is N,N,N',N'-tetramethylethylenediamine. Ruthenium precursors

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

[0261] Tungsten can be deposited using a variety of volatile precursors. In some embodiments, a halogen-containing tungsten precursor is used, such as WHal x , where Hal is a halogen (e.g., F, Cl, Br, and / or I) and x is from 2 to 6. In some embodiments, tungsten chlorides are used. Tungsten chlorides include tungsten pentachloride (WCl5), tungsten hexachloride (WCl6), tungsten tetrachloride (WCl4), tungsten dichloride (WCl2), and mixtures thereof. In other examples, tungsten fluorides can be used, such as tungsten hexafluoride. Additional precursors

[0262] In some embodiments, other useful precursors include vanadium-containing precursors such as tetrakis(dimethylamino)vanadium, tris(dimethylamino)cyclopentadienylvanadium, tetrakis(ethylmethylamino)vanadium; niobium-containing precursors such as (tert-butylimino)bis(diethylamino)niobium, (tert-butylimino)bis(dimethylamino)niobium, and (tert-butylimino)bis(ethylmethylamino)niobium; tantalum-containing precursors such as tert-butyliminotris(dimethylamino)tantalum and tantalum pentachloride; iron-containing precursors such as tert-butoxyiron(III) dimer, ferrocene, and pentacarbonyliron; nickel-containing precursors such as allyl(cyclopentadienyl)nickel(II) and bis(acetylacetone)nickel(II); zinc-containing precursors such as zinc acetate and diethylzinc; and chromium-containing precursors such as chromium carbonyl and bis(cyclopentadienyl)chromium(II).

[0263] Return Figure 2A , and in operation 220, an iodine-containing reagent is introduced into the processing chamber to react with the metal-containing precursor. The iodine-containing reagent can be hydrogen iodide (HI); iodine (I2); alkyl iodides such as CH3I, C2H5I, C3H7I, C4H9I, CH2I2, 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)H2I.

[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; tert-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)methyldiiodide; (trimethylsilyl)methyltriiodide; bis(trimethylsilyl)methyl iodide; bis(trimethylsilyl)methyldiiodide; tris(trimethylsilyl)methyl iodide; 1-(trimethylsilyl)-1-iodoethane; 1-(trimethylsilyl)-2-iodoethane; 1-(trimethylsilyl)-1,2-diiodoethane; 1,1-bis(trimethylsilyl)-1,2-diiodoethane; 1,2-bis(trimethylsilyl)-1,2-diiodoethane; CHI3; CI4; 1-iodoethylene; 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-iodo-but-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-tetraiodoethylene; SiI4; SiHI3; SiH2I2; SiH3I; Si(CH3)I3; Si(CH3)2I2; Si(CH3)3I; Si(CH3)HI2; Si(CH3)2HI; Si(CH3)H2I; Si2I6; GeI4; GeHI3; GeH2I2; GeH3I; AlI3; BI3; TiI4; SnI4; HfI4; N-iodosuccinimide; 1,3-diiodo-5,5-dimethylhydantoin; N-iodophthalimide; N-iodosaccharin; 1-chloro-2-iodoethane; IF5; iodoacetic acid; iodopropargyl 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, an iodine-containing reagent can act as a surface ligand exchange catalyst and react with a metal precursor in a processing chamber to in-situ form a metal species containing an iodine bond.

[0266] Non-limiting examples of reactive species that constitute a metal-iodine reaction site or a reactive species containing an iodine bond can include free radicals, metastable species, ions, neutral species, plasmas, photons, radiation, excited molecules, excited atoms, or other species described herein. In one non-limiting embodiment, the metastable species has an energy of about 0.01 - 1 eV. In another non-limiting embodiment, the ion has an energy of about 100 - 1000 eV. In yet another non-limiting embodiment, the reactive species has an energy of about 0.01 - 1000 eV. In some non-limiting instances, any description herein regarding free radicals and metastable species can encompass any reactive species described herein. The metal species containing an iodine bond can be any reactive species including a metal and iodine as defined above. When the metal is molybdenum, the metal species containing an iodine bond can be MoI x , such as MoI2 or MoI3; or a reactive Mo-I* site. Additionally, the reactive species can include molybdenum halides, such as MoI2 or MoI3.

[0267] In operation 230, the metal species containing an iodine bond is exposed to a reducing agent to form a metal-containing film. Suitable reducing agents include, but are not limited to, hydrogen (H2), ammonia (NH3), ammonia plasma, hydrazine (N2H4), alkyl hydrazines (such as tert-butyl hydrazine (C4H 12 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 mentioned, other reducing agents can be provided by plasmas generated by one or more of the listed reducing agents.

[0268] Exposing the substrate to the reducing agent can include contacting the substrate with the reducing agent for a time between about 0.1 second and about 180 seconds; between about 0.5 second and 60 seconds; or between about 0.1 second and 10 seconds. During the exposure of the substrate, the flow rate of the reducing agent can 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 in some embodiments even less than 0.1 slm. The flow rate of the reducing agent can be in the range of about 0.1 to 30 slm, about 5 to 15 slm, or equal to or greater than 10 slm.

[0269] As shown in operation 240, if the deposited film has sufficient thickness, the method is complete and ends. As used herein, a "metal-containing film" refers to a film that contains only metal or a film that contains metal and additional components. Metal-containing films can be deposited for various semiconductor applications. Accordingly, the desired thickness will depend on the particular application. In some embodiments, the metal-containing film can be deposited on the substrate as a conformal layer to a thickness between about 0.1 and 10 nm.

[0270] If a thicker film is desired, operation 250 indicates a process flow path where operation 210 can start again and repeat n times 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 cycles of operations 210, 220, and 230 can be repeated as many times as needed. As used herein, the term "cycle" refers to a particular set of sequential operations.

[0271] The metal-containing film formed by method 200 can have fewer halogen-based impurities or other impurities than metal-containing films produced by conventional processes at higher temperatures.

[0272] In addition to the steps of method 200 as described above, in some embodiments, purge 215 can optionally be performed after operation 210. In some embodiments, purge 225 can optionally be performed after operation 220; or in some embodiments both purge 215 and purge 225 can be performed. Purging the chamber can involve flowing a purge gas or gases, which can be the carrier gas used in other operations or can be a different gas. In some embodiments, purging can involve evacuating the chamber. Examples of purge gases include argon (Ar), nitrogen (N2), hydrogen (H2), helium (He), oxygen (O2), krypton (Kr), xenon (Xe), neon (Ne), and combinations thereof. In various embodiments, the purge gas is an inert gas. The purge gas can include one or more gases. In some embodiments, operation 215 and / or 225 can include one or more evacuation sub-stages for evacuating the processing chamber. Alternatively, it should be understood that purging can be omitted in some embodiments. Operations 215 and / or 225 can have any suitable duration, such as between about 0 seconds and about 60 seconds, such as about 0.01 seconds. In some embodiments, increasing the flow rate of one or more purge gases can reduce the duration of purging. For example, the purge gas flow rate can be adjusted according to various reactant thermodynamic properties and / or the geometric properties of the processing chamber and / or the processing chamber plumbing to vary the duration of purging. In a non-limiting example, the duration of the purge stage can be adjusted by regulating the purge gas flow rate. This can reduce the deposition cycle time and thus improve substrate throughput. After purging, organosilicon precursor molecules still adsorb on the substrate surface.

[0273] The purge gas can flow to the chamber containing the substrate at a flow rate between about 1000 sccm and about 40000 sccm (e.g., about 100 sccm to 2000 sccm). The purge gas can flow for any available time period (e.g., about 0.1 to 10 seconds) and at any available pressure (e.g., about 0.5 to 25 Torr).

[0274] Figure 3 FIG. 300 is a flow chart showing another sequential and optionally cyclic deposition process, which begins at operation 310, where a metal-containing precursor is introduced into the processing chamber. 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 discussed above. In method 300, operation 320 simultaneously introduces an iodine-containing reagent and a reducing agent, which combines operations 220 and 230 as described in method 200 above. During operation 320, the iodine-containing bond material described above is formed and reduced. Subsequently, in operation 325, the processing chamber is purged. In operation 330, it is determined whether the deposited film has the desired thickness. If not, the process flow path 340 indicates that the cycle can be repeated n times by returning and re-running operation 310 n times. Additionally, after operation 310, the processing chamber can optionally be purged in operation 315.

[0275] Figure 4 FIG. 400 is a flow chart showing another sequential and optionally cyclic deposition process, which begins at operation 410, where a metal-containing precursor is introduced into the processing chamber. In some embodiments, the metal-containing precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. Operation 410, introducing the metal-containing precursor into the processing chamber, 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. A metal substance with an iodine-containing bond is formed, and then in operation 430, the metal substance with the iodine-containing bond is reduced upon exposure to a reducing agent to form a metal-containing film. It is determined 440 whether the deposited film has sufficient thickness, and if a thicker film is desired, the cycle of operations 410, 420, and 430 can be repeated n times, as shown by the process flow path 450.

[0276] The process flow path 460 shows that after operation 420, operation 410 can be repeated m times. In operation 460, m is the number of cycles, which can be 1 to 50 or 20 to 40. The cycles of operations 410 and 420 can be repeated as many times as needed. In certain embodiments, the method includes a double cycle, where different sets of steps are repeated. The double cycle can also be described as a sub-cycle within a cycle, as shown by the process flow path 450 and the process flow path 460.

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

[0278] Figure 5 FIG. 5 is a flow chart showing another sequential and optionally cyclic deposition process method 500 that begins with operation 510, where a substrate is pre-treated in a processing chamber. The pre-treatment 510 may specify exposing the substrate to an iodine-containing reagent or a passivation gas. The pre-treatment may prevent metal nucleation in certain regions, thereby promoting deposition first at the bottom of the features.

[0279] Suitable passivation 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 to introduce a metal precursor into the processing chamber as described above with respect to operation 210. In some embodiments, the metal precursor is a molybdenum-containing precursor, and the deposited metal-containing film is a molybdenum-containing film. Then, in operation 530, an iodine-containing reagent is introduced into the processing chamber to react with the metal precursor and form an iodine-bonded substance, as described above with respect to operation 220. When an iodine-containing reagent is selected for the pre-treatment in operation 510, the iodine-containing reagent selected for operation 530 may be the same or different iodine-containing reagent. In operation 540, the iodine-bonded metal substance is exposed to a reducing agent to form a metal-containing film, as described in operation 230 above.

[0281] As shown in operation 550, if the deposited film has sufficient thickness, the method is completed and ends. If a thicker film is desired, the process flow path 555 indicates that after operation 540, operation 510 may start again and be repeated n times. For the process flow path 555, n is the number of cycles, which can be from 1 to 50 or from 20 to 40. The cycles of operations 510, 520, 530, and 540 may be repeated as many times as needed to achieve the desired thickness. In addition to the steps of method 500 as described above, in some embodiments, cleaning 515 may optionally be performed after operation 510. In some embodiments, cleaning 525 may optionally be performed after operation 520, and in some embodiments, cleaning 535 may optionally be performed after operation 530. In some embodiments, cleanings 515, 525, and 535 may all be performed during one cycle, as discussed above with respect to method 200. A method with introducing an iodine-containing reagent as the first step

[0282] Figure 6A flowchart showing another sequential and optionally cyclic deposition process, method 600, which begins at operation 610, where the substrate is pretreated in the processing chamber by introducing a passivation gas and simultaneously introducing an iodine-containing reagent.

[0283] Suitable passivation 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 to introduce a metal precursor into the processing chamber as described above with respect to operation 210. In some embodiments, the metal 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 processing chamber to form a metal-containing film as described above for operation 230.

[0285] As shown in operation 640, if the deposited film has sufficient thickness, the method is complete and ends. If a thicker film is desired, the process flow path 650 indicates that after operation 640, operation 610 can start again and be repeated n times. For the process flow path 650, n is the number of cycles, which can be from 1 to 50 or from 20 to 40. The cycles of operations 610, 620, and 630 can be repeated as many times as needed to achieve the desired thickness. In addition to the steps of method 600 as described above, in some embodiments, a purge 615 can optionally be performed after operation 610. In some embodiments, a purge 625 can optionally be performed after operation 620; or in some embodiments, both purges 615 and 625 can be performed, as discussed above with respect to method 200. Method for forming a molybdenum-containing material

[0286] Molybdenum-containing materials can be deposited using the precursors described herein by various deposition methods, such as CVD (including thermal and PECVD) and ALD (including thermal and PEALD). Figure 7The process flow diagram shown illustrates an exemplary method 700. The process begins at 701, where a molybdenum precursor as described herein is introduced into a processing chamber containing a semiconductor substrate. The precursor may be introduced in vaporized form into a stream of an inert gas such as argon, helium, or nitrogen (N2). In operation 703 (which may occur before, after, or during the introduction of the molybdenum-containing precursor 701), a second reactant is introduced into the processing chamber containing the substrate. In some embodiments, the introduction of the molybdenum precursor and the second reactant is sequential. The chemical nature of the second reactant depends on the chemical nature of the target molybdenum-containing film. For example, for the deposition of molybdenum metal, the second reactant is typically a reducing reactant (including reactants that form a reducing environment when activated in a plasma). Examples of suitable reactants for forming molybdenum metal include hydrogen (H2), ammonia (NH3), hydrazine (N2H4), amines, diborane (B2H6), silane (SiH4), disilane (Si2H6), alcohols, hydrogen sulfide (H2S), or thiols. In some embodiments, H2 is the preferred reducing reactant for depositing molybdenum metal. In some embodiments, the molybdenum-containing precursor reacts sequentially with several reactants. For example, in some embodiments, molybdenum metal is deposited by adsorbing a layer of the molybdenum-containing precursor on the substrate, reacting it with a second reactant, and then reacting it with a third reactant.

[0287] In one implementation, the molybdenum-containing precursor (the first reactant) first reacts with at least one of water, H2S, and thiols (the second reactants). Next, the substrate containing the reacted precursor is treated with hydrogen (H2) (the third reactant). In some embodiments, the processing chamber is purged and / or evacuated after the introduction of each reactant. In some embodiments, the first reactant (e.g., water, H2S, or thiol) is selected to facilitate the removal of ligands from the molybdenum precursor, while the third reactant (e.g., H2) is selected to remove the remaining portion of the ligands (e.g., C, N, S, O-containing impurities) from the substrate surface and / or reduce the molybdenum to the zero oxidation state and form high-purity molybdenum metal.

[0288] When depositing a molybdenum-containing film other than molybdenum metal, a second reactant can be selected such that it serves as the source of the essential elements of the molybdenum-containing film, but in some embodiments, these elements can be entirely derived from the ligands. The processing conditions (such as temperature, pressure, reactant flow rates, and optionally plasma power) can be adjusted to favor a particular film chemistry. For example, in some embodiments, borane and silane reactants can be used to deposit materials containing molybdenum boride or molybdenum silicide, while under different conditions, these reactants alone or in combination with other reactants (e.g., H2) can produce molybdenum metal. For the deposition of molybdenum nitride, a nitrogen-containing second reactant can be selected in some embodiments and the processing conditions can be adjusted to allow nitrogen to be incorporated into the film. For example, NH3, N2H4, N2, alkylamines, and alkyl hydrazines can be used as the second reactant for the deposition of molybdenum nitride. For the deposition of molybdenum carbide, a carbon-containing second reactant can be used and the processing conditions can be adjusted to allow carbon to be incorporated into the film. For example, a hydrocarbon can 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 of the molybdenum precursor itself can serve as the nitrogen and / or carbon source. Molybdenum oxide films can be formed by introducing an oxygen-containing second reactant (such as O2, O3, N2O, CO2, etc.). The second reactant can be introduced into the processing chamber in the form of 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 the processing conditions to allow sulfur from the sulfur-containing molybdenum precursor to be incorporated into the film. Sulfur-containing reactants include H2S, dialkyl sulfides, dialkyl disulfides, and thiols, such as methanethiol or tert-butyl mercaptan.

[0289] In some embodiments, the precursor and the second reactant are allowed to mix in the body of the processing chamber. In other embodiments, after the molybdenum precursor has been introduced and adsorbed on the surface of the substrate, the processing chamber is purged with an inert gas and / or evacuated to remove the unadsorbed precursor from the processing chamber. In some embodiments, the precursor layer on the substrate is adsorption-limited. In other embodiments, a thicker molybdenum precursor layer can be formed on the surface of the substrate before purging and / or evacuating the processing 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 is introduced first and allowed to adsorb on the surface of the substrate. Then the processing chamber is purged and / or evacuated to remove the second reactant from the volume of the processing chamber, and then the molybdenum precursor is introduced.

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

[0291] After the reaction is complete, the formed molybdenum-containing layer can optionally be annealed, as shown in operation 707. The annealing can be carried out by raising the temperature. For example, if the reaction is carried out at a relatively low temperature, such as at a temperature below about 450 °C (e.g., below about 400 °C), the temperature can be raised, for example, 50 - 200 °C during annealing. In some embodiments, the annealing is carried out at a temperature between about 300 - 500 °C.

[0292] Figure 8The process flow diagram shown illustrates an example of a surface-based deposition process 800 for forming a molybdenum metal film on a substrate. In operation 801, a molybdenum precursor layer and / or a reducing reactant layer is formed on the surface of the substrate. In some embodiments, the layer is an adsorption-limited layer. Next, in operation 803, the processing chamber is purged and / or evacuated. This step ensures that the molybdenum precursor and / or the reducing reactant is present only on the surface of the substrate and not in the volume of the processing chamber. Then, in 805, optionally under plasma activation, 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 801, a reducing agent can be introduced into the processing chamber and reacted with the molybdenum precursor on the surface. If both the molybdenum precursor layer and the reducing reactant layer are formed on the surface of the substrate in 801, the processing conditions (e.g., using plasma treatment of the surface or temperature increase) can be adjusted in 803 to activate the reaction. Next, in 807, the processing chamber is purged and / or evacuated, and in 809, operations 801 - 807 are repeated to form more molybdenum metal. In some embodiments, each cycle of operations 801 - 807 deposits on average about of molybdenum metal. In some embodiments, 2 - 100 cycles are performed. For example, 2 - 20 cycles can be performed. A molybdenum layer having a thickness between about can be formed with a high degree of control over the layer thickness (e.g., ). This method can be used to form a conformal molybdenum metal layer with excellent step coverage.

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

[0294] In some embodiments, the molybdenum-containing film is selectively deposited on the dielectric in the presence of an exposed metal, and in other embodiments, selectively deposited on the metal in the presence of an exposed dielectric. As used herein, "selective deposition" means deposition on a target surface at a higher rate compared to a non-target surface. In some embodiments, the selectivity (the ratio of the deposition rate on the target surface to the deposition rate on the non-target surface) 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) and is substantially not deposited on the exposed metal surface.

[0295] The provided molybdenum-containing film can be deposited on various surfaces, including on metals (e.g., copper, nickel, cobalt, tungsten, etc.), dielectrics (e.g., silicon oxide-based dielectrics, silicon nitride, silicon carbide, metal oxides, metal nitrides, etc.), and on amorphous and crystalline silicon. In some embodiments, the film is deposited as a liner or diffusion barrier layer.

[0296] In one implementation, 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 above the semiconductor layer and defining a channel region in the semiconductor layer between the source region and the drain region. The semiconductor layer includes a semiconductor material, such as silicon (Si), germanium (Ge), or silicon germanium (SiGe). In one embodiment, the gate dielectric layer includes a high-k dielectric having a dielectric constant greater than about 3.9. For example, the gate dielectric layer can include a high-k material, such as HfO, HfSiO, HfSiON, and the like. The gate dielectric layer is typically very thin, e.g., about thick. A layer is disposed above the gate dielectric layer and together forms the gate electrode. An optional capping layer can be directly formed above and in contact with the gate dielectric layer. In some embodiments, the capping layer includes TiN, TaN, and / or WN and has a thickness of about between.

[0297] The layer above the capping layer is called the work function metal-containing layer. This layer includes the molybdenum-containing material provided herein, where the material has a high work function, e.g., a work function greater than about 4.9 eV, greater than about 5.0 eV, or greater than about 5.1 eV. In some embodiments, this 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 additionally treated with a plasma-treated reactant to increase its work function.

[0298] For example, in some embodiments, the deposited molybdenum-containing material is treated with a plasma-activated nitrogen-containing reactant (e.g., N2) to increase the nitrogen content and the work function of the formed layer. In some embodiments, this layer has a thickness of about or between. In one implementation, the work function metal-containing layer has a thickness of about . In some embodiments, the metal-containing layer is directly deposited onto the capping layer. When there is no capping layer, this layer can be directly deposited onto the gate dielectric layer. Finally, the device can optionally include one or more conductive layers formed above the metal-containing layer. In some embodiments, the conductive layer includes one or more of TiAl, TiAlC, TiAlON, and / or a conductive metal filler (e.g., Mo, Co, or W).

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

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

[0301] The molybdenum-containing films provided herein, particularly high-purity molybdenum metal, can be used in interconnect metallization (e.g., for filling recessed features to form contacts), in logic gate applications in FinFETs, as an adhesion layer or a diffusion barrier layer, and in 3D NAND fabrication. Examples of applications include logic and memory contact filling, DRAM buried word line filling, vertical integrated memory gate and word line filling, and 3D integration using through-silicon vias (TSVs). The resistivity of molybdenum is better than that of tungsten, and in some embodiments, molybdenum is a particularly advantageous metal for filling narrow recessed features (e.g., features with a width less than about 20 nm).

[0302] In one application, molybdenum metal is used to fabricate a barrierless contact. In this application, molybdenum metal is directly deposited into recessed features (contact holes) with a width of about 5 - 100 nm (e.g., about 5 - 20 nm), where the recessed features are formed in a dielectric layer and include exposed dielectric (e.g., silicon oxide, silicon nitride, or low-k materials such as silicon carbon oxide) at the sidewalls and silicon or silicon germanium at the bottom. In an alternative embodiment, the contact hole before deposition can be lined with a barrier layer (e.g., WN, MoN, MoC, or TiN) on which molybdenum metal is deposited. Device

[0303] The deposition methods described herein can be performed in various devices. Suitable devices include a processing chamber having one or more input ports for introducing one or more reactants; a substrate holder located in the processing chamber and configured to hold the substrate in place during deposition; and optionally a plasma generation mechanism configured to generate a plasma in the process gas. The device can include a controller having program instructions for causing any of the method steps described herein. The deposition methods described herein can be performed in corresponding ALD and CVD devices.

[0304] For example, in some embodiments, the apparatus includes a controller having program instructions that include instructions for: introducing a molybdenum precursor into a processing chamber, where the precursor is any of the precursors described herein; and causing a reaction between the molybdenum precursor and a second reactant to form a molybdenum-containing material layer on a substrate. The controller may include program instructions for causing any of the methods described herein.

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

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

[0307] Some molybdenum precursors can be stored in solid or liquid form before vaporization and subsequent delivery to the processing station. For example, Figure 9Embodiments include a vaporization point 903 for vaporizing solid reactants to be supplied to a mixing vessel 904. In some embodiments, the vaporization point 903 can be a heated vaporizer. In some embodiments, an inert gas stream passes through a heated solid molybdenum precursor at a pressure below atmospheric pressure or is bubbled through a heated liquid molybdenum precursor and transports the precursor vapor to the processing chamber. The precursor vapor generated from such a vaporizer will condense in the downstream delivery conduit. Exposure of incompatible gases to the condensed reactants can produce small particles. These small particles can clog the conduit, impede valve operation, contaminate the substrate, etc. Some methods of dealing with these problems involve purging and / or evacuating the delivery conduit to remove residual reactants. However, purging the delivery conduit increases the process station cycle time and reduces the process station throughput. Thus, in some embodiments, the delivery conduit downstream of the vaporization point 903 can be heat traced. In some examples, the mixing vessel 904 can also be heat traced. In one non-limiting example, the conduit downstream of the vaporization point 903 has a temperature profile that rises from about 100 °C to about 200 °C at the mixing vessel 904.

[0308] The showerhead 906 distributes the process gas towards the substrate 912. In Figure 9 the illustrated embodiment, the substrate 912 is located below the showerhead 906 and is shown mounted on a pedestal 908. It should be understood that the showerhead 906 can have any suitable shape and can have any suitable number and arrangement of ports for distributing the process gas to the substrate 912. Although not explicitly shown, in some embodiments, the showerhead 906 is a dual plenum showerhead that includes at least two types of conduits, where the first type of conduit is dedicated to transporting the molybdenum-containing precursor vapor and the second type of conduit is dedicated to transporting a second (or other) reactant. In these embodiments, the molybdenum-containing precursor and the reactant are not allowed to mix in the conduit before entering the processing chamber and do not share a conduit if continuously delivered to the processing chamber.

[0309] In some embodiments, a microvolume 907 is located below the showerhead 906. Performing ALD and / or CVD processing in the microvolume rather than in the entire volume of the process station can reduce reactant exposure and purge time, can reduce the time to change process conditions (e.g., pressure, temperature, etc.), can limit exposure of the process station manipulator to the process gas, etc. Exemplary microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. This microvolume also affects the productivity throughput. When the deposition rate per cycle decreases, the cycle time also decreases simultaneously. In some cases, for a given target film thickness, the effect of the reduced cycle time is significant enough to increase the overall throughput of the module.

[0310] In some embodiments, the pedestal 908 can be raised or lowered to expose the substrate 912 to the microvolume 907 and / or to change the volume of the microvolume 907. For example, during the substrate transfer stage, the pedestal 908 can be lowered so that the substrate 912 can be loaded onto the pedestal 908. During the deposition process stage, the pedestal 908 can be raised to position the substrate 912 within the microvolume 907. In some embodiments, the microvolume 907 can completely surround the substrate 912 and a portion of the pedestal 908 to form a region of high flow impedance during the deposition process.

[0311] Optionally, the pedestal 908 can be lowered and / or raised during portions of the deposition process to adjust the processing pressure, reactant concentration, etc. within the microvolume 907. In a case where the process chamber body 902 is maintained at a base pressure during the deposition process, lowering the pedestal 908 can allow the microvolume 907 to be evacuated. Exemplary ratios of the microvolume to the process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It should be understood that in some embodiments, the pedestal height can be adjusted programmatically by a suitable computer controller.

[0312] Although the exemplary microvolume variations described herein relate to a height-adjustable pedestal, it should be understood that in some embodiments, the position of the showerhead 906 can be adjusted relative to the pedestal 908 to change the volume of the microvolume 907. Additionally, it should be understood that the vertical positions of the pedestal 908 and / or the showerhead 906 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 908 can include a rotational axis for rotating the orientation of the substrate 912. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more suitable computer controllers.

[0313] Back to Figure 9In the illustrated embodiment, the showerhead 906 and the pedestal 908 are in electrical communication with an RF power source 914 and a matching network 916 for powering the plasma. In other embodiments, devices without a plasma generator are used to deposit molybdenum-containing films using the provided method. In some embodiments, the energy of the plasma can be controlled by controlling one or more of the pressure of the processing station, the concentration of the gas, the RF source power, the RF source frequency, and the plasma power pulse timing. For example, the RF power source 914 and the matching network 916 can be operated at any suitable power to form a plasma having a composition of desired radical species. Similarly, the RF power source 914 can provide RF power at any appropriate frequency. In some embodiments, the RF power source 914 can be configured to control a high-frequency RF power source and a low-frequency RF power source independently of each other. Exemplary low-frequency RF frequencies can include, but are not limited to, frequencies between 50 kHz and 700 kHz. Exemplary high-frequency RF frequencies can include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It should be understood that any suitable parameters can be adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power can be pulsed intermittently relative to a continuously powered plasma to reduce ion bombardment of the substrate surface.

[0314] In some embodiments, the plasma can be monitored in situ by one or more plasma monitors. In one case, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another case, the plasma density and / or the concentration of the processing gas can be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on measurements from such in situ plasma monitors. For example, the OES sensor can be used in a feedback loop to provide programmed control of the plasma power. It should be understood that in some embodiments, other monitors can be used to monitor the plasma and other processing characteristics. Such monitors can include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0315] In some embodiments, the plasma can be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting the plasma conditions for a plasma processing stage can be included in the corresponding plasma activation recipe stage of a deposition processing recipe. In some cases, the processing recipe stages can be sequenced such that all instructions for a deposition processing stage are executed concurrently with that processing stage. In some embodiments, instructions for setting one or more plasma parameters can be included in a recipe stage prior to the plasma processing stage. For example, a first recipe stage can include instructions for setting the flow rates of an inert gas and / or a reactant gas, instructions for setting the plasma generator to a power set point, and a time delay instruction for the first recipe stage. A subsequent second recipe stage can include instructions for enabling the plasma generator and a time delay instruction for the second recipe stage. A third recipe stage can include instructions for disabling the plasma generator and a time delay instruction for the third recipe stage. It should be understood that these recipe stages can be further subdivided and / or iterated in any suitable manner within the scope of the present disclosure.

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

[0317] Figure 10 FIG. shows a schematic diagram of an embodiment of a multi-station processing tool 1000 having an in-station load lock 1002 and an out-station load lock 1004, one or both of which can include a remote plasma source. Such a tool can be used to process substrates using the methods provided herein. At atmospheric pressure, a robotic arm 1006 is configured to move a wafer from a cassette loaded via a susceptor 1008 through an atmospheric port 1010 into the in-station load lock 1002. The wafer is placed by the robotic arm 1006 on a susceptor 1012 within the in-station load lock 1002, the atmospheric port 1010 is closed, and the load lock is evacuated. When the in-station load lock 1002 includes a remote plasma source, the wafer can be exposed to remote plasma processing within the load lock before being introduced into the processing chamber 1014. Additionally, the wafer can also be heated within the in-station load lock 1002, for example to remove moisture and adsorbed gases. Next, a chamber transfer port 1016 leading to the processing chamber 1014 is opened, and another robotic arm (not shown) places the wafer onto the susceptor at the first station shown in the reactor for processing. Although Figure 10The illustrated embodiments include a load lock, but it should be understood that in some embodiments, wafers can be introduced directly into the processing station.

[0318] The illustrated processing chamber 1014 includes four processing stations, Figure 10 numbered 1 through 4 in the illustrated embodiment. Each station has a heated pedestal (shown as 1018 for station 1) and a gas line inlet. It should be understood that in some embodiments, each processing station can have different or multiple uses. Although the illustrated processing chamber 1014 includes four stations, it should be understood that a processing chamber according to the present disclosure can have any suitable number of stations. For example, in some embodiments, the processing chamber can have five or more stations, while in other embodiments, the processing chamber can have three or fewer stations.

[0319] Figure 10 An embodiment of a wafer handling system 1090 for transferring wafers within the processing chamber 1014 is also illustrated. In some embodiments, the wafer handling system 1090 can transfer wafers between various processing stations and / or between a processing station and the load lock. It should be understood that any suitable wafer handling system can be employed. Non-limiting examples include a wafer turntable and a robotic arm for handling wafers. Figure 10 An embodiment of a system controller 1050 for controlling the processing conditions and hardware state of the processing tool 1000 is also illustrated. The system controller 1050 can include one or more memory devices 1056, one or more mass storage devices 1054, and one or more processors 1052. The processor 1052 can include a CPU or a computer, analog and / or digital input / output connections, a stepper motor controller board, and the like.

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

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

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

[0323] The substrate positioning program may include program code for a processing tool component that loads a substrate onto the pedestal 1018 and controls the spacing between the substrate and other parts of the processing tool 1000.

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

[0325] The heater control program may include code for controlling the current flowing to a heating unit that heats the substrate. Alternatively, the heater control program may control the transfer 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 disclosed range.

[0326] The plasma control program may include code for setting the RF power level and frequency applied to a processing electrode in one or more processing stations, for example, using any RF power level disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

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

[0328] In some embodiments, the parameters regulated by the system controller 1050 may relate to processing conditions. Non-limiting examples include processing gas composition and flow rate, temperature, pressure, plasma conditions (e.g., 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 input using the user interface.

[0329] Signals for monitoring the processing may be provided by the analog and / or digital input connectors of the system controller 1050 from various processing tool sensors. Signals for controlling the processing may be output through the analog and / or digital output connectors of the processing tool 1000. Non-limiting examples of processing tool sensors that may be monitored include mass flow controllers, pressure sensors (e.g., pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain the processing 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 as needed to perform a specific function / method.

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

[0332] Also mounted on transfer module 1103 can be one or more single- or multi-station modules 1107 capable of performing plasma or chemical (non-plasma) pre-cleaning, or any other processing related to the disclosed methods. In some cases, module 1107 can be used for various processes to, for example, prepare substrates for deposition processes. Module 1107 can also be designed / configured to perform various other processes, such as etching or polishing. 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 atmospheric transfer chamber 1119 can first move wafers from source module 1101 to load lock 1121. A wafer transfer device (usually a robotic arm unit) in transfer module 1103 moves wafers from load lock 1121 into and out of modules mounted on transfer module 1103.

[0333] In various embodiments, system controller 1129 is used to control processing conditions during deposition. Controller 1129 will generally include one or more memory devices and one or more processors. The processor may include a CPU or calculator, analog and / or digital input / output connections, a stepper motor controller board, and the like.

[0334] Controller 1129 can control all of the activities of the deposition apparatus. System controller 1129 executes system control software that includes sets of instructions for controlling timing, gas mixtures, chamber pressure, room temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters for special processing. Other computer programs stored in memory devices associated with controller 1129 can be employed in some embodiments.

[0335] There will generally be a user interface associated with controller 1129. The user interface can include a display screen, a graphical software display of the apparatus and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0336] System control logic can be configured in any suitable manner. Generally, the logic can be designed or configured in hardware and / or software. Instructions for controlling drive circuits can be hard-coded or provided as software. The instructions can 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 with specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions executable on a general purpose processor. System control software can be encoded in any suitable computer-readable programming language.

[0337] The computer program code for controlling the germanium-containing reductant pulse, the hydrogen flow, the tungsten-containing precursor pulse, and other processes in the process sequence can be written in any common computer-readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. The compiled object code or script is executed by the processor to complete the tasks identified in the program. Also as indicated, the program code can be hard-coded.

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

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

[0340] In some implementations, the controller 1129 is part of a system that can be part of the above embodiments. Such systems can include semiconductor processing equipment that includes one or more processing tools, one or more processing chambers, one or more platforms for processing, and / or specific processing components (wafer pedestal, gas flow system, etc.). These systems can be integrated with electronics for controlling their operation before, during, and after processing semiconductor wafers or substrates. The electronics can be referred to as a "controller" that can control various components or sub-components of one or more systems. Depending on the processing requirements and / or the type of system, the controller 1129 can be programmed to control any of the processes disclosed herein, including controlling process gas delivery, 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 other transfer tools, and / or load locks connected or interfaced to a specific system.

[0341] Broadly speaking, a controller can be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receives instructions, issues instructions, controls operations, enables cleaning operations, enables endpoint measurements, and so on. The integrated circuits can include chips in the form of firmware that stores 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). The program instructions can be instructions transmitted to the controller in various individual settings (or program files), which settings define the operating parameters for performing specific processing on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer for performing one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0342] In some implementations, the controller can be part of or coupled to a computer that is integrated with, coupled to, or networked to the system or a combination thereof. For example, the controller can be in the "cloud" or be all or part of a fab host system, thereby allowing remote access to wafer processing. The computer can enable remote access to the system to monitor the current progress of manufacturing operations, examine the history of past manufacturing operations, examine trends or performance criteria for multiple manufacturing operations, change the parameters of the current process, set up the processing steps to follow the current process, or initiate a new process. In some embodiments, a remote computer (e.g., a server) can provide a processing recipe to the system via a network, which network can include a local network or the Internet. The remote computer can include a user interface that allows for the input or programming of parameters and / or settings, which are then transmitted from the remote computer to the system.

[0343] In some embodiments, the controller receives instructions in the form of data that specify the parameters for each processing step to be performed during one or more operations. It should be understood that the parameters can be for the type of processing to be performed as well as the type of tool that the controller is configured to connect to or control. Thus, as described above, the controller can be distributed, for example, by including one or more discrete controllers that are connected together via a network and work towards a common goal (e.g., the processing and control described herein). An example of a distributed controller for these purposes can be one or more integrated circuits on a chamber that communicate with one or more remote integrated circuits (e.g., at the platform level or as part of a remote computer) that are combined to control in-chamber processing.

[0344] Exemplary systems can include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin clean chambers or modules, metal electroplating chambers or modules, cleaning chambers or modules, bevel edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing systems that can be associated with or used in the fabrication and / or manufacture of semiconductor wafers.

[0345] As described above, depending on one or more processing steps to be performed by the tool, the controller can communicate with one or more of the following: other tool circuits or modules, other tool components, combined tools, other tool interfaces, adjacent tools, adjoining tools, tools located throughout the factory, hosts, another controller, or tools used in material handling that transport a container of wafers between tool locations and / or load ports in a semiconductor manufacturing facility. Additional embodiments

[0346] The devices and processes described herein can be used in conjunction with lithographic patterning tools or processes, for example, for the preparation or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, etc. Generally, although not necessarily, these devices and processes will be used or operated together in a common manufacturing facility. Lithographic patterning of a film typically includes some or all of the following steps, each step enabling multiple viable tools: (1) coating a photoresist on a workpiece, i.e., a substrate, using a spin coat or spray tool; (2) curing the photoresist using a hot plate or furnace or ultraviolet curing tool; (3) exposing the photoresist to visible light or ultraviolet or X-rays using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern to the underlying film or workpiece by using a dry or plasma-assisted etch tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper. Conclusion

[0347] While the foregoing embodiments have been described in detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and devices of this embodiment. Accordingly, this embodiment should be regarded as illustrative and not restrictive, and the embodiment is not limited to the details given herein.

Claims

1. A method of depositing a film on a semiconductor substrate, the method comprising: Providing a semiconductor substrate in a processing chamber; Forming a metal species having iodine bonds in the processing chamber; And Exposing the metal species having iodine bonds to a reducing agent to form a metal-containing film on the semiconductor substrate; wherein the reducing agent comprises a hydrogen-containing gas source.

2. The method according to claim 1, wherein forming the metal species having iodine bonds comprises (i) introducing a metal precursor into the processing chamber containing the semiconductor substrate; and (ii) introducing an iodine-containing reagent to react with the metal precursor, or wherein forming the metal species having iodine bonds comprises (i) introducing an iodine-containing reagent into the processing chamber containing the semiconductor substrate; and (ii) introducing a metal precursor to react with the iodine-containing reagent.

3. The method according to claim 2, wherein the metal precursor comprises a molybdenum-containing precursor, and wherein the iodine-containing reagent comprises hydrogen iodide, iodine, alkyl iodide, iodosilane, alkyl iodosilane, metal iodide or metal bromide.

4. The method according to claim 1, wherein the hydrogen-containing gas source comprises hydrogen, deuterium, hydrogen and argon, hydrogen and helium, hydrogen and oxygen, hydrogen and nitrogen, ammonia, monodeuterated ammonia, dideuterated ammonia, trideuterated ammonia, hydrazine, alcohol, aldehyde or a combination thereof.

5. A method of 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, Wherein the low-valent molybdenum precursor has an oxidation state of zero, one, two or three, and Wherein the low-valent molybdenum precursor has a structure of 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 ligand, a multidentate ligand, a bidentate ligand or a tridentate ligand, L' is a connecting moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3; and Reacting the low-valent molybdenum precursor with the at least one reactant to form a molybdenum-containing layer on the substrate.

6. The method according to claim 5, wherein the low-valent molybdenum precursor has a structure of formula MoL4, and wherein the low-valent molybdenum precursor has a structure of formula (V): where each R 1 independently comprises an alkyl or haloalkyl group; Each R 2 independently includes a carbonyl group, a cyano group, an isocyanoalkyl group, an isocyanohaloalkyl group, an isocyanoaryl group, an isocyanohaloaryl group, an isocyanate group or an isothiocyanate group; and n is 0, 1, 2 or 3.

7. The method according to claim 5, wherein The low-valent molybdenum precursor has a structure of formula MoL4, and wherein the low-valent molybdenum precursor has a structure of formula (VI): wherein each R 4 is independently aliphatic, alkylsilyl or haloalkyl; or R 4 The substituents can be linked to form a ring.

8. The method according to claim 5, wherein the low-valent molybdenum precursor has a structure of formula MoL5, and wherein the low-valent molybdenum precursor has a structure of formula (X) or formula (XI): Each R 7 independently includes -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; and Each R 8 independently includes allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 9 , wherein R 9 comprises an aliphatic, aryl or heterocyclic group.

9. The method according to claim 5, wherein the low-valent molybdenum precursor has a structure of formula MoL3, and wherein the low-valent molybdenum precursor has a structure of formula (XIV): wherein each R 15 independently comprises aliphatic, alkylsilyl or haloalkyl; or R 15 The substituents can be linked to form a ring.

10. A metal coordination complex comprising a structure of formula (VI), formula (IX), formula (X), formula (XI) or formula (XV): Mo2(OR 16 )6(XV), wherein R 4 、R 6 、R 7 and R 16 each independently comprises -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 comprises =O, =NR, =S or =CR2, Wherein each R independently comprises aliphatic, aryl, haloalkyl or haloaryl; and Each R 8 independently includes allyl, alleny, vinyl, mesityl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilino, N,N-dimethylanilino, tetrahydrofuranyl, piperidyl, pyrrolyl, pyrrolidinyl, pyridyl, piperidyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR 9 , wherein R 9 includes an aliphatic group, an aryl group or a heterocyclic group.

11. A method of depositing a film on a semiconductor substrate, the method comprising: Providing a semiconductor substrate in a processing chamber; Forming a metal species having iodine bonds in the processing chamber; And Expose the iodine-bonded metal substance to a reducing agent, thereby forming a metal-containing film on the semiconductor substrate; wherein forming the iodine-bonded metal substance includes (i) introducing a metal precursor into the processing chamber containing the semiconductor substrate; and (ii) introducing an iodine-containing reagent to react with the metal precursor, or wherein forming the iodine-bonded metal substance includes (i) introducing an iodine-containing reagent into the processing chamber containing the semiconductor substrate; and (ii) introducing a metal precursor to react with the iodine-containing reagent; wherein the metal precursor includes a low-valent molybdenum precursor, the low-valent molybdenum precursor includes an oxidation state of zero, one, two, or three, and wherein the low-valent molybdenum precursor includes a structure of 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 ligand, a multidentate ligand, a bidentate ligand, or a tridentate ligand, L' is a connecting moiety, n is 2, 3, 4, 5, or 6, and m is 1, 2, or 3.

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