Metal halophosphine complexes for thin film deposition

Abstract

Methods and related apparatus for forming a metal layer or metal phosphine on a substrate using a phosphorus-containing metal precursor are provided. The disclosed methods and apparatus may be used to deposit a metal layer on a metal-containing substrate or to selectively deposit metal on a substrate having an exposed metal and an exposed dielectric material. Also provided is a phosphorus-containing metal precursor for depositing metal via ALD.

Description

Docket No. LAM1P069WOMETAL HALOPHOSPHINE COMPLEXES FOR THIN FILM DEPOSITIONCROSS-REFERENCE TO RELATED APPLICATIONS

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

[0002] Deposition of conductive materials is an integral part of many semiconductor fabrication processes. These materials may be used for horizontal interconnects, vias between adjacent metal layers, contacts between metal layers and devices, and as lines in memory devices. In an example of deposition, a tungsten (W) layer may be deposited on a titanium nitride (TiN) barrier layer to form a TiN / W bilayer by chemical vapor deposition (CVD) process using tungsten hexafluoride (WFe).

[0003] For some applications, molybdenum (Mo) offers several benefits over other metals such as cobalt (Co), ruthenium (Ru), and tungsten (W): (i) barrierless and linerless deposition is more feasible on oxides and nitrides as compared to deposition of cobalt, ruthenium, and tungsten, (ii) Mo resistivity scaling is better than that of tungsten, (iii) Mo intermixing with underlying Co is not expected compared to Ru intermixing with Co at temperatures less than 450°C, and (iv) there is relatively easy Mo integration into current W schemes compared to copper and ruthenium.

[0004] For some applications, integrated circuits are manufactured by a complex process in which various layers of materials are sequentially constructed in a predetermined arrangement on a semiconductor substrate.

[0005] The predetermined arrangement of materials on a semiconductor substrate is often accomplished by deposition of a material over the entire substrate surface, followed by removal of the material from predetermined areas of the substrate, such as by deposition of a mask layer and subsequent selective etching process. Multiple steps are typically required when one material is to be deposited only on a first surface while another material is to be deposited on a second surface. To accomplish the desired arrangement, one material may be deposited over the entire substrate surface. Then a photolithography process is used to pattern the materialDocket No. LAM1P069WOexposing the material not on the first surface. The first surface is then etched until the material only remains on the first surface. The same steps must then be repeated in order to deposit another material on the second surface. Such processes are not only cumbersome but also can result in the formation of undesirable materials in undesirable locations on a substrate.

[0006] Semiconductor processing efficiency could be improved if a single process suitable for advanced semiconductor applications could be utilized to both deposit a first material on a first surface of a substrate and a second material on a second surface of the substrate.

[0007] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.SUMMARY

[0008] Provided herein are methods and related apparatus for forming a metal layer or metal phosphine on a substrate using a phosphorus-containing metal precursor. The methods and apparatus disclosed herein may be used to deposit a layer of metal on a metal-containing substrate or to selectively deposit a metal on a substrate having an exposed metal and an exposed dielectric material. In some cases, the methods may be used to form laminated metal layers.

[0009] One general aspect includes exposing a substrate to a phosphorus-containing metal precursor to form a phosphorus- and metal-containing layer on the substrate and converting the phosphorus- and metal-containing layer to a layer of the metal. Implementations may include one or more of the following features.

[0010] In some embodiments, the phosphorus-containing metal precursor is a homoleptic complex having one or more phosphorus-containing ligands. In some embodiments, the phosphorus-containing metal precursor is a heterlopetic complex having two or more different ligands, where at least one ligand is a phosphorus-containing ligand.

[0011] In some embodiments, the phosphorus-containing metal precursor is MaLb, where M is one of copper (Cu), cobalt (Co), nickel (Ni), platinum (Pt), chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), and gold (Au). L is a phosphorus-containing ligand, a > 1, and b > 1. In some embodiments, the phosphorus-containing ligand may be one of PF3, P(CF3)3, PFI.2(CF3)2-3, OPF3, and OP(CF3)3.

[0012] In some embodiments, the phosphorus-containing metal precursor is characterized byDocket No. LAM1P069WOMaLbYc, where M is one of Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, and Au. L is a phosphorus-containing ligand, Y is an organic ligand different from L, a > 1, b > 1, and c > 1. In some embodiments, the phosphorus-containing ligand may be one of PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3.

[0013] In some embodiments, organic ligands in MaLbYcmay include optionally substituted carbonyl, optionally substituted isocyanide, optionally substituted nitriles, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted silyl, halo, optionally substituted aliphatic, 1,4-diazadiene (DAD), and a second phosphorus-containing ligand different from L.

[0014] In some embodiments, the organic ligand in MaLbYcis one of the: CO, -CNRa, -NCRa, tetrahydrofuran, pyridine, cyclopentadienyl, benzene, 1,4-diazadiene (DAD), -PRb3, halo, and CH2=CHSiMe3, where Raincludes methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, secbutyl, cyclohexyl, phenyl, benzyl, xylyl, mesityl, and Rbincludes methyl, ethyl, n-propyl, n-butyl, phenyl.

[0015] In some embodiments, the phosphorus-containing metal precursor is characterized by MaLbYcZd, where M is one of Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, and Au. L is a phosphorus-containing ligand, Y is an organic ligand different from L, Z is a halo, a > 1 , b > 1, c > 1, and d > 1. The phosphorus-containing ligand is one of PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3.

[0016] In some embodiments, organic ligands in MaLbYcZamay include optionally substituted carbonyl, optionally substituted isocyanide, optionally substituted nitriles, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted silyl, halo, optionally substituted aliphatic, 1,4-diazadiene (DAD), and a second phosphorus-containing ligand different from L.

[0017] In some embodiments, the organic ligand in MaLbYcZa is one of the: CO, -CNRa, -NCRa, tetrahydrofuran, pyridine, cyclopentadienyl, benzene, 1,4-diazadiene (DAD), -PRb3, halo, and CH2=CHSiMe3, where Raincludes methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl, cyclohexyl, phenyl, benzyl, xylyl, mesityl, and Rbincludes methyl, ethyl, n-propyl, n-butyl, phenyl.

[0018] In some embodiments, converting the phosphorus- and metal-containing layer to a layer of the metal involves introducing a co-reactant to a process chamber containing the substrate. In some embodiments, this may involve introducing a halide gas to a process chamber. In some embodiments, plasma may be generated from a halide gas. In some embodiments, halide gas is one of fluorine-containing gas, chlorine-containing gas, bromine-containing gas, or iodine-Docket No. LAM1P069WOcontaining gas. In some embodiments, introducing the co-reactant involves introducing plasma formed from a halide gas to the process chamber. In some embodiments, the co-reactant reacts with the phosphorus- and metal-containing layer to form a metal halide.

[0019] In some embodiments, converting the phosphorus- and metal-containing layer to a layer of the metal involves exposing the metal halide to a reducing agent to form the metal. In such implementations, the co-reactant may include a hydrogen-containing gas.

[0020] In some embodiments, hydrogen-containing gas is one of H2 gas, a silicon-containing gas, a boron-containing gas, and a phosphorus-containing gas. In some embodiments, hydrogen-containing gas is one of S i H4 gas, B2H6 gas, and PH3 gas.

[0021] In some embodiments, the co-reactant is co-flowed with the phosphorus-containing metal precursor. In some embodiments, the co-reactant and the phosphorus-containing metal precursor are introduced sequentially to a chamber containing the substrate.

[0022] In some embodiments, converting the phosphorus- and metal-containing layer to a layer of the metal involves reducing the phosphorus- and metal-containing layer to form the layer of the metal.

[0023] In some embodiments, converting the phosphorus- and metal-containing layer to a layer of the metal involves forming a phosphorus-containing compound wherein the phosphorus in the phosphorus-containing compound has an oxidation state +5.

[0024] In some embodiments, converting the phosphorus- and metal-containing layer to a layer of the metal involves a thermal decomposition of the phosphorus- and metal-containing layer. In some embodiments, the substrate temperature may be between 100°C and 450°C for thermal decomposition of the phosphorus- and metal-containing layer.

[0025] In some embodiments, the phosphorus- and metal-containing material is a metal phosphide (MxPy).

[0026] In some embodiments, the substrate includes an exposed metal surface and can further include an exposed dielectric surface.

[0027] In some embodiments, when used, the method selectively deposits phosphorus- and metal-containing material on the exposed metal surface.

[0028] Another general aspect includes a method for selectively depositing a metal layer on a metal-containing surface. The method may include the following operations: (a) providing a substrate having an exposed metal-containing surface and an exposed dielectric surface; (b) exposing the substrate to a first phosphorus-containing metal precursor; (c) selectively depositing a first phosphorus- and metal-containing layer on the exposed metal surface and forming an adsorbate on the exposed dielectric surface; and (d) converting the first phosphorus-Docket No. LAM1P069WOand metal-containing layer to a first metal layer.

[0029] In some embodiments, the exposed metal-containing surface includes tungsten or titanium nitride.

[0030] In some embodiments, the adsorbate is phosphoric acid.

[0031] In some embodiments, the adsorbate prevents the deposition of a second metalcontaining material on the dielectric.

[0032] In some embodiments, the method further include (e), removing the adsorbate after (d). In some embodiments, adsorbate may be removed by exposing the substrate to water or an oxygen-containing plasma.

[0033] In some embodiments, the method may involve repeating (b), (c), and (d).

[0034] In some embodiments, the method further involves the following operations: (f) exposing the substrate to a second phosphorus-containing metal precursor; (g) selectively depositing a second phosphorus- and metal-containing layer on the first metal layer; and (h) converting the second phosphorus- and metal-containing layer to a second metal layer.

[0035] In some embodiments, one or more of the operations may be repeated. For example, operations (b), (c), (d), (f), (g), and (h) may be repeated.

[0036] In some embodiments, adsorbate may be removed before or after depositing the second metal-containing layer.

[0037] In some embodiments, the second phosphorus-containing metal precursor is different from the first phosphorus-containing metal precursor.

[0038] In some embodiments, the metals in the first metal layer and the second metal layer are different.

[0039] Another general aspect includes a method of inhibiting the deposition of metalcontaining material using phosphine-containing gas. The method involves: providing a substrate having an exposed metal-containing material; introducing phosphine-containing gas; and binding phosphine-containing gas to form a monolayer on the surface of the exposed metalcontaining material to thereby inhibit deposition on the metal-containing material. The method may further include exposing the monolayer to at least one of: water, hydrogen-containing plasma, or oxygen-containing plasma. In some embodiments, the monolayer may be converted to a layer of phosphate.

[0040] In some embodiments, the phosphine-containing gas comprises PF3 gas. In some embodiments, the phosphine-containing gas is delivered in an argon gas. In some embodiments, the argon gas comprises between 0.1% and 95% of the total volume of the argon gas and the phosphine-containing gas.Docket No. LAM1P069WO

[0041] Another general aspect includes a method of selectively etching the metal-containing material using a phosphine-containing gas. The method involves: providing a substrate having a first exposed material and a second exposed material thereon; introducing phosphine-containing gas; and elevating the temperature above 200°C to selectively etch the first exposed material, where the first exposed material is a metal-containing material. In some embodiments, the phosphine-containing gas comprises PF3 gas.

[0042] Another general aspect includes a method of selectively etching the silicon-containing material using a phosphine-containing gas. The method involves: providing a substrate having a first material and a second material thereon; introducing a phosphine-containing gas; igniting a plasma to generate fluorine radicals from the phosphine-containing gas; and selectively etching the first material, wherein the first material is a silicon-containing material. In some embodiments, he silicon-containing material is SiC>2, SiOxCyNz, SiOxCy. In some embodiments, the plasma is capacitively coupled plasma (CCP), inductively coupled plasma (ICP), or microwave plasma.

[0043] One general aspect includes an apparatus for processing a substrate. The apparatus may include the following elements: a process chamber; a pedestal; one or more gas inlets for flowing gases into the processing chamber; a controller including machine-readable instructions for: (a) providing the substrate; (b) introducing a phosphorus-containing precursor to form a phosphorus- and metal-containing layer; and (c) converting the phosphorus- and metal-containing layer to a layer of the metal.

[0044] One general aspect includes an apparatus for processing a substrate. The apparatus may include the following elements: a process chamber having one or more stations; a pedestal; one or more gas inlets for flowing gases into the processing chamber; a controller including machine-readable instructions for: (a) providing the substrate to a first station in the process chamber; (b) in the first station, introducing a phosphorus-containing precursor to form a phosphorus- and metal-containing layer; (c) transferring the substrate to a second station in the process chamber; and (d) in the second station, converting the phosphorus- and metalcontaining layer to a metal layer.BRIEF DESCRIPTION OF DRAWINGS

[0045] Figures 1A and IB are schematic examples of material stacks according to various embodiments.

[0046] Figures 2A-2J are schematic examples of various structures into which metal may be deposited in accordance with disclosed embodiments.Docket No. LAM1P069WO

[0047] Figure 3 is a schematic example of features that are filled to contact underlying metals.

[0048] Figure 4 is a schematic example of a metal-on-metal integration scheme.

[0049] Figure 5 is a flow diagram depicting an example process for performing disclosed embodiments.

[0050] Figure 6 is a flow diagram illustrating an example process for performing selective deposition according to disclosed embodiments.

[0051] Figure 7 depicts a schematic illustration of an embodiment of an ALD process station.

[0052] Figure 8A and Figure 8B show examples of semiconductor processing tools.

[0053] Figure 9 provides an example of a solid precursor delivery system.DETAILED DESCRIPTION

[0054] In the following descriptions, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.Definitions

[0055] By “aliphatic” is meant a hydrocarbon moiety having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (Ci-10), and which includes saturated groups such as alkanes (or alkyl) and unsaturated groups such as alkenes (or alkenyl), alkynes (or alkynyl), and also includes cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. Such a hydrocarbon can be unsubstituted or substituted with one or more groups, such as halogens or groups described herein for an alkyl group.

[0056] By “alkenyl” is meant an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. Non-limiting unsubstituted alkenyl groups include C2-8 alkenyl, C2-6 alkenyl, C2-5 alkenyl, C2-4 alkenyl, or C2-3 alkenyl. Exemplary, non-limiting alkenyl groups include vinyl or ethenyl (-CH=CH2), 1-propenyl (-CH=CHCH3), allyl or 2-propenyl (-CH2-CH=CH2), 1-butenyl (-CH=CHCH2CH3), 2-butenyl (-CH2CH=CHCH3), 3-butenyl (e.g. -CH2CH2CH=CH2), 2-butenylidene (e.g., =CH-Docket No. LAM1P069WOCH=CHCH3), and the like.

[0057] By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, which is an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenylene group can be cyclic (e.g., C3-24 cycloalkenyl) or acyclic. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkenylene groups include -CH=CH- or -CH=CHCH2-.

[0058] By “alkoxy” is meant -OR, where R is an optionally substituted alkyl group, as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, Ci-16, C1-18, C1-20, or Ci-24 alkoxy groups.

[0059] By “alkyl” and the prefix “alk” is meant a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (n-Pr or nPr), isopropyl (i-Pr or iPr), cyclopropyl, n-butyl (n-Bu or nBu), isobutyl (i-Bu or iBu), s-butyl (s-Bu or sBu), t-butyl (t-Bu or tBu), cyclobutyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can be cyclic (e.g., C3-24 cycloalkyl) or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group can include haloalkyl, in which the alkyl group is substituted by one or more halo groups, as described herein. In another example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-Ak, wherein Ak is optionally substituted C1-6 alkyl); (2) amino (e.g., -NRN1RN2, where each of RN1and RN2is, independently, H or optionally substituted alkyl, or RN1and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group); (3) aryl; (4) arylalkoxy (e.g., -O-Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl and Ar is optionally substituted aryl); (5) aryloyl (e.g., -C(O)-Ar, wherein Ar is optionally substituted aryl); (6) cyano (e.g., -CN); (7) carboxyaldehyde (e.g., -C(O)H); (8) carboxyl (e.g., -CO2H); (9) C3-8 cycloalkyl (e.g., a monovalent saturated or unsaturated non-aromatic cyclic C3-8 hydrocarbon group); (10) halo (e.g., F, Cl, Br, or I); (11) heterocyclyl (e.g., a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms, such as nitrogen, oxygen, phosphorus, sulfur, or halo); (12) heterocyclyloxy (e.g.,Docket No. LAM1P069WO-O-Het, wherein Het is heterocyclyl, as described herein); (13) heterocyclyloyl (e.g., -C(O)-Het, wherein Het is heterocyclyl, as described herein); (14) hydroxyl (e.g., -OH); (15) N-protected amino; (16) nitro (e.g., -NO2); (17) oxo (e.g., =0); (18) -C02RA, where RAis selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) (C4-18 aryl) C1-6 alkyl (e.g., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl); (19) -C(0)NRBRc, where each of RBand Rcis, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) (C4-18 aryl) C1-6 alkyl (e.g., -Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl); and (20) -NRGRH, where each of RGand RHis, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl (e.g., optionally substituted alkyl having one or more double bonds), (e) C2-6 alkynyl (e.g., optionally substituted alkyl having one or more triple bonds), (f) C4-18 aryl, (g) (C4-18 aryl) C1-6 alkyl (e.g., Lk-Ar, wherein Lk is a bivalent form of optionally substituted alkyl group and Ar is optionally substituted aryl), (h) C3-8 cycloalkyl, and (i) (C3-8 cycloalkyl) C1-6 alkyl (e.g., -Lk-Cy, wherein Lk is a bivalent form of optionally substituted alkyl group and Cy is optionally substituted cycloalkyl, as described herein), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-2, C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, Ci-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkyl group.

[0060] By “alkylene” is meant a multivalent (e.g., bivalent) form of an alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, Ci-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substitution groups, as described herein for alkyl.

[0061] By “alkylcarbonyl” is meant an alkyl group as previously defined appended to the parent molecular moiety through a carbonyl group. Exemplary, non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl among others.

[0062] By “alkynyl” is meant an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, asDocket No. LAM1P069WOdescribed herein for alkyl. Non-limiting unsubstituted alkynyl groups include C2-8 alkynyl, C2-6 alkynyl, C2-5 alkynyl, C2-4 alkynyl, or C2-3 alkynyl. Exemplary, non-limiting alkynyl groups include ethynyl (-C=CH), 1-propynyl (-OCCH3), 2-propynyl or propargyl (-CH2OCH), 1-butynyl (-OCCH2CH3), 2-butynyl (-CH2OCCH3), 3-butynyl (-CH2CH2C=CH), and the like.

[0063] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, which is an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynylene group can be cyclic or acyclic. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary, non-limiting alkynylene groups include -C=C-or -OCCH2-.

[0064] By “amido” is meant -N(RN1)C(O)-, where RN1is H, optionally substituted alkyl, or optionally substituted aryl.

[0065] By “amino” is meant -NRN1RN2, where each of RN1and RN2is, independently, H, optionally substituted alkyl, or optionally substituted aryl, or RN1and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein.

[0066] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein.

[0067] By “aminoaryl” is meant an aryl group, as defined herein, substituted by an amino group, as defined herein.

[0068] By “aryl” is meant a group that contains any carbon-based aromatic group including, but not limited to, phenyl, benzyl, anthracenyl, anthryl, benzocyclobutenyl, benzocyclooctenyl, biphenylyl, chrysenyl, dihydroindenyl, fluoranthenyl, indacenyl, indenyl, naphthyl, phenanthryl, phenoxybenzyl, picenyl, pyrenyl, terphenyl, and the like, including fused benzo-C4-8 cycloalkyl radicals (e.g., as defined herein) such as, for instance, indanyl, tetrahydronaphthyl, fluorenyl, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents, such as any described herein for alkyl.

[0069] By ‘ ‘azido” is meant -N3.

[0070] By ‘ ‘branched alkenyl” is meant an isomer of a straight chain alkenyl compound; oneDocket No. LAM1P069WOhaving alkyl groups bonded to the main carbon chain.

[0071] By ‘ ‘cyano” is meant -CN.

[0072] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0073] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic or aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclopentadienyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.]heptyl, and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl.

[0074] By “deposition” or “vapor deposition” is meant a process in which a metal layer is formed on one or more surfaces of a substrate from vaporized precursor composition(s) including one or more metal containing compounds. The metal-containing compounds are vaporized and directed to and / or contacted with one or more surfaces of a substrate (i.e., semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal containing compounds form a non-volatile, thin, uniform metal-containing layer on the surface(s) of the substrate. One operation of the method is one cycle, and the process can be repeated for as many cycles necessary to obtain the desired metal thickness.

[0075] By “dicarbonyl” is meant any moiety or compound including two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., Rcl-C(O)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group); 1,3-dicarbonyl (e.g., Rcl-C(O)-C(RlaR2a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of Rlaand R2ais, independently, H or an optional substituent provided for alkyl, as defined herein); and 1,4-dicarbonyl (e.g., Rcl-C(O)-C(RlaR2a)-C(R3aR4a)-C(O)RC2, in which each of RC1and RC2is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of Rla, R2a, R3a, and R4ais, independently, H or an optional substituent provided for alkyl, as defined herein).

[0076] By “halo” is meant F, Cl, Br, or I.

[0077] By ‘ ‘halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group.

[0078] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo.Docket No. LAM1P069WO

[0079] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo.

[0080] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo.

[0081] By “haloalkyl” is meant an alkyl group, as defined herein, substituted with one or more halogen. Non-limiting unsubstituted haloalkyl groups include C1-2 haloalkyl, C1-3 haloalkyl, C1-4 haloalkyl, C1-5 haloalkyl, C1-6 haloalkyl, C2-3 haloalkyl, C2-4 haloalkyl, C2-5 haloalkyl, C2-6 haloalkyl, or C3-6 haloalkyl. Other non-limiting haloalkyl groups include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXziH2-ziCXZ2H2-Z2CXyH3-y, wherein each of zl and z2 is, independently, 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of zl, z2, or y is not 0; and -CXzHi-z[CXyiH3-yi][CXy2H3-y2], wherein z is 0 or 1, wherein each of yl and y2 is, independently, 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z, yl, or y2 is not 0.

[0082] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo.

[0083] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). The 3-membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl,Docket No. LAM1P069WObenzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl, benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl, benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., P-carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., IH-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., IH-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,Docket No. LAM1P069WOpyrimidyl, 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-l,2,5-thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl, thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and / or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for aryl.

[0084] By “halophosphine” is meant a phosphine having one or more halogens (chlorine, bromine, iodine, and fluorine). The halogen may form a bond with phosphorus, and halophosphine may have at least one P-X bond, where X may be chlorine, bromine, fluorine, or iodine. A halophosphine may be an optionally substituted fluorophosphine. Examples include phosphorus trifluoride (PF3), phosphorus trichloride (PCI3), phosphorus tribromide (PBrs), phosphorus triiodide (PI3), phosphoryl fluoride (OPF3), or PFI-2(CF3)2-3. In some cases, one or more halogens in the halophosphine ligand may not have a halogen that directly forms a bond with phosphorus. In some examples of halophosphine phosphorus bonded to oxygen, carbon, or both. Non-limiting examples include tris(trifhroromethyl)phosphine (P(CF3)s), PFi-2(CF3)2-3, or OP(CF3)3. Halophosphine may be optionally substituted with aliphatic such as branched or unbranched alkyl, or optionally substituted aryl. The branched or unbranched alkyl chain may be methyl, ethyl, n-butyl, n-propyl. The aryl may be phenyl.

[0085] By “heteroleptic” is meant a metal-containing compound having two or more ligand(s) in having at least two or more of ligands surrounding the central metal atom that are different.

[0086] By “homoleptic” is meant a metal-containing compound having one or more ligand(s) in which all the ligands surrounding or bonded to the central metal atom are the same.

[0087] By “hydroxyl” is meant -OH.

[0088] By “imino” is meant -NR-, in which R can be H or optionally substituted alkyl.Docket No. LAM1P069WO

[0089] By “isocyanate” is meant -NCO.

[0090] By “isothiocyanate” is meant -N=C=S.

[0091] By ‘ ‘isocyano” is meant -C=NR, where R may be an alkyl group such as in an alkylisocyano or an aryl group such as in an arylisocyano. The alkyl or aryl group may be optionally substituted with substituents described below.

[0092] By “laminated metal layer” is meant a composite material stack which may be alternating layers of two or more metals. For example, a laminated metal layer may be an alternating molybdenum and tungsten layers, Mo / W / Mo / W or W / Mo / W / Mo.

[0093] By “oxo” is meant an =0 group.

[0094] By “oxy” is meant -O-.

[0095] By “phosphine,” it means PH3 or organophosphine (PHs-nRn), which may be optionally substituted, where one or more hydrogen may be substituted with a functional group, phosphine may be an optionally substituted phosphine, optionally substituted with aliphatic such as branched or unbranched alkyl, or optionally substituted aryl. For example, optionally substituted phosphine may be tertiary phosphine, PR3, where R is a branched or unbranched alkyl chain such as methyl, ethyl, n-butyl, n-propyl, or an aryl such as phenyl.

[0096] By “silyl” is meant a -SiR!R2R3or -SiR!R2- group. In some embodiments, each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c > 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0097] By “silyloxy” is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR!R2R3, in which each of R1, R2, and R3is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionallyDocket No. LAM1P069WOsubstituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c > 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0098] Use of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohols, ethers, esters, amides, sulfones, sulfides, hydroxyl, nitro, cyano, carboxy, amines, heteroatoms, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxy alkoxy, acyloxy, halogens, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl, cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl and aralkyaminocarbonyl, or any of the substituents of the preceding paragraphs or any of those substituents either directly attached or by suitable linkers. The linkers are typically short chains of 1-3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or -S(O)O-. Rings may be substituted multiple times.

[0099] The term “lower” modifying “alkyl”, “alkenyl”, “alkynyl”, “alkoxy” or “alkoxycarbonyl” refers to a Ci-Ce unit for a particular functionality. For example, “lower alkyl” means Ci-Ce alkyl.

[0100] By ‘ ‘substituted” is meant having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcaronyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether, ester, silicon-containing moieties, thioester or a combination thereof. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring).

[0101] By “thiocyanate” is meant -SCN.

[0102] By ‘ ‘unsubstituted” is meant any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified, then it is hydrogen.Docket No. LAM1P069WO

[0103] As used herein, the term “about” is understood to account for minor increases and / or decreases beyond a recited value, which changes do not significantly impact the desired function of the parameter beyond the recited value(s). In some cases, “about” encompasses + / -10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges.

[0104] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus.

[0105] The term “aspect ratio” generally represents the ratio of the height dimension to the width dimension of particular openings into which an electrical contact is to be placed. For example, a via opening which typically extends in a cylindrical form through multiple layers has a height and a diameter, and the aspect ratio would be the height of the cylinder divided by the diameter. The aspect ratio of a trench would be the height of the trench divided by the minimal width of the trench at its base.

[0106] The term “flow control hardware” generally represents components configured to place one or more chemical sources in fluid connection with a processing chamber. Flow control hardware can comprise one or more mass flow controllers and / or valves, for example. Example chemical sources include dielectric film precursor sources, halogen-containing precursor sources, reactant gas sources, and inert gas sources.

[0107] The term “forming a gas mixture” generally represents either of or both of mixing a plurality of gases before introducing the plurality of gases into the processing chamber, or mixing a plurality of gases in the processing chamber.

[0108] The term “inert gas” generally represents a gas phase material that does not react with other chemicals in a processing chamber during substrate processing. Example inert gases include helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe), as well as nitrogen (N2) in some processes.

[0109] The term “plasma” generally represents a gas comprising cations, free radicals and free electrons. The term “in-situ plasma” generally represents a plasma formed at a processing station in a processing chamber. The term “remote plasma” generally represents a plasma formed at a location away from a processing station in a processing chamber.

[0110] The term “plasma generator” generally represents a combination of components that can be used to form a plasma. Example components include a radiofrequency power source, an impedance matching network, and one or more electrodes.Docket No. LAM1P069WO

[0111] The term “precursor” generally represents a chemical species that adsorbs to a substrate surface in an ALD process. The precursor is reacted with a reactant to convert the adsorbed precursor to a film layer.

[0112] The term “processing chamber” or “process chamber” generally represents an enclosure in which chemical and / or physical processes are performed on substrates. The pressure, substrate temperature and atmospheric composition within a processing chamber can be controllable to perform the chemical and / or physical processes.

[0113] The term “processing tool” may generally represent a machine comprising a processing chamber and other hardware configured to enable processing to be carried out in the processing chamber.

[0114] The term “processing station” generally represents a location in a processing chamber at which a substrate is positioned during processing.

[0115] The term “reactant” generally represents a chemical species that reacts with a precursor adsorbed to a substrate surface to form a film layer in an ALD process. A reaction between a reactant and a precursor can be facilitated by thermal energy and / or a plasma in various processes.

[0116] The implementations disclosed below describe deposition of a material on a substrate such as a wafer, substrate, or other work piece. The work piece may be of various shapes, sizes, and materials. In this application, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication thereon. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. Unless otherwise stated, the processing details recited herein (e.g., flow rates, power levels, etc.) are relevant for processing 300 mm diameter substrates, or for treating chambers that are configured to process 300 mm diameter substrates and can be scaled as appropriate for substrates or chambers of other sizes. In addition to semiconductor wafers, other work pieces that may be used implementations disclosed herein include various articles such as printed circuit boards and the like. The processes and apparatuses can be used in the fabrication of semiconductor devices, displays, LEDs, photovoltaic panels and the like.

[0117] “Silicon oxide” is referred to herein as including chemical compounds including silicon and oxygen atoms, including any and all stoichiometric possibilities for SixOy, including integer values of x and y and non-integer values of x and y. For example, “silicon oxide”Docket No. LAM1P069WOincludes compounds having the formula SiOn, where 1 < n < 2, where n can be an integer or non-integer values. “Silicon oxide” can include sub- stoichiometric compounds such as SiOi.s. “Silicon oxide” also includes silicon dioxide (SiCh) and silicon monoxide (SiO). “Silicon oxide” also includes both natural and synthetic variations and also includes any and all crystalline and molecular structures, including tetrahedral coordination of oxygen atoms surrounding a central silicon atom. “Silicon oxide” also includes amorphous silicon oxide and silicates.

[0118] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds.

[0119] By “unsaturated substituent” is meant a double or triple bond containing an aliphatic chain, cyclic, aryl, or heteroaryl group.

[0120] Provided herein are methods and related apparatus for forming a metal layer or metal phosphine on a substrate using a phosphorus-containing metal precursor. The methods and apparatus disclosed herein may be used to deposit a metal layer on a metal-containing substrate or to selectively deposit a metal on a substrate having an exposed metal and an exposed dielectric material. In some cases, the methods may be used to form laminated metal layers. For example, laminated stacks of alternating molybdenum and tungsten layers (e.g., Mo / W / Mo / W or W / Mo / W / Mo) may be deposited.

[0121] Also provided herein are phosphorus-containing metal precursors for depositing the metal on a substrate. In some implementations, phosphorus-containing precursors may be used to inhibit the subsequent deposition of metal-containing material or to selectively etch a dielectric material in the presence of metal-containing material.

[0122] Methods for depositing a metal layer, particularly for group VI metals (e.g., Mo and W), involve a metal halide precursor such as tungsten hexafluoride (WFe), molybdenum pentachloride (M0CI5), or molybdenum dichloride dioxide (MO2O2CI2).

[0123] In some cases, organometallic precursors may be used to deposit a metal layer. However, it can be challenging to deposit pure metal using the organometallic precursors. For instance, forming a metal film using the organometallic precursors often results in the incorporation of various impurities, such as carbon or nitrogen, into the film.

[0124] In embodiments described herein, a phosphorus-containing metal precursor may be used to form a metal layer. The phosphorus-containing metal precursor have one or more phosphine ligands such as a halophosphine ligand (e.g., PF3, PFI-2(CF3)2-3, OPF3, P(CF3)3). Utilizing the phosphine-containing metal precursor can be advantageous for the following reasons. The phosphine ligands can be easily labilized from the metal under appropriate conditions, such as suitable thermal conditions or via co-reactants. Moreover, carbonyl (-C(O))Docket No. LAM1P069WOor isocyano (CN-R), halophosphine ligands are one of the few ligands that are capable of stabilizing a low-valent metal complex. Further, when used, the unique reactivity of the phosphine ligand can be leveraged. For instance, a P(III) species / ligand can be transformed into a P(V) species which is more easily removed from the metal. As used herein, (III) and (V) following the element symbol refers to the oxidation state of the element. In some implementations, the phosphine ligands may be absent of carbon, nitrogen, or oxygen that may be incorporated into the resulting film during the deposition process. When used, the phosphorus-containing metal precursor may produce a pure or nearly metal, largely free of carbon or nitrogen.

[0125] In some embodiments, the phosphorus-containing metal precursors may be used to selectively deposit a metal layer on a metal-containing substrate. For example, in interconnect metallization, the incoming bottom surface may be a conductive surface, and the sidewall surfaces may be dielectric surfaces. Selective deposition may be useful for bottom-up deposition by preferentially depositing the metal on a conductive surface in a feature. Examples of metal surfaces include elemental metal films such as tungsten, molybdenum, copper, cobalt, titanium, and ruthenium or metal-containing conductive compound films such as titanium nitride and tungsten nitride. Examples of dielectric surfaces include silicon oxides, silicon nitrides, silicon carbides, silicon oxycarbides (SiOxCy), silicon oxynitrides, aluminum oxides, and the low-k dielectric material such as silicon oxycarbonitride (SiOxCyNz), and the like.

[0126] Figures 1A and IB are schematic examples of the material stack, i.e., substrate, according to various embodiments. Figures 1A and IB illustrate the order of materials in examples of particular stacks and may be used with any appropriate architecture and application, as described further below. Figure 1 A shows the first material stack 111 featuring a substrate 102 and a conductive layer 108 deposited thereon. The substrate 102 may be a silicon or other semiconductor wafer, e.g., a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semiconducting material deposited thereon. In some embodiments, substrate 102 may be or include silicon (Si) or silicon germanium (SiGe). The methods may also be applied to form metallization stack structures on other substrates, such as glass, plastic, and the like.

[0127] The stack 111 has a dielectric layer 104 on the substrate 102. The dielectric layer 104 may be deposited directly on a semiconductor surface (e.g., a Si or SiGe surface) of the substrate 102, or there may be any number of intervening layers. For example, the substrate 102 may include any number of layers deposited in various arrangements on a semiconductor surface.Docket No. LAM1P069WO

[0128] Examples of dielectric layers include doped and undoped silicon oxide, silicon nitride, silicon carbides, silicon oxycarbides, silicon oxynitrides, aluminum oxide layers, and the like. Specific examples include doped or undoped layers of silicon nitride (SiN), silicon dioxide (SiCE), and aluminum oxide (AI2O3). The stack 111 has a layer 106 disposed between the conductive layer 108 and the dielectric layer 104. The layer 106 may be a diffusion barrier and / or an adhesion layer, for example. A diffusion barrier is a layer that prevents the diffusion of species between layers. An adhesion layer is a layer that promotes the adhesion of a layer to an underlying layer. Examples of diffusion barrier and adhesion layers include titanium nitride (TiN), titanium / titanium nitride (Ti / TiN), tungsten (W), tungsten nitride (WN), and tungsten carbon nitride (WCN). The conductive layer 108 is the main conductor of the structure. In some embodiments, the conductive layer 108 may include multiple bulk layers deposited at different conditions. The conductive layer 108 may or may not include a nucleation layer. In the depicted example of Figure 1A, the conductive layer 108 is deposited directly on the layer 106. In other embodiments (not depicted), the conductive layer 108 may be deposited on a separate layer such as a growth initiation layer that includes another material, such as a tungsten (W) or W-containing growth initiation layer. The growth initiation layer may be used to facilitate nucleation and growth of the conductive layer 108.

[0129] Figure IB shows another example of a stack 121. In this example, the stack 121 includes the substrate 102, and dielectric layer 104, with conductive layer 108 deposited directly on the dielectric layer 104, without an intervening diffusion barrier or adhesion layer. The conductive layer 108 is as described with respect to Figure 1A. By using conductive as the main conductor, low-resistivity thin films can be obtained. Examples of low-resistivity thin films include films with a resistivity less than 40 uOhm-cm at 60 angstroms thickness and less than 15 uOhm-cm at 200 angstroms thickness.

[0130] In some embodiments, a stack (not shown) may include the substrate, a conductive layer, and a molybdenum layer deposited onto the conductive layer. As used herein, a conductive layer is a layer having a conductivity of at least 104 -1-cm-1at room temperature. As used herein, a conductive layer, a conductive material, or a conductor may refer to a metal, a metal-containing material, or a metal-containing layer. . Examples include molybdenum on a metal layer (e.g., a W layer, or another Mo layer). In these embodiments, there is no dielectric layer between the molybdenum layer and the conductive layer. Similarly, the stack may include molybdenum deposited directly on a metal compound layer. Examples include molybdenum on a metal nitride layer (e.g., TiN, WN, or MoN). In still some other embodiments of a stack (not shown), the stack may include a substrate and a molybdenum layer depositedDocket No. LAM1P069WOdirectly on the substrate, including directly on a semiconducting surface, on a dielectric surface, or on a conductive surface. Figures 1A and IB illustrate examples of the order of materials in a particular stack and may be used with any appropriate architecture and application, with examples described further below.

[0131] The methods described herein are performed on a substrate that may be housed in a chamber. The substrate may be a silicon or other semiconductor wafer, including wafers having one or more layers of material, such as dielectric, conducting, or semiconducting material deposited thereon. The methods are not limited to semiconductor substrates and may be performed to fill any feature with metal.

[0132] Substrates may have features such as vias or contact holes, which may be characterized by one or more narrow and / or re-entrant openings, constrictions within the feature, and high aspect ratios. A feature may be formed in one or more of the above-described stacks or layers within a stack. For example, the feature may be formed at least partially in a dielectric layer. In some embodiments, a feature may have an aspect ratio of at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, at least about 25:1, or higher. One example of a feature is a hole or via in a semiconductor substrate or a layer on the substrate.

[0133] Figure 2A depicts a schematic example of a DRAM architecture, including a metal buried wordline (bWL) 208 in a silicon substrate 202. The bWL is formed in a trench etched in the silicon substrate 202. Lining the trench is a conformal barrier layer 206 and an insulating layer 204. The conformal barrier layer 206 is disposed between the insulating layer 204 and the silicon substrate 202. In this example, the insulating layer 204 may be a gate oxide layer formed from a high-k dielectric material such as silicon oxide or silicon nitride material. In some embodiments disclosed herein, the conformal barrier layer 206 is TiN or a tungsten-containing layer, such as WN or WCN layer. In some embodiments, a conformal tungsten-containing growth initiation layer (not shown) may be present between the conformal barrier layer 206 and the bWL 208. Alternatively, the bWL 208 may be deposited directly on a TiN or other diffusion barrier. In some embodiments, one or both of layers 204 and 206 are not present.

[0134] The bWL structure shown in Figure 2A is one example of an architecture that includes a metal fill layer. During fabrication of the bWL, the metal is deposited into a feature that may be defined by an etched recess in the silicon substrate 202 that is conformally lined with layers 206 and / or 204, if present.

[0135] Figures 2B-2H are additional schematic examples of various structures into which metal may be deposited in accordance with disclosed embodiments. Figure 2B shows anDocket No. LAM1P069WOexample of a cross-sectional depiction of a vertical feature 201 to be filled with metal. The feature can include a feature hole 205 in a silicon substrate 202. The feature hole 205 may have an underlayer 203 lining the sidewall or interior of the feature hole 205 and may form the interior surfaces. The feature hole 205 or other feature may have a dimension near the opening, e.g., an opening diameter or line width of between about 10 nm to 500 nm, for example, between about 25 nm and about 300 nm. The feature hole 205 can be referred to as an unfilled feature or simply a feature. The vertical feature 201, and any feature, may be characterized in part by an axis 218 that extends through the length of the feature, with vertically-oriented features having vertical axes and horizontally-oriented features having horizontal axes. The underlayer 203 can be, for example, a diffusion barrier layer, an adhesion layer, a nucleation layer, a combination of thereof, or any other applicable material. Non-limiting examples of underlayers can include dielectric layers and conducting layers. Examples of dielectric materials include oxides, such as SiCE and AI2O3; nitrides, such as SiN; carbides, such as nitrogen-doped silicon carbide (NDC) and oxygen-doped silicon carbide (ODC); and low k dielectrics, such as carbon-doped SiCb. In particular implementations, an underlayer can be one or more of titanium, titanium nitride, tungsten nitride, titanium aluminide, tungsten, and molybdenum. In some embodiments, the under-layer is tungsten-free. In some embodiments, the underlayer is molybdenum-free.

[0136] In some embodiments, features are wordline features in a 3D NAND structure. For example, a substrate may include a wordline structure having an arbitrary number of wordlines (e.g., 50 to 450) with vertical channels at least 200A deep. Examples of wordline features are described further below. Another example of a feature is a trench in a substrate or layer. Features may be of any depth. In various embodiments, the feature may have an underlayer, such as a barrier layer or adhesion layer. Non-limiting examples of underlayers include dielectric layers and conducting layers, e.g., silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers.

[0137] Figure 2C shows an example of a vertical feature 201 that has a re-entrant profile. A re-entrant profile is a profile that narrows from the bottom, closed-end, or interior of the feature to the feature opening. According to various implementations, the profile may narrow gradually and / or include an overhang at the feature opening. Figure 2C shows an example of the latter, with an underlayer 213 lining the sidewall or interior surfaces of the feature hole 205. Similar to Figure 2B, underlayer 213 can be a diffusion barrier layer, an adhesion layer, a nucleation layer, a combination thereof, or any other applicable material. Non-limiting examples of under-layers can include dielectric layers and conducting layers. The underlayerDocket No. LAM1P069WO213 forms an overhang 215 such that the underlayer 213 is thicker near the opening of the vertical feature 201 than inside the vertical feature 201.

[0138] In some implementations, features having one or more constrictions within the feature may be filled. Figure 2D shows examples of views of various filled features having constrictions. Each of the examples (a), (b), and (c) in Figure 2D includes a constriction 209 at a midpoint within the feature. The constriction 209 can be, for example, between about 15nm and 20nm wide. Constrictions can cause pinch-offs during the deposition of metal in the feature using conventional techniques, with deposited metal blocking further deposition past the constriction before that portion of the feature is filled, resulting in voids in the feature. Example (b) further includes an overhang 215 (such as a liner / barrier overhand) at the feature opening. Such an overhang could also be a potential pinch-off point. Example (c) includes a constriction 212 further away from the field region than the overhang 215 in example (b).

[0139] Horizontal features, such as 3-D memory structures, can also be filled. Figure 2E shows an example of a horizontal feature 250 that includes a constriction 251. For example, horizontal feature 250 may be a word line in a 3-D NAND (also referred to as vertical NAND or VNAND) structure. In some implementations, the constrictions can be due to the presence of pillars in a 3D NAND or other structure. Figure 2F presents a cross-sectional side view of a 3-D NAND structure 210 (formed on a silicon substrate 202) having 3-D NAND stacks (left 225 and right 226), central vertical structure 230, and a plurality of stacked horizontal wordline features 220 with openings 222 on opposite sidewalls 240 of central vertical structure 230. Note that Figure 2F displays two “stacks” of the exhibited 3-D NAND structure 210, which together form the “trench-like” central vertical structure 230. However, in certain embodiments, there may be more than two such stacks arranged in sequence and running spatially parallel to one another, the gap between each adjacent pair of stacks forming a central vertical structure 230, like that explicitly illustrated in Figure 2F. In this embodiment, the horizontal wordline features 220 are 3-D memory wordline features that are fluidically accessible from the central vertical structure 230 through the openings 222. Although not explicitly indicated in the figure, the horizontal wordline features 220 present in both the 3-D NAND stack 225 and 226 shown in Figure 2F (i.e., the left 3-D NAND stack 225 and the right 3-D NAND stack 226) are also accessible from the other sides of the stacks (far left and far right, respectively) through similar vertical structures formed by additional 3-D NAND stacks (to the far left and far right, but not shown). Each 3-D NAND stack 225, 226 contains a stack of wordline features that are fluidically accessible from both sides of the 3-D NAND stack through a central vertical structure 230. In the particular example schematically illustrated in Figure 2F, each 3-DDocket No. LAM1P069WONAND stack contains 6 pairs of stacked wordlines. However, a 3-D NAND memory layout may contain any number of vertically stacked pairs of wordlines.

[0140] The wordline features in a 3-D NAND stack can be formed by depositing an alternating stack of silicon oxide and silicon nitride layers, and then selectively removing the nitride layers leaving a stack of oxide layers having gaps between them. These gaps are the wordline features. Any number of wordlines may be vertically stacked in such a 3-D NAND structure so long as there is a technique for forming them available, as well as a technique available to successfully accomplish (substantially) void-free fills of the vertical features. Thus, for example, a VNAND stack may include between 2 and 512 horizontal wordline features, between 2 and 256 horizontal wordline features, between 8 and 128 horizontal wordline features, or between 16 and 64 horizontal wordline features, and so forth (the listed ranges understood to include e the recited endpoints).

[0141] Figure 2G presents a cross-sectional top-down view of the same 3-D NAND structure 210 shown in the side view in Figure 2F with the cross-section taken through the horizontal section 260 as indicated by the dashed horizontal line in Figure 2F. The cross-section of Figure 2G illustrates several rows of pillars 255, which are shown in Figure 2F to run vertically from the base of substrate 202 to the top of the 3-D NAND structure 210. In some embodiments, pillars 255 are formed from a poly silicon material and are structurally and functionally significant to the 3-D NAND structure 210. In some embodiments, such polysilicon pillars may serve as gate electrodes for stacked memory cells formed within the pillars. The top view of Figure 2G illustrates that pillars 255 form constrictions in the openings 222 to wordline features 220. Fluidic accessibility of wordline features 220 from the central vertical structure 230 via openings 222 (as indicated by the arrows in Figure 2G) is inhibited by pillars 255. In some embodiments, the size of the horizontal gap between adjacent poly silicon pillars is between about 1 and 20 nm. This reduction in fluidic accessibility increases the difficulty of uniformly filling wordline features 220 with the material. The structure of the wordline features 220 and the challenge of uniformly filling them with metal-containing material due to the presence of pillars 255 is further illustrated in Figures 2H, 21, and 2 J.

[0142] Figure 2H exhibits a vertical cut through a 3-D NAND structure similar to that shown in Figure 2F, but here focused on a single pair of wordline features 220 and additionally schematically illustrating a fill process which resulted in the formation of a void 275 in the filled wordline features 220. Figure 21 also schematically illustrates void 275, but in this figure illustrated via a horizontal cut through pillars 255, similar to the horizontal cut exhibited in Figure 2G. Figure 2J illustrates the accumulation of metal-containing material around theDocket No. LAM1P069WOconstriction-forming pillars 255, the accumulation resulting in the pinch-off of openings 222, so that no additional metal-containing material can be deposited in the region of voids 275. Apparent from Figures 2H and 21 is that void-free metal fill relies on the migration of sufficient quantities of deposition precursor down through central vertical structure 230, through openings 222, past the constricting pillars 255, and into the furthest reaches of wordline features 220, prior to the accumulated deposition of metal around pillars 255 causing a pinch-off of the openings 222 and preventing further precursor migration into wordline features 220. Similarly, Figure 2J exhibits a single wordline feature 220 viewed cross-sectionally from above and illustrates how a generally conformal deposition of metal-containing material begins to pinch-off the interior of wordline feature 220 due to the fact that the significant width of pillars 255 acts to partially block, and / or narrow, and / or constrict what would otherwise be an open path through wordline feature 220. (It should be noted that the example in Figure 2J can be understood as a 2-D rendering of the 3-D features of the structure of the pillar constrictions shown in Figure 21, thus illustrating constrictions that would be seen in a plan view rather than in a cross-sectional view.)

[0143] Three-dimensional structures may need longer and / or more concentrated exposure to precursors to allow the innermost and bottommost areas to be filled. Three-dimensional structures can be particularly challenging when employing metal halide and / or metal oxyhalide precursors because of their proclivity to etch, with longer and more concentrated exposure allowing for more etch as parts of the structure.

[0144] In some embodiments, the methods are used to fill features to contact an underlying metal. An example of such a feature is shown in Figure 3. At 301, an unfilled feature 312 is shown. The unfilled feature 312 is formed in an oxide layer 305 and is to be filled with metal to make contact with an underlying metal-containing layer 303. The unfilled feature 312 is defined by sidewall surfaces 315 and bottom surface 317. The metal-containing layer may be, e.g., an elemental metal or a metal silicide in some embodiments.

[0145] According to various embodiments, the sidewall surfaces 315 and the bottom surface 317 may be the same or different materials. In some embodiments, the oxide layer 305 may be exposed to form the sidewall surfaces 315. Similarly, the underlying metal-containing layer 303 may be exposed to form the bottom surface 317. In some embodiments, surface oxidation may result in the bottom surface 317 being a metal oxide. In some embodiments, a liner layer (not shown) may be formed on the sidewall and / or bottom of the feature to form the sidewall surfaces 315 and / or bottom surface 317. Examples of liner layers include TiN, WN, and WCN. In some embodiments, a liner layer may be a molybdenum-containing liner layer such as aDocket No. LAM1P069WOmolybdenum nitride (MoN) layer.

[0146] In some embodiments, the sidewall surfaces 315 and bottom surface 317 are different. In a subsequent deposition operation, metal may be deposited at conditions under which it preferentially nucleates on the bottom surface 317. This can promote bottom-up fill and prevent the formation of voids.

[0147] Examples of underlying metals and / or bottom surfaces include TiN, titanium aluminum carbide (TiAlC), Ti, W, Co, Mo, Ru, Cu, nickel (Ni), iridium (Ir), rhodium (Rh), tantalum (Ta), and tantalum nitride (TaN).

[0148] The methods described herein address various challenges that occur as feature size decreases. For example, void-free gap fill becomes more challenging in small features due to deeper features, re-entrant profiles near the feature openings, and / or insufficient growth selectivity between feature bottom metal surfaces and sidewall dielectric surfaces. Smaller features can lead to more frequent pattern misalignment. An example of a misaligned feature is shown at 350 in which the unfilled feature 312 is not centered over the underlying metal 303. As a result, the bottom surface 317 includes metal and dielectric material.

[0149] In some embodiments, the methods may be used in metal-on-metal integration schemes. An example of such an integration scheme is shown in Figure 4. Fay er 401 includes dielectric 402 and metal 403. An etch stop layer (ESE) 404 is disposed over layer 401. The ESE 404 may be SiN, for example. A dielectric layer 405 is deposited over the ESL 404. The dielectric layer 405 is then patterned and etched, with the etch stopping at the ESL 404 (not shown). The ESL 404 is then removed from feature 412, forming the unfilled feature 412.

[0150] A metal layer 410 may formed at the surface of metal 403 during the previous processing operations. The metal layer 410 may be relatively thin, e.g., on the order of 0.5 nm to 3 nm. It may contain various impurities such as oxygen, nitrogen, and / or other halogens. While surface oxidation can be removed by a hydrogen (H2) plasma, the metal layer 410 is generally resistant to H2 plasma. If left in the device, the metal layer 410 can cause higher resistance at the interface between metal 403 and the subsequently deposited metal film. A surface treatment may be performed prior to the deposition of metal in a feature. According to various embodiments, the surface treatment involves exposure to a metal halide. In some embodiments, the metal halide is provided without a co-reactant, and no deposition occurs. In some embodiments, the metal halide is provided with a co-reactant. A thin metal layer may be deposited.

[0151] Provided below are the methods for forming a metal layer on a substrate. The methods described herein may be used to deposit a molybdenum or tungsten on a metal-containingDocket No. LAM1P069WOsubstrate. In some embodiments, the method may be used to deposit metal on a material stack and / or in a featured substrate, such as the examples shown in Figures 1A, IB, and 2A-2J. It should be noted that various descriptions provided herein are in the context of molybdenum or tungsten deposition, the method may be used to form any suitable metal.

[0152] Figure 5 is an illustrative diagram depicting method 500 of forming a metal layer on a substrate 520. Method 500 includes introducing a phosphorus-containing metal precursor in an operation 503 and exposing the substrate 520 to the phosphorus-containing metal precursor to form a phosphorus and metal-containing layer 530 on the substrate 520. Subsequently, as depicted in operation 505, the phosphorus metal-containing layer 530 is converted into a metal layer 540.

[0153] In some embodiments, the substrate 520 is or includes a metal-containing layer, a conductive material, or a metal. In some embodiments, the substrate 520 may be a material stack or a featured substrate having an exposed metal-containing surface. In some embodiments, the metal-containing surface is an elemental metal surface. In some cases, there may be some oxide formed on the metal-containing surface. In some embodiments, the substrate 520 has an exposed metal-containing surface and an exposed dielectric surface. In some embodiments, method 500 selectively deposits the metal layer 540 on the exposed metalcontaining surface without significant deposition on the exposed dielectric surface.

[0154] In some embodiments, the substrate 520 may be a metal. Non-limiting examples of metal include transition metals such as cobalt (Co), copper (Cu), tungsten (W), ruthenium (Ru), tantalum (Ta), iridium (Ir), rhodium (Rh), tantalum (Ta), nickel (Ni), iron (Fe), gold (Au), platinum (Pt), chromium (Cr), titanium (Ti), hafnium (Hf), zirconium (Zr), and / or molybdenum (Mo), as well as combinations thereof and doped forms thereof.

[0155] In some embodiments, the substrate 520 may be a metal-containing material such as titanium nitride (TiN), titanium / titanium nitride (Ti / TiN), molybdenum nitride (MoNx), tungsten nitride (WN), tungsten carbonitride (WCxNy), titanium aluminum carbide (TiAlxCy), titanium silicide (TiSiz), or tantalum nitride (TaN).

[0156] As depicted in operation 503, a phosphorus-containing metal precursor may be introduced to the process chamber, exposing substrate 520 to the phosphorus-containing metal precursor and thereby forming a metal-containing layer 530 on substrate 520. In various implementations, the phosphorus-containing metal precursors are gaseous precursors. Used herein, the ‘metal precursor’ refers to a metal-containing precursor for depositing a metalcontaining layer or a metal layer. The metal in the metal precursor corresponds to the metal in the deposited metal-containing layer.Docket No. LAM1P069WO

[0157] The phosphorus-containing metal precursor is a metal-containing compound having one or more ligands, where at least one of its ligands is a phosphorus-containing ligand. The phosphorus-containing ligand may be or may include phosphorus, an optionally substituted phosphine, or an optionally substituted halophosphine. In some embodiments, a phosphorus-containing metal precursor has one or more P(III) species or ligands. In some embodiments, the phosphine may be a tertiary phosphine. In some embodiments, phosphorus-containing ligands may be absent of carbon, nitrogen, or oxygen. In some cases, the phosphorus-containing ligand may include carbon, oxygen, and / or nitrogen.

[0158] In some embodiments, the phosphorus-containing ligand is a halophosphine. In some embodiments, halophosphine may be a phosphine having one or more halogens. In some embodiments, halogen may form a bond with phosphorus, and halophosphine may have at least one P-X bond, where X may be chlorine, bromine, fluorine, or iodine. In some embodiments, phosphine-containing gas may be an optionally substituted fluorophosphine. Non-limiting examples include phosphorus trifluoride (PF3), phosphorus trichloride (PCI3), phosphorus tribromide (PBrs), phosphorus triiodide (PI3), phosphoryl fluoride (OPF3), or PFI-2(CF3)2-3. In some embodiments, one or more halogens in the halophosphine ligand may not have a halogen that directly forms a bond with phosphorus. In some embodiments, halophosphine may include phosphorus bonded to oxygen, carbon, or both. Non-limiting examples include tris(trifhioromethyl)phosphine (P(CF3)s), PFI-2(CF3)2-3, or OP(CF3)3.

[0159] In some embodiments, the phosphorus-containing ligand is an optionally substituted phosphine, optionally substituted with aliphatic such as branched or unbranched alkyl, or optionally substituted aryl. For example, optionally substituted phosphine may be tertiary phosphine, PR3, where R is a branched or unbranched alkyl chain such as methyl, ethyl, n-butyl, n-propyl, or an aryl such as phenyl.

[0160] In some embodiments, the phosphorus-containing metal precursor is a homoleptic complex having one or more phosphorus-containing ligands. The homoleptic phosphorus-containing metal precursor may be represented by the formula (I):MaLb (I)where M is a metal corresponding to the metal to be formed on a substrate. For example, M is Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, Au, or any other suitable metal. L in the formula (I) is a phosphorus-containing ligand, such as those described above. In some embodiments, L is one of PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3. In various implementations a > 1 and b > 1, a and b are integers. In some embodiments, a is 1 and b is 6. In some implementations, a is 1 or 2, and b is 1-10. In some cases, the sum of a and b is 4-8.Docket No. LAM1P069WO

[0161] Non-limiting examples of homoleptic phosphorus-containing precursors include but are not limited to Mo(PF3)6, Cr(PF3)6, W(PF3)6, MoP(CF3)3, CrP(CF3)3, WP(CF3)3, MoOPF3, WOPF3, CrOPF3, MOOP(CF3)3, CrOP(CF3)3, or WOP(CF3)3.

[0162] In some embodiments, the phosphorus-containing metal precursor is a heteroleptic complex having two or more different ligands, where at least one ligand is a phosphorus-containing ligand. In some implementations, the heteroleptic phosphorus-containing metal precursor having two different ligands may be represented by the formula (II):MaLbYc (II)where M is a metal corresponding to the metal to be formed on a substrate. For example, M is Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, Au, or any other suitable metal. Lis a phosphorus-containing ligand, and Y is a ligand, such as an organic ligand or a halo, that is different from L, a > 1, b > 1, and c > 1. As used herein, a, b, and c are integers. In some embodiments, a is 1 or 2, b is 1-7, such as 1-5 or 1-3, and c is 1-8, such as 1-5 or 1-4. In some embodiments, the sum of b and c is 4, 6, 8 or between 4-8.

[0163] The phosphorus-containing ligand is any phosphorus-containing ligand, such as those described above, but may be any other appropriate phosphorus-containing ligand. In some implementations, the phosphorus-containing ligand is one of: PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3

[0164] In some embodiments, the organic ligand may include optionally substituted carbonyl. Examples of carbonyl ligands include but are not limited to CO and alkylcarbonyl, such as methylcarbonyl, ethylcarbonyl, or isopropyl carbonyl.

[0165] In some embodiments, the organic ligand may include optionally substituted isocyanide (-C=NR) or an optionally substituted nitrile(R-C=N). The isocyanide or nitrile may have a functional group R, which may be a branched or unbranched alkyl group (alkylisocyano or alkylated nitrile) such as methyl, ethyl, isopropyl, n-propyl, t-butyl, s-butyl. In some embodiments, the functional group R may be an optionally substituted aryl group such as cyclohexyl, phenyl, benzyl, xylyl, or mesityl. Optionally, the alkyl or aryl groups may be further substituted with substituents.

[0166] In some embodiments, the organic ligand may include an optionally substituted heterocyclyl. Examples of optionally substituted heterocyclyl include but are not limited to tetrahydrofuran (OC4H8), pyridine (NC5H5), and cyclopentadienyl. Heterocyclyl may be optionally substituted with any suitable functional groups, such as alkyl or aryl.

[0167] In some embodiments, the organic ligand may be an optionally substituted aryl such as an optionally substituted benzene.Docket No. LAM1P069WO

[0168] In some embodiments, the organic ligand is an optionally substituted silyl. Non-limiting examples of substituted silyl include, but are not limited to, (CH2=CHSiMe3)x, where x is between 1 and 5.

[0169] In some embodiments, the organic ligand is an optionally substituted aliphatic. For example, the organic ligand may be according to R-CCH. In some embodiments, R-CCH is a terminal alkyne, where R may be methyl, ethyl, isopropyl, n-propyl, t-butyl, n-butyl, or s-butyl. In some implementations, the phosphorus-containing metal precursor includes no more than one R-CCH.

[0170] In some embodiments, the organic ligand is a 1,4-diazadiene (DAD).

[0171] In some embodiments, the ligand Y may be a halo, e.g., chlorine, bromine, or iodine.

[0172] In some embodiments, the ligand Y may be another phosphorus-containing ligand that is different from L. For example, L may be PF3, and Y may be PR3 where R is methyl, ethyl, n-propyl, n-butyl, or phenyl.

[0173] In some embodiments, the phosphorus-containing metal precursor is a bimetallic complex, i.e., a is 2.

[0174] Non-limiting examples of the phosphorus-containing metal precursor represented by the formula (II) include, but are not limited to, Mo(CO)(PF3)5, Mo(CO)2(PF3)4, MO(CO)4(PF3)2, MO(CO)5(PF3), MO(CO)(P(CF3)3)5, MO(CO)2(P(CF3)3)4, MO(CO)3(P(CF3)3)3, MO(CO)4(P(CF3)3)2, MO(CO)5(P(CF3)3), MO(NCCH3)3(PF3)3, MO(NCCH3)2(PF3)4, MO(NCCH3)I(PF3)5, MO(OC4H8)3(PF3)3, MO(OC4H8)2(PF3)4, MO(OC4H8)I(PF3)5, MO(NC5H5)3(PF3)3, MO(NC5H5)2(PF3)4, MO(NC5H5)I(PF3)5, W(CO)(PF3)5, W(CO)2(PF3)4, W(CO)4(PF3)2, W(CO)5(PF3), W(CO)(P(CF3)3)5, W(CO)2(P(CF3)3)4, W(CO)3(P(CF3)3)3, W(CO)4(P(CF3)3)2, W(CO)5(P(CF3)3), W(NCCH3)3(PF3)3, W(NCCH3)2(PF3)4, W(NCCH3)I(PF3)5, W(OC4H8)3(PF3)3, W(OC4H8)2(PF3)4, W(OC4H8)I(PF3)5, W(NC5H5)3(PF3)3, W(NC5H5)2(PF3)4, W(NC5H5)I(PF3)5, W(DAD)(PF3)4, or W(DAD)2(PF3)2.

[0175] Other non-limiting examples of phosphorus-containing metal precursors represented by the formula (II) are the precursors containing at least one isocyano ligand (CNR) where R is methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, s-butyl, cyclohexyl, phenyl, benzyl, xylyl, or mesityl. Examples include, Mo(CNR)(PF3)s, Mo(CNR)2(PF3)4, Mo(CNR)3(PF3)3, MO(CNR)4(PF3)2, MO(CNR)5(PF3), MO(CNR)(P(CF3)3)5, MO(CNR)2(P(CF3)3)4, MO(CNR)3(P(CF3)3)3, MO(CNR)4(P(CF3)3)2, MO(CNR)5(P(CF3)3), W(CNR)(PF3)5, W(CNR)2(PF3)4, W(CNR)3(PF3)3, W(CNR)4(PF3)2, W(CNR)5(PF3), W(CNR)(P(CF3)3)5, W(CNR)2(P(CF3)3)4, W(CNR)3(P(CF3)3)3, W(CNR)4(P(CF3)3)2, W(CNR)5(P(CF3)3), Cr(CNR)(PF3)5, Cr(CNR)2(PF3)4, Cr(CNR)3(PF3)3, Cr(CNR)4(PF3)2, Cr(CNR)5(PF3),Docket No. LAM1P069WOCr(CNR)(P(CF3)3)5, Cr(CNR)2(P(CF3)3)4, Cr(CNR)3(P(CF3)3)3, Cr(CNR)4(P(CF3)3)2, Cr(CNR)5(P(CF3)3).

[0176] Other non-limiting examples of the phosphorus-containing metal precursors represented by the formula (II) are those containing at least one cyclopentadienyl (Cp) or benzene (Bz), or 1,4-diazadiene (DAD) ligand. Examples include Mo2(Cp)2(PF3)e, MO(BZ)(PF3)3, MO(DAD)(PF3)4, MO(DAD)2(PF3)2, W2(Cp)2(PF3)6, W(Bz)(PF3)3, W(DAD)(PF3)4, W(DAD)2(PF3)2, Cr2(Cp)2(PF3)6, Cr(Bz)(PF3)3, Cr(DAD)(PF3)4, or Cr(DAD)2(PF3)2.

[0177] Other examples of the phosphorus-containing metal precursors represented by the formula (II) are those containing two different phosphorus-containing ligands. For example, the first phosphorus-containing ligand is PF3, and the second phosphorus-containing ligand is PR3, where R is methyl, ethyl, n-propyl, n-butyl, or phenyl. Examples of such precursors include but are not limited to, Mo(PR3)(PF3)5, Mo(PR3)2(PF3)4, Mo(PR3)3(PF3)3, MO(PR3)4(PF3)2, MO(PR3)5(PF3), W(PR3)(PF3)5, W(PR3)2(PF3)4, W(PR3)3(PF3)3, W(PR3)4(PF3)2, W(PR3)5(PF3), Cr(PR3)(PF3)5, Cr(PR3)2(PF3)4, Cr(PR3)3(PF3)3, Cr(PR3)4(PF3)2, or Cr(PR3)5(PF3).

[0178] Other examples of the phosphorus-containing metal precursors represented by the formula (II) are those containing the halo group. Examples include MO(PF3)5C1, Mo(PF3)5Br, MO(PF3)5I, MO(PF3)4C12, Mo(PF3)4Br2, Mo(PF3)4I2, W(PF3)5C1, W(PF3)5Br, W(PF3)5I, W(PF3)4C12, W(PF3)4Br2, W(PF3)4I2, Cr(PF3)5Cl, Cr(PF3)5Br, Cr(PF3)5I, Cr(PF3)4Cl2, Cr(PF3)4Br2, or Cr(PF3)4I2.

[0179] Other examples of the phosphorus-containing metal precursor represented by the formula (II) may be a nickel or platinum complex. For example, Ni(CO)x(PF3)y, or Pt(CO)x(PF3)y, where x is 1, 2, 3; y is 1, 2, 3, 4; and the sum of x and y is 4.

[0180] Other examples of phosphorus-containing metal precursors represented by the formula (II) is the bimetallic complex. Examples include Mo2(Cp)2(PF3)e, W2(Cp)2(PF3)e, Cr2(Cp)2(PF3)e. In some embodiments, a bimetallic complex may be a cobalt or ruthenium complex. Examples include Co2(CO)x(PF3)yor Ru2(CO)x(PF3)ywhere x = 1,2, 3, 4, 5, 6, 7 and y = 1,2, 3, 4, 5, 6, 7, 8 and the sum of x and y equals 8.

[0181] In some embodiments, the phosphorus-containing metal precursor is a heteroleptic complex having three different ligands, where at least one ligand is a phosphorus-containing ligand. In some implementations, the heteroleptic phosphorus-containing metal precursor may be represented by the formula (III):MaLbYcZd (III)Docket No. LAM1P069WOwhere M is a metal corresponding to the metal to be formed on a substrate. For example, M is Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, Au, or any other suitable metal. Lis a phosphorus-containing ligand, and Y is a ligand, such as an organic ligand, that is different from L, Z is a halo, a > 1, b > 1, c > 1, and d > 1. As used herein, a, b, c, and d are integers. In some embodiments, a is 1 or 2, b is 1-7, such as 1-6, 1-3, 3, or 2, and c is 1-8, such as 1-5, 1 or 2, and d is 1 or 2. In some embodiments, the sum of b and c is 4, 6, 8, or between 4-8. In some embodiments, Z is an optionally substituted aliphatic. In some embodiments, the ligand Z may be according to R-CCH. In some embodiments, R-CCH is a terminal alkyne, where R may be methyl, ethyl, isopropyl, n-propyl, t-butyl, n-butyl, or s-butyl. In some implementations, the phosphorus-containing metal precursor includes no more than one R-CCH.

[0182] The phosphorus-containing ligand is any phosphorus-containing ligand, such as those described above, but may be any other appropriate phosphorus-containing ligand. In some implementations, the phosphorus-containing ligand is one of: PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3

[0183] In some embodiments, the ligand Y may include optionally substituted carbonyl. Examples of carbonyl ligands include but are not limited to CO and alkylcarbonyl, such as methylcarbonyl, ethylcarbonyl, or isopropyl carbonyl.

[0184] In some embodiments, the ligand Y may be an optionally substituted aryl, such as an optionally substituted benzene or cyclopentadienyl.

[0185] In some embodiments, the ligand Z may be a halo, e.g., chlorine, bromine, or iodine.

[0186] In some embodiments, the phosphorus-containing metal precursor is a bimetallic complex, i.e., a is 2.

[0187] Non-limiting examples of the phosphorus-containing metal precursor represented by the formula (III) include, but are not limited to, Mo(Cp)(PF3)3Cl, Mo(Cp)(PF3)3Br, Mo(Cp)(PF3)3I, where Cp is refers to cyclopentadienyl, MO(CO)2(PF3)3C1, Mo(CO)2(PF3)3Br, Mo(CO)2(PF3)3l, MO(CO)2(PF3)2C12, Mo(CO)2(PF3)2Br2, Mo(CO)2(PF3)2l2, MO(CO)(PF3)3C1, Mo(CO)(PF3)3Br, Mo(CO)(PF3)3I, Mo(CO)(PF3)2C12, Mo(CO)(PF3)2Br2, Mo(CO)(PF3)2l2, W(Cp)(PF3)3Cl, W(Cp)(PF3)3Br, W(Cp)(PF3)3I, W(CO)2(PF3)3C1, W(CO)2(PF3)3Br, W(CO)2(PF3)3l, W(CO)2(PF3)2C12, W(CO)2(PF3)2Br2, W(CO)2(PF3)2l2, W(CO)(PF3)3C1, W(CO)(PF3)3Br, W(CO)(PF3)3I, W(CO)(PF3)2C12, W(CO)(PF3)2Br2, W(CO)(PF3)2l2, Cr(Cp)(PF3)3Cl, Cr(Cp)(PF3)3Br, Cr(Cp)(PF3)3I, Cr(CO)2(PF3)3Cl, Cr(CO)2(PF3)3Br, Cr(CO)2(PF3)3I, Cr(CO)2(PF3)2C12, Cr(CO)2(PF3)2Br2, Cr(CO)2(PF3)2l2, Cr(CO)(PF3)3Cl, Cr(CO)(PF3)3Br, Cr(CO)(PF3)3I, Cr(CO)(PF3)2C12, Cr(CO)(PF3)2Br2, or Cr(CO)(PF3)2l2.

[0188] Yet another example of phosphorus-containing metal precursors represented by theDocket No. LAM1P069WOformula (III) is the bimetallic complex. Examples include Co2(CO)x(PF3)y(R-CCH)or Ru2(CO)x(PF3)y(R-CCH) where x = 1-5 and y = 1-6 and the sum of x and y equals 6, and R may include one of methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, or s-butyl.

[0189] As depicted in Figure 5, the phosphorus-containing metal precursors may be used to form a phosphorus- and metal-containing layer 530 on substrate 520. In some embodiments, the phosphorus- and metal-containing layer 530 may be a layer of phosphorus-containing metal, chemisorbed or physisorbed phosphorus-containing metal precursor, a layer of metal phosphine (MxPy), a phosphorus-terminated surface, or combinations thereof. In some embodiments, the phosphorus- and metal-containing layer 530 may be a monolayer.

[0190] In various embodiments, the phosphorus- and metal-containing layer 530 may be deposited by implementing various deposition techniques using one or more of the abovedescribed phosphorus-containing metal precursors. For example, thermal or plasma-enhanced atomic layer deposition (AED) or chemical vapor deposition (CVD) may be used.

[0191] Once formed, the phosphorus- and metal-containing layer 530 may be converted to a metal layer 540, as depicted by operation 505. The metal layer 540 may be, or substantially, an elemental metal, i.e., M(0), or pure metal that is at least 90% pure, at least 95% pure, at least 99% pure, at least 99.5% pure, or at least 99.9% pure. In some cases, the metal layer 540 may be absent of other elements such as C, N, or O, in some embodiments, small amounts of other elements may be present (e.g., less than 10%, less than 5%, less than 1%, less than 0.5%, or less than 0.1%)

[0192] In various implementations, operation 505 involves introducing a co-reactant to the process chamber containing the substrate 520 having the phosphorus- and- metal-containing layer 530 thereon.

[0193] In various embodiments, the co-reactant may be a halide gas such as a chlorine-containing gas, fluorine-containing gas, bromine-containing gas, or iodine-containing gas. In some embodiments, the halide-containing gas may be one or more of chlorine (Ch), fluorine (F2), bromine (Br2), and / or iodine (h). The halide gas may be introduced with an inert gas (e.g., argon gas or nitrogen gas).

[0194] In some embodiments, the co-reactant may be a hydrogen-containing gas, such as th gas, a silicon-containing gas, a boron-containing gas, a phosphorus-containing gas, or a combination thereof. Non-limiting examples of the hydrogen-containing gas include S i F gas, B2H6, and PH3 gas. The hydrogen-containing gas may be introduced with an inert gas (e.g., argon gas or nitrogen gas).

[0195] In some embodiments, converting the phosphorus- and metal-containing layer 530 toDocket No. LAM1P069WOthe metal layer 540 involves generating plasma from the halide gas or the hydrogen-containing gas, and introducing the plasma formed from the halide gas or the hydrogen-containing gas to the process chamber.

[0196] In various embodiments, the plasma may be co-flown with an inert gas (e.g., Ar gas or N2 gas). For example, the plasma formed from hydrogen-containing gas, such as H2 gas, may be introduced with Ar co-flow where the Ar is between 0.5 % and 90% of the total volume. In some embodiments, inert gas is between 0.1 % and 95%, between 0.1 and 90%, between 1% and 90%, between 5% and 90%, between 30% and 90%, between 1% and 98%, between 5% and 95%, between 10% and 95%, between 30% and 95%, less than 95%, or less than 90% of the total volume.

[0197] In some embodiments, plasma is ignited using power less than 500W, 1000W, 2500W, 5000W, 6000W, 7000W, or 8000W. In some embodiments, plasma is ignited using power between 100W and 6000W, between 200W and 6000W, between 500W and 6000W, between 1000W and 6000W, between 100W and 7000W, between 100W and 8000W, between 200W and 7000W, or between 200W and 8000W.

[0198] In some embodiments, the plasma may be generated using an inductively coupled plasma generator, a capacitively coupled plasma generator, or a microwave generator using a suitable frequency (e,g, 10 Hz, 13 Hz, 15 Hz, 20 Hz, or 30 Hz).

[0199] In some embodiments, the co-reactant is co-flowed with the phosphorus-containing metal precursor. In some embodiments, the co-reactant and the phosphorus-containing metal precursor are introduced sequentially to a chamber containing the substrate. For example, a phosphorus-containing metal precursor may be introduced first, and a co-reactant is introduced subsequently. Alternatively, the co-reactant may be introduced first, followed by the phosphorus-containing metal precursor. In some embodiments, alternating doses or pulses of the phosphorus-containing metal precursors and co-reactants are provided to the process chamber in a cycle or repeated manner (e.g., A / B / A / B or B / A / B / A, where A refers to the phosphorus-containing precursor and B refers to the co-reactant).

[0200] In some embodiments, a dose of phosphorus-containing metal precursor may be provided to the process chamber for the duration of 0.05s - 5s, 0.05s - 10s, 0.05s - 15s, 0.05s - 20s, 0.1s - 5s, 0.1s - 10s, 0.1s - 15s, 0.1s - 20s, 0.5s - 5s, 0.5s - 10s, 0.5s - 15a, 0.5s -20s, Is - 5s, Is - 10s, Is - 15s, Is - 20s, 2s - 5s, 2s - 10s, 2s - 15s, 2s - 20s, 5s - 10s, 5s -15s, or 5s - 20s.

[0201] In some embodiments, a dose of co-reactant is provided to the process chamber for the duration 0.05s - 5s, 0.05s - 10s, 0.05s - 15s, 0.05s - 20s, 0.05s - 40s, 0.05s - 50s, 0.1s - 5s,Docket No. LAM1P069WO0.1s - 10s, 0.1s - 15s, 0.1s - 20s, 0.1s - 30s, 0.1s - 40s, 0.1s - 50s, 0.5s - 5s, 0.5s - 10s, 0.5s - 15a, 0.5s - 20s, 0.5s - 30s, 0.5s - 40s, 0.5s - 50s, Is - 5s, Is - 10s, Is - 15s, Is - 20s, Is -30s, Is - 40s, Is - 50s, 2s - 5s, 2s - 10s, 2s - 15s, 2s - 20s, 2s - 30s, 2s - 40s, 2s - 50s, 5s -10s, 5s - 15s, 5s - 20s, 5s - 30s, 5s - 40s, or 5s - 50s.

[0202] In some embodiments, each of the phosphorus-containing precursor doses and / or each of the co-reactant doses may be followed by a purge. The each of purge, independently, may be for a duration of 0.05s - 5s, 0.05s - 10s, 0.05s - 15s, 0.05s - 20s, 0.05s - 40s, 0.05s - 50s, 0.1s - 5s, 0.1s - 10s, 0.1s - 15s, 0.1s - 20s, 0.1s - 30s, 0.1s - 40s, 0.1s - 50s, 0.5s - 5s, 0.5s - 10s, 0.5s - 15a, 0.5s - 20s, 0.5s - 30s, 0.5s - 40s, 0.5s - 50s, Is - 5s, Is - 10s, Is - 15s, Is - 20s, Is - 30s, Is - 40s, Is - 50s, 2s - 5s, 2s - 10s, 2s - 15s, 2s - 20s, 2s - 30s, 2s - 40s, 2s -50s, 5s - 10s, 5s - 15s, 5s - 20s, 5s - 30s, 5s - 40s, or 5s - 50s.

[0203] A non-limiting example of the dose and purge sequence is:Phosphorus-containing metal precursor dose: 0.05s - 10sPurge: 0.05s - 20sCo-reactant dose: 0.05s - 40sPurge: 0.05s - 20s

[0204] In some embodiments, converting phosphorus- and metal-containing layer 530 to the metal layer 540, as depicted in operation 505, involves reducing the phosphorus- and metalcontaining layer 530 by exposing the layer 530 to an oxidant. In some embodiments, forming the metal layer 540 leverages the reactivity of the phosphine ligands having phosphorus with an oxidation state of +3 and transforming it to a phosphorus species having an oxidation state of +5. In various implementations, the co-reactant may act as an oxidant (e.g., F2, CI2, or Br2), reducing the metal to form a pure or elemental metal, M(0). An exemplary redox reaction includes:M(PF3)6+ 6 F2M(s) + 6 PF5

[0205] In some embodiments, the phosphorus- and metal-containing layer 530 may be first converted to a metal halide surface (e.g., metal fluoride, metal chloride, metal bromide, or metal iodide). In various implementations, the metal halide surfaces may be more amenable to subsequent reduction to a pure or elemental metal. The metal halide surfaces may be exposed to a reducing agent, such as H2 gas, to form the metal layer 540.

[0206] In some embodiments, during method 500, fluoride-containing byproducts may be formed. The fluoride-containing byproduct may be volatilized and removed from the process chamber via purge or vacuum. Fluoride-containing byproducts may be advantageous as fluoride-containing byproducts may be more easily removed from the reaction chamberDocket No. LAM1P069WOcompared to other halide-containing byproducts, such as chloride-containing byproducts.

[0207] In some embodiments, converting phosphorus- and metal-containing layer 530 to the metal layer 540, as depicted in operation 505, involves thermal decomposition of the phosphorus- and metal-containing layer 530. In some embodiments, a substrate 520 having a layer of phosphorus- and metal-containing layer 530 may be exposed to a temperature of at least 100°C, at least 200°C, at least 300°C, at least 400°C, between 50°C and 400°C, between 50°C and 450°C, between 50°C and 500°C, between 50°C and 600°C, between 100°C and 450°C, between 100°C and 500°C, between 100°C and 600°C, between 150°C and 450°C, between 150°C and 500°C, between 150°C and 600°C, between 250°C and 450°C, between 250°C and 500°C, or between 250°C and 600°C.

[0208] In some embodiments, converting phosphorus- and metal-containing layer 530 to the metal layer 540, as depicted in operation 505, involves exposing the phosphorus- and metalcontaining layer 530 to a plasma formed in hydrogen-containing gas (e.g., H2 gas).

[0209] In some implementations, operations 503 and 505 may be repeated to form a metal layer 540 having a desired depth. In some implementations, operations 503 and 505 may be repeated, where the phosphorus-containing metal precursor may be varied to form a laminated metal layer 540. For example, the first cycle utilizes a phosphorus-containing molybdenum precursor, and the second cycle utilizes a phosphorus-containing tungsten precursor to form a Mo / W / Mo / W laminated metal layer.

[0210] In other non-limiting embodiments, the method provided herein may be used to selectively deposit a metal on a substrate having an exposed metal (or exposed conductive surface) and an exposed dielectric material. Selective deposition refers to deposition that preferentially occurs on one surface type over another.

[0211] Selective deposition may be useful for bottom-up deposition, by preferentially depositing the metal on a conductive surface in a feature. According to various embodiments, a feature may be provided to the chamber with two material types (e.g., a conductive metal bottom and dielectric sidewalls). In other embodiments, a feature may be provided to the chamber having a single material type that is treated to allow selective deposition. As an example, a feature may be provided with a TiN liner conformally lining the bottom and sidewalls of the feature. The feature may be exposed to a high-temperature metal halide that preferentially etches the TiN layer at the top of the surface to form a TiN cup at the feature bottom, exposing dielectric sidewalls at the top of the surface. Metal or conductive material may then be selectively deposited on the TiN cup. The metal halide exposure may be performed as part of the pre-treatment process described above. In another example, a featureDocket No. LAM1P069WOhaving uniform surface materials may be treated by inhibiting deposition on a portion of the feature. For example, an inhibition treatment may be performed to inhibit deposition at the feature opening.

[0212] Figure 5 is an illustrative example depicting method 600 for selectively depositing a metal layer on a substrate 610. Method 600 involves providing a substrate 610 having an exposed metal-containing surface 611 and an exposed dielectric surface 613. In operation 601, a phosphorus-containing metal precursor is introduced, exposing the substrate 610 to the phosphorus-containing metal precursor. When introduced, phosphorus- and metal-containing layer 630 is deposited on the exposed metal-containing surface 611, and a layer of adsorbate 640 is formed on the exposed dielectric surface 614. In operation 603, phosphorus- and metalcontaining layer 630 is converted to a metal 633. As depicted by operation 605, the layer of adsorbate 640 may be removed to expose the underlying dielectric surface 613.

[0213] In some embodiments, the exposed metal-containing surface 611 on the substrate 610 may be or include a metal-containing layer, a conductive material, or a metal. In some embodiments, substrate 610 may be a material stack or a featured substrate having an exposed metal-containing surface. For example, the featured substrate may have an exposed metal at the feature bottom and exposed dielectric material on the feature sidewalls. In some embodiments, the exposed metal-containing surface 611 is an elemental metal surface. In some cases, there may be some oxide formed on the metal-containing surface 611.

[0214] In some embodiments, the exposed metal-containing surface 611 may be a metal. Nonlimiting examples of metal include transition metals such as cobalt (Co), copper (Cu), tungsten (W), ruthenium (Ru), tantalum (Ta), iridium (Ir), rhodium (Rh), tantalum (Ta), nickel (Ni), iron (Fe), gold (Au), platinum (Pt), chromium (Cr), titanium (Ti), hafnium (Hf), zirconium (Zr), and / or molybdenum (Mo), as well as combinations thereof and doped forms thereof.

[0215] In some embodiments, the exposed metal-containing surface 611 may be a metalcontaining material such as titanium nitride (TiN), titanium / titanium nitride (Ti / TiN), molybdenum nitride (MoNx), tungsten nitride (WN), tungsten carbonitride (WCxNy), titanium aluminum carbide (TiAlxCy), titanium silicide (TiSiz), or tantalum nitride (TaN).

[0216] In some embodiments, the exposed dielectric surface 613 in the substrate 610 may be silicon oxides, silicon nitrides, silicon carbides, silicon oxycarbides (SiOxCy), silicon oxynitrides, aluminum oxides, and the low-k dielectric material such as silicon oxycarbonitride (SiOxCyNz), and the like.

[0217] As depicted by operation 610, a phosphorus-containing metal precursor may be introduced to the process chamber, exposing substrate 610 to the phosphorus-containing metalDocket No. LAM1P069WOprecursor. When performed, phosphorus- and metal-containing layer 630 is deposited on the exposed metal-containing surface 611, and a layer of adsorbate 640 is formed on the exposed dielectric surface 614.

[0218] In various implementations, the phosphorus-containing metal precursors are vaporous precursors where the metal in the metal precursor corresponds to the metal in the deposited metal-containing layer are the same.

[0219] The phosphorus-containing metal precursor is a metal-containing compound having one or more ligands, where at least one of its ligands is a phosphorus-containing ligand. The phosphorus-containing ligand may be or may include phosphorus, an optionally substituted phosphine, or an optionally substituted halophosphine. In some embodiments, a phosphorus-containing metal precursor has one or more P(III) species or ligands. In some embodiments, the phosphine may be a tertiary phosphine.

[0220] In various implementations, the phosphorus-containing ligand is a halophosphine. In some embodiments, halophosphine may be a phosphine having one or more halogens. In some embodiments, halogen may form a bond with phosphorus, and halophosphine may have at least one P-X bond, where X may be chlorine, bromine, fluorine, or iodine. Non-limiting examples include phosphorus trifluoride (PF3), phosphorus trichloride (PCI3), phosphorus tribromide (PBrs), phosphorus triiodide (PI3), phosphoryl fluoride (OPF3), or PFI-2(CF3)2-3. In some embodiments, one or more halogens in the halophosphine ligand may not have a halogen that directly forms a bond with phosphorus. In some embodiments, halophosphine may include phosphorus bonded to oxygen, carbon, or both. Non-limiting examples include tris(trifhioromethyl)phosphine (P(CF3)s), PFI-2(CF3)2-3, or OP(CF3)3.

[0221] In some embodiments, the phosphorus-containing ligand is an optionally substituted phosphine, optionally substituted with aliphatic such as branched or unbranched alkyl, or optionally substituted aryl. For example, optionally substituted phosphine may be tertiary phosphine, PR3, where R is a branched or unbranched alkyl chain such as methyl, ethyl, n-butyl, n-propyl, or an aryl such as phenyl.

[0222] In some embodiments, the phosphorus-containing metal precursor is any of the phosphorus-containing metal precursors described previously. In some embodiments, the phosphorus-containing metal precursor may be a homoleptic complex, which may be represented by the formula (I) described elsewhere herein.MaLb (I)In some embodiments, the phosphorus-containing metal precursor is a heteroleptic complex according to the formulae (II) or (III) described elsewhere herein.Docket No. LAM1P069WOMaLbYc (II)MaLbYcZd (III)

[0223] In some embodiments, the phosphorus- and metal-containing layer 630 may be a layer of phosphorus-containing metal, chemisorbed or physisorbed phosphorus-containing metal precursor, a layer of metal phosphine (MxPy), a phosphorus-terminated surface, or combinations thereof. In some embodiments, the phosphorus- and metal-containing layer 630 may be a monolayer.

[0224] In various embodiments, the phosphorus- and metal-containing layer 630 may be deposited by implementing various deposition techniques using one or more of the abovedescribed phosphorus-containing metal precursors. For example, thermal or plasma-enhanced atomic layer deposition (ALD) or chemical vapor deposition (CVD) may be used.

[0225] In some embodiments, the adsorbate 640 is selectively formed on the exposed dielectric surface 614. The adsorbate 640 may be or include phosphoric acid. In some embodiments, the adsorbate 640 may prevent the deposition of metal-containing material on the dielectric material 613 during subsequent deposition, thereby allowing continued deposition of the metal on conductive surfaces without depositing the metal on the dielectric.

[0226] Referring to operation 603, the phosphorus metal-containing layer 630 is converted to a metal layer 633 on the metal-containing surface 611. The metal layer 633 may be, or substantially, an elemental metal, i.e., M(0), or pure metal that is at least 90% pure, at least 95% pure, at least 99% pure, at least 99.5% pure, or at least 99.9% pure. In some cases, the metal layer 633 may be absent of other elements such as C, N, or O, in some embodiments, small amounts of other elements may be present (e.g., less than 10%, less than 5%, less than 1%, less than 0.5%, or less than 0.1%)

[0227] In various embodiments, operation 603 involves introducing a co-reactant to the process chamber containing the substrate 610 having the phosphorus- and metal-containing layer 630. In some embodiments, operation 603 may be performed using various co-reactants and operating conditions as described in operation 505. The co-reactant may be any of the above-described co-reactants. The co-reactant may be a hydrogen-containing gas such as H2 gas, a silicon-containing gas, a boron-containing gas, a phosphorus-containing gas, or a combination thereof. Non-limiting examples of the hydrogen-containing gas include SiFU gas, B2H6, and PH3 gas. The hydrogen-containing gas may be introduced with an inert gas (e.g., argon gas or nitrogen gas).

[0228] In some embodiments, converting the phosphorus- and metal-containing layer 630 to the metal layer 633 involves generating plasma from the halide gas or the hydrogen-containingDocket No. LAM1P069WOgas, and introducing the plasma formed from the halide gas or the hydrogen-containing gas to the process chamber.

[0229] In various embodiments, the plasma may be co-flown with an inert gas (e.g., Ar gas or N2 gas). For example, the plasma formed from hydrogen-containing gas, such as H2 gas, may be introduced with Ar co-flow where the Ar is between 0.5 % and 90% of the total volume.

[0230] In some embodiments, plasma is ignited using power less than 500W, 1000W, 2500W, 5000W, 6000W, 7000W, or 8000W. In some embodiments, plasma is ignited using power between 100W and 6000W, between 200W and 6000W, between 500W and 6000W, between 1000W and 6000W, between 100W and 7000W, between 100W and 8000W, between 200W and 7000W, or between 200W and 8000W.

[0231] In some embodiments, the plasma may be generated using an inductively coupled plasma generator, a capacitively coupled plasma generator, or a microwave generator using a suitable frequency (e,g, 10 Hz, 13 Hz, 15 Hz, 20 Hz, or 30 Hz).

[0232] In some embodiments, the co-reactant is co-flowed with the phosphorus-containing metal precursor. In some embodiments, the co-reactant and the phosphorus-containing metal precursor are introduced sequentially to a chamber containing the substrate. For example, a phosphorus-containing metal precursor may be introduced first, and a co-reactant is introduced subsequently. Alternatively, the co-reactant may be introduced first, followed by the phosphorus-containing metal precursor. In some embodiments, alternating doses or pulses of the phosphorus-containing metal precursors and co-reactants are provided to the process chamber in a cycle or repeated manner (e.g., A / B / A / B or B / A / B / A, where A refers to the phosphorus-containing precursor and B refers to the co-reactant).

[0233] In some embodiments, converting phosphorus- and metal-containing layer 630 to the metal layer 633, as depicted in 603, involves reducing the phosphorus- and metal-containing layer 630 by exposing the layer 630 to an oxidant. In some embodiments, forming the metal layer 633 leverages the reactivity of the phosphine ligands having phosphorus with an oxidation state of +3 and transforming it to a phosphorus species having an oxidation state of +5. In various implementations, the co-reactant may act as an oxidant (e.g., F2, CI2, or Br2), reducing the metal to form a pure or elemental metal, M(0). An exemplary redox reaction includes:M(PF3)6+ 6 F2M(s) + 6 PF5

[0234] In some embodiments, the phosphorus- and metal-containing layer 630 may be first converted to a metal halide surface (e.g., metal fluoride, metal chloride, metal bromide, or metal iodide). In various implementations, the metal halide surfaces may be more amenable to subsequent reduction to a pure or elemental metal. The metal halide surfaces may be exposedDocket No. LAM1P069WOto a reducing agent, such as H2 gas, to form the metal layer 633.

[0235] In some embodiments, converting phosphorus- and metal-containing layer 630 to the metal layer 633, as depicted in 603, involves thermal decomposition of the phosphorus- and metal-containing layer 630. In some embodiments, a substrate 610 having a layer of phosphorus- and metal-containing layer 630 may be exposed to a temperature of at least 100°C, at least 200°C, at least 300°C, at least 400°C, between 50°C and 400°C, between 50°C and 450°C, between 50°C and 500°C, between 50°C and 600°C, between 100°C and 450°C, between 100°C and 500°C, between 100°C and 600°C, between 150°C and 450°C, between 150°C and 500°C, between 150°C and 600°C, between 250°C and 450°C, between 250°C and 500°C, or between 250°C and 600°C.

[0236] In some embodiments, converting phosphorus- and metal-containing layer 630 to the metal layer 633, as depicted in 603, involves exposing the phosphorus- and metal-containing layer 630 to a plasma formed in hydrogen-containing gas (e.g., H2 gas).

[0237] In some embodiments, operation 603 selectively converts the phosphorus metalcontaining layer 630 to the metal layer 633 without modifying adsorbate 640.

[0238] In some embodiments, adsorbate 640 may be removed according to operation 605 and revealing the underlying dielectric surface 613.

[0239] In some embodiments, operation 605 involves exposing the substrate to a pulse of water or to an oxygen-containing plasma (e.g., H2O, O2, or H2O2).

[0240] In some embodiments, operations 601 and 603 may be repeated to form a metal layer 633 having a desired depth or thickness. In some implementations, 601 and 603 may be repeated, where the phosphorus-containing metal precursor may be varied to form a laminated metal layer 633. For example, the first cycle utilizes a phosphorus-containing molybdenum precursor, and the second cycle utilizes a phosphorus-containing tungsten precursor to form a Mo / W / Mo / W laminated metal layer.

[0241] In some embodiments, operations 601 and 603 may be repeated without or prior to removing the adsorbate 640 according to operation 605.

[0242] In some embodiments, operations 601, 603, and 605 may be repeated in a cyclic manner to deposit the metal layer 633 to a desired thickness.

[0243] Other non-limiting aspects include a method for inhibiting the deposition of the metalcontaining material on the exposed metal-containing layer. The method involves providing a substrate having an exposed metal-containing material, introducing phosphine-containing gas, and binding phosphine-containing gas to form a monolayer on the surface of the exposed metalcontaining material to thereby inhibit deposition on the metal-containing material.Docket No. LAM1P069WO

[0244] The substrate may be or include any of the above-described metal-containing materials (e.g., TiN, W, or Mo), a material stack, or a featured substrate having an exposed metalcontaining material and an exposed dielectric surface.

[0245] In some embodiments, phosphine-containing gas may be or include an optionally substituted phosphine or an optionally substituted halophosphine. In some embodiments, phosphine-containing gas has one or more P(III) species or ligands. In some embodiments, phosphine-containing gas may include a tertiary phosphine. In some embodiments, phosphine-containing gas may be absent of carbon, nitrogen, or oxygen. In some cases, the phosphine-containing gas may include some amount of carbon, oxygen, and / or nitrogen.

[0246] In some embodiments, the phosphine-containing gas is or includes a halophosphine. In some embodiments, halophosphine may be a phosphine having one or more halogens. In some embodiments, halogen may form a bond with phosphorus, and halophosphine may have at least one P-X bond, where X may be chlorine, bromine, fluorine, or iodine. Non-limiting examples include phosphorus trifluoride (PF3), phosphorus trichloride (PCI3), phosphorus tribromide (PBrs), phosphorus triiodide (PI3), phosphoryl fluoride (OPF3), or PFI-2(CF3)2-3. In some embodiments, one or more halogens in the halophosphine may not have a halogen that directly forms a bond with phosphorus. In some embodiments, halophosphine may include phosphorus bonded to oxygen, carbon, or both. Non-limiting examples include tris(trifhioromethyl)phosphine (P(CF3)s), PFI-2(CF3)2-3, or OP(CF3)3.

[0247] In some embodiments, the phosphine-containing gas is an optionally substituted phosphine, optionally substituted with aliphatic such as branched or unbranched alkyl, or optionally substituted aryl. For example, optionally substituted phosphine may be tertiary phosphine, PR3, where R is a branched or unbranched alkyl chain such as methyl, ethyl, n-butyl, n-propyl, or an aryl such as phenyl.

[0248] In some embodiments, the phosphine-containing gas may be delivered in a process gas. The process gas may be an inert gas such as argon gas, nitrogen gas, helium gas, xenon gas, krypton gas, or any other suitable gas. In some embodiments, phosphine-containing gas is coflowed with the inert gas. For example, phosphorus trifluoride gas may be delivered with argon gas. In some embodiments, the argon gas may be less than 99%, less than 97%, less than 95%, less than 90%, or less than 75% of the total volume of the argon gas and phosphine-containing gas. In some embodiments, the argon gas is between 0.1% and 95%, between 0.5% and 95%, between 1% and 95%, between 5% and 95%, between 10% and 95%, between 25% and 95%, between 50% and 95%, 0.1% and 99%, between 0.5% and 99%, between 1% and 99%, between 5% and 99%, between 10% and 99%, between 25% and 99%, between 50% and 99%, 0.1%Docket No. LAM1P069WOand 90%, between 0.5% and 90%, between 1% and 90%, between 5% and 90%, between 10% and 90%, between 25% and 90%, or between 50% and 90% of the total volume of the argon gas and phosphine-containing gas.

[0249] When introduced, phosphine-containing gas may undergo a thermal reaction with the metal-containing surface.

[0250] In various implementations, phosphine-containing gas may bind to the substrate to form a monolayer or a sub-monolayer on the surface of the exposed metal-containing material. In some embodiments, the monolayer may be a phosphine-containing material itself, a phosphorus-terminated surface, or a combination of both. Once formed, the monolayer may inhibit additional film growth during the subsequent process.

[0251] In some embodiments, the monolayer or sub-monolayer may be converted to a layer of phosphate by exposure to a pulse of water, an oxygen-containing gas, an oxygen-containing plasma, or hydrogen-containing plasma (e.g., a plasma generated from H2O, O2, H2 / O2, or H2O2). The plasma may be a capacitively coupled plasma (CCP), inductively coupled plasma (ICP), microwave plasma, or any other suitable plasma.

[0252] Yet another non-limiting aspect includes using phosphine-containing gas to selectively etch the metal-containing material. The method may involve the following operations, (a) providing a substrate to the process chamber, (b) introducing a phosphine-containing gas to the process chamber, and (c) elevating the temperature to selectively etch a material.

[0253] The substrate may include a first exposed material and a second exposed material thereon. The first exposed material may be a metal-containing material such as the earlier described metal-containing material. In some embodiments, the second exposed material may be another metal-containing material, which may be different from the first exposed material. In some embodiments, the second exposed material may be a dielectric material such as those described earlier. In some embodiments, the substrate may be a multi-material surface.

[0254] After the substrate is provided, a phosphine-containing gas may be introduced to the process chamber. The phosphine-containing gas may be or include an optionally substituted phosphine or an optionally substituted halophosphine. In some embodiments, the phosphine-containing gas is a phosphorus trifluoride.

[0255] The method further includes raising the temperature and selectively etching the first exposed material. In some embodiments, the temperature may be raised above 100°C, above 150°, above 175°C, above 200°C, above 225°C, above 250°C, above 275°C, above 300°C, above 400°C, or above 500°C. At such temperatures, phosphine-containing gas selectively etches metal-containing material. In some embodiments, the temperature may be raised but noDocket No. LAM1P069WOmore than 800°C, no more than 700°C, no more than 650°C, no more than 600°C, no more than 550°C, no more than 500°C, no more than 400°C, or no more than 300°C.

[0256] Yet other non-limiting aspect involves using phosphine-containing gas to selectively etch the silicon-containing material. The method may involve the following operations, (a) providing a substrate to the process chamber, (b) introducing a phosphine-containing gas to the process chamber, and (c) igniting a plasma to generate fluorine radicals from the phosphine-containing gas and selectively etching the silicon-containing material.

[0257] The substrate may include a first material and a second material thereon. The first material may be a silicon-containing material such as those described above. In some embodiments, the silicon-containing material may be silicon oxide (SiCL), silicon oxycarbonitride (SiOxCyNz), silicon oxycarbide (SiOxCy), and the like. In some embodiments, silicon-containing material is a low-k dielectric material.

[0258] In some embodiments, the second material may be metal-containing material, such as those described above. In some embodiments, the second material is a dielectric material, which may be different from the first material. In some embodiments, the substrate may be a multi-material surface.

[0259] After the substrate is provided, a phosphine-containing gas may be introduced to the process chamber. The phosphine-containing gas may be or include an optionally substituted phosphine or an optionally substituted halophosphine. In some embodiments, phosphine-containing gas may be an optionally substituted fluorophosphine. In some embodiments, the phosphine-containing gas is a phosphorus trifluoride.

[0260] In various embodiments, the plasma is ignited to generate fluorine radicals from the phosphine-containing gas. Plasma may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), or microwave plasma.

[0261] The methods described herein include atomic layer deposition (ALD) processes. The processes include both temporal ALD, in which a substrate is exposed to different reactants while remaining stationary, and spatial ALD, in which a substrate is moved between different operations, as well as processes that incorporate both timing and positional control of different operations.Apparatus

[0262] Figure 7 depicts a schematic illustration of an embodiment of an ALD process station 1600 having a process chamber 1602 for maintaining a low-pressure environment. In some embodiments, a plurality of ALD process stations may be included in a common low-pressure process tool environment. For example, Figures 8A and 8B depict embodiments of aDocket No. LAM1P069WOmulti-station processing tool 1700. In some embodiments, one or more hardware parameters of ALD process station 1600, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers 1750. In some other embodiments, a process chamber may be a single- station chamber.

[0263] ALD process station 1600 fluidly communicates with reactant delivery system 1601a for delivering process gases to a distribution showerhead 1606. Reactant delivery system 1601a includes a mixing vessel 1604 for blending and / or conditioning process gases, such as a Mo precursor-containing gas, a hydrogen-containing gas, an argon or other carrier gas, or other reactant-containing gas, for delivery to showerhead 1606. One or more mixing vessel inlet valves 1620 may control introduction of process gases to mixing vessel 1604. In various embodiments, deposition of an initial Mo layer is performed in process station 1600 and in some embodiments, other operations such as in-situ clean or Mo gap fill may be performed in the same or another station of the multi-station processing tool 1700 as further described below with respect to Figure 8A.

[0264] As an example, the embodiment of Figure 7 includes a vaporization point 1603 for vaporizing liquid reactant to be supplied to the mixing vessel 1604. In some embodiments, vaporization point 1603 may be a heated vaporizer. In some embodiments, a liquid precursor or liquid reactant may be vaporized at a liquid injector (not shown). For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel 1604. In one embodiment, a liquid injector may vaporize the reactant by flashing the liquid from a higher pressure to a lower pressure. In another example, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 1603. In one scenario, a liquid injector may be mounted directly to mixing vessel 1604. In another scenario, a liquid injector may be mounted directly to showerhead 1606.

[0265] Reactant delivery system 1601a may also include one or more solid precursor delivery components including one or more on-board ampoules 1613 and / or bulk delivery components 1615. Figure 9 below provides an example of a bulk delivery system.

[0266] In some embodiments, a liquid flow controller (LFC) upstream of vaporization point 1603 may be provided for controlling a mass flow of liquid for vaporization and delivery to process chamber 1602. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjustedDocket No. LAM1P069WOresponsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend a time for dosing a liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by disabling a sense tube of the LFC and the PID controller.

[0267] Showerhead 1606 distributes process gases toward substrate 1612. In the embodiment shown in Figure 7, the substrate 1612 is located beneath showerhead 1606 and is shown resting on a pedestal 1608. Showerhead 1606 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to substrate 1612.

[0268] In some embodiments, pedestal 1608 may be raised or lowered to expose substrate 1612 to a volume between the substrate 1612 and the showerhead 1606. In some embodiments, pedestal 1608 may be temperature controlled via heater 1610. Pedestal 1608 may be set to any suitable temperature, such as between about 250°C and about 800°C during operations for performing various disclosed embodiments. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller 850. At the conclusion of a process phase, pedestal 1608 may be lowered during another substrate transfer phase to allow removal of substrate 1612 from pedestal 1608.

[0269] In some embodiments, a position of showerhead 1606 may be adjusted relative to pedestal 1608 to vary a volume between the substrate 1612 and the showerhead 1606. Further, it will be appreciated that a vertical position of pedestal 1608 and / or showerhead 1606 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, pedestal 1608 may include a rotational axis for rotating an orientation of substrate 1612. It will be appreciated that, in some embodiments, one or more of these example adjustments may be performed programmatically by one or more suitable computer controllers 1650. The computer controller 1650 may include any of the features described below with respect to controller 1650 of Figure 7.

[0270] In some embodiments where plasma may be used as discussed above, showerhead 1606 and pedestal 1608 electrically communicate with a radio frequency (RF) power supply 1614 and matching network 1616 for powering a plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 1614 and matching network 1616 may be operated at any suitable power to form a plasma having a desired composition of radical species. Likewise, RF power supplyDocket No. LAM1P069WO1614 may provide RF power of any suitable frequency. In some embodiments, RF power supply 1614 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 900 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 80 MHz, or greater than 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.

[0271] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0272] In some embodiments, instructions for a controller 1650 may be provided via input / output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and / or a reactant gas (e.g., a Mo precursor), instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the second recipe phase. A third recipe phase may include instructions for modulating a flow rate of a second reactant gas such as H2, instructions for modulating the flow rate of a carrier or purge gas, instructions for igniting a plasma, and time delay instructions for the third recipe phase. A fourth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and / or a reactant gas, andDocket No. LAM1P069WOinstructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fourth recipe phase. It will be appreciated that these recipe phases may be further subdivided and / or iterated in any suitable way within the scope of the present disclosure.

[0273] Further, in some embodiments, pressure control for process station 1600 may be provided by butterfly valve 1618. As shown in the embodiment of Figure 7, butterfly valve 1618 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of process station 1600 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 1600.

[0274] Figure 8A and Figure 8B show examples of processing systems. Figure 8A shows an example of a processing system including multiple chambers. The system 1700 includes a transfer module 1703. The transfer module 1703 provides a clean, vacuum environment to minimize risk of contamination of substrates being processed as they are moved between various modules. Mounted on the transfer module 1703 is a multi-station chamber 1709 capable of performing in-situ clean and / or ALD processes described above. Surface treatment and / or initial Mo layer deposition may be performed in the same or different station or chamber as the subsequent Mo gap fill.

[0275] Chamber 1709 may include multiple stations 1711, 1713, 1715, and 1717 that may sequentially perform operations in accordance with disclosed embodiments. For example, chamber 1709 may be configured such that station 1711 performs an in-situ treatment using a MoClx precursor. Station 1713 may be configured to selectively treat the field region and upper sidewalls and stations 1715 and 1717 may be configured to perform ALD of bulk Mo using an molybdenum oxyhalide precursor and H2. In another example, chamber 1709 may be configured such that station 1711 performs in-situ clean, station 1713 performs ALD of an initial Mo layer, station 1713 selectively treats the layer, and 1714 deposition of bulk Mo. In another example, the chamber 1709 may be configured to do parallel processing of substrates, with each station performing multiple processes sequentially.

[0276] Two or more stations may be included in a multi-station chamber, e.g., 2-6, with the operations appropriately distributed. For example, a two-station chamber may be configured to perform ALD of an initial Mo layer in a first station followed by ALD of bulk Mo in a second station. Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate.

[0277] Also mounted on the transfer module 1703 may be one or more single or multi-station modules 1707. In some embodiments, a preclean as described above may be performed in a module 1707, after which the substrate is transferred under vacuum to another module (e.g.,Docket No. LAM1P069WOanother module 1707 or chamber 1709) for ALD. In another example, a module for selective treatment of a film may be mounted on the transfer module. An example is shown in Figure 10.

[0278] The system 1700 also includes one or more wafer source modules 1701, where wafers are stored before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 1719 may first remove wafers from the source modules 1701 to loadlocks 1721. A wafer transfer device (generally a robot arm unit) in the transfer module 1703 moves the wafers from loadlocks 1721 to and among the modules mounted on the transfer module 1703.

[0279] Referring to Figures 6A and 6B, for example, in some embodiments, chamber 1709 is configured to perform pre-treatment, selective fill, conformal liner deposition, and final fill. In one example, station 1711 is configured to perform pre-treatment, station 1713 is configured to perform selective fill, station 1713 is configured to perform conformal liner deposition, and station 1715 is configured to perform final fill. In some embodiments, etch and / or inhibition processes may be performed. For example, station 1711 is configured to perform pretreatment, station 1713 is configured to perform selective fill, station 1713 is configured to perform inhibition, and station 1715 is configured to perform final fill. Similarly, chamber 1709 may be configured to perform all processes described in Figures 6C-6F and Figure 15B.

[0280] Chamber 1709 may have one or more of the following features to enable singlechamber metallization processes:Individually addressable plasma power generators associated with each station;Individually addressable reactant inputs associated with each station;Multi-plenum showerheads on each station;Dual solid precursor delivery systems.

[0281] Solid precursor delivery systems may include bulk delivery systems and / or on-board ampoules. Figure 9 below provides an examples of a solid precursor delivery system that may be employed.

[0282] Figure 8B is an embodiment of a system 1700. The system 1700 in Figure 8B has wafer source modules 1701, a transfer module 1703, atmospheric transfer chamber 1719, and loadlocks 1721, as described above with reference to Figure 8A. The system in Figure 8B has three single station modules 1757a-1775c. The system 1700 may be configured to sequentially perform operations in accordance with disclosed embodiments. For example, the single station modules 1757a-1757c may be configured so that a first module 1757a performs a surface treatment, a second module 957b performs ALD of an initial Mo layer using a molybdenumDocket No. LAM1P069WOhalide precursor, and a third module 957c performs ALD of bulk Mo using a molybdenum oxyhalide precursor. In this example, an in-situ clean may be optionally performed in second module 1757b instead of or in addition to a preclean in first module 1757a. In another example, the single station modules 1757a-1757c may be configured so that a first module 1757a performs a deposition of an initial metal layer, a second module 1757b performs selective treatment, and a third module 1757c performs ALD of bulk Mo using a molybdenum oxyhalide precursor. In yet another example, one module may be configured for deposition, another module for selective treatment, and another module for etch.

[0283] Stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate as described above with reference to Figure 7.

[0284] Returning to Figure 8 A and 8B, in various embodiments, a system controller 1729 is employed to control process conditions during deposition. The controller 1729 will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc. Such a system controller may be employed in control of any of the processes and apparatus described herein.

[0285] The controller 1729 may control all the activities of the apparatus. The system controller 1729 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the controller 1729 may be employed in some embodiments.

[0286] Typically, there will be a user interface associated with the controller 1729. The user interface may include a display screen, graphical software displays of the apparatus and / or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.

[0287] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and / or software. The instructions for controlling the drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application- specific integrated circuits, and other devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general-purpose processor. System control software may be coded in any suitable computer readableDocket No. LAM1P069WOprogramming language.

[0288] The computer program code for controlling the Mo precursor pulses, hydrogen pulses, and argon flow, and other processes in a process sequence can be written in any conventional computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded.

[0289] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and may be entered utilizing the user interface.

[0290] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 1729. The signals for controlling the process are output on the analog and digital output connections of the deposition apparatus.

[0291] The system software may be designed or configured in many ways. For example, various chamber component subroutines or control objects may be written to control operation of the chamber components necessary to carry out the deposition processes in accordance with the disclosed embodiments. Examples of programs or sections of programs for this purpose include substrate positioning code, process gas control code, pressure control code, and heater control code.

[0292] In some implementations, a controller 1729 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller 1729, depending on the processing requirements and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0293] Broadly speaking, the controller may be defined as electronics having variousDocket No. LAM1P069WOintegrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0294] The controller 1729, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller 1729 may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. The parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, the controller may be distributed, such as by including one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0295] Without limitation, example systems may include a plasma etch chamber or module, aDocket No. LAM1P069WOdeposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a PVD chamber or module, a CVD chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and / or manufacturing of semiconductor wafers.

[0296] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0297] The controller 1729 may include various programs. A substrate positioning program may include program code for controlling chamber components that are used to load the substrate onto a pedestal or chuck and to control the spacing between the substrate and other parts of the chamber such as a gas inlet. A substrate tilt and rotation program may include for tilt and rotation. A process gas control program may include code for controlling gas composition, flow rates, pulse times, and optionally for flowing gas into the chamber prior to deposition in order to stabilize the pressure in the chamber. A pressure control program may include code for controlling the pressure in the chamber by regulating, e.g., a throttle valve in the exhaust system of the chamber. A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas such as helium to the wafer chuck.

[0298] Examples of chamber sensors that may be monitored during deposition include mass flow controllers, pressure sensors such as manometers, and thermocouples located in the pedestal or chuck. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain desired process conditions.

[0299] Figure 9 depicts an example precursor delivery system according to various implementations. The precursor delivery system 1800, which may also be referred to herein as the system 1800, includes an ampoule 1802 that is configured to have a precursor 1804 (shown with cross-hatching) and heat that precursor 1804 to vaporize it and create a precursor vapor in the headspace 1806 of the ampoule 1802. The ampoule includes an inlet 1808 and an outlet 1810. The inlet 1808 is configured to receive inert gas from an inert gas source 1812. The inert gas and precursor vapor in the headspace of the ampoule form a mixture that is flowed out ofDocket No. LAM1P069WOthe outlet 1810. In some implementations, like in Figure 9, the pressure in the ampoule 1802 may be maintained or controlled by pressure flow control which may include a controller and / or flow control valve 1814, which in some implementations may be a throttle valve. As the mixture of inert gas and precursor vapor flows out of the outlet 1810, the pressure flow control of the ampoule flows inert gas into the ampoule 1802 through the inlet 1808 to maintain the pressure in the ampoule 1802. The ampoule also includes an inlet valve 1816 configured to control flow of the inert gas into the ampoule and an outlet valve 1818 configured to control flow out of the outlet 1810, as well as bypass valve 1820 through which the inert gas can flow downstream of the ampoule 1802 without flowing through the ampoule 1802.

[0300] The ampoule 1802 is located in one location of a fabrication facility, such as a “sub-fab,” that is different than the location of the semiconductor processing tool, and the processing modules, to where the mixture is flowed. For example, the semiconductor processing tool may be located on a fabrication floor that is a different level in the facility than where the ampoule is located. The different locations of the ampoule and semiconductor processing tool / processing modules is exemplified by the vertical dashed line.

[0301] The mixture of precursor vapor and inert gas is configured to flow out of the outlet 1810 and towards a plurality of flow paths configured to flow the mixture to a plurality of processing modules and into a process volume of each processing module. These flow paths span from the location of the ampoule, e.g., in the sub-fab, to the separate location of the processing tools and / or modules, e.g., the fab floor. The system 1800 of Figure 9 includes four flow paths 1822A-D that each span from the location of the ampoule on the left side of the dashed dividing line, e.g., the sub-fab, to a corresponding processing module 1824A-D on the right side of the dashed dividing line, e.g., on the fab floor. Each flow path 1822A-D is configured to flow the mixture of precursor vapor and inert gas which includes having delivery conduits and other flow elements to contain and direct the flow of mixture to the corresponding processing module 1824A-D. Each flow path is also configured to maintain the mixture at a temperature between about 100 C and 150 C which may include having heating elements that heat the delivery conduits of the flow path and / or thermal insulation around the delivery conduits. Each flow path also has a high-temperature mass flow controller located at or near the corresponding processing module 1824A-D that is configured to control the flow of the mixture along the flow path. Although four flow paths and four processing modules are shown, the number of flow paths and processing modules may vary such that there are 2, 3, 4, 5, 6, 7, 8, or 10 processing modules and corresponding flow paths.

[0302] In some implementations, the apparatus for processing substrate includes the followingDocket No. LAM1P069WOelements. The apparatus may include a process chamber, a pedestal, one or more gas inlets for flowing gases into the process chamber, and a controller with machine-readable instructions for: (a) providing the substrate, (b) introducing a phosphorus-containing precursor to form a layer of phosphorus- and metal-containing material, and (c) converting the layer of phosphorus-and metal-containing metal to a metal. In some embodiments, such an apparatus may be used to perform a temporal ALD where a substrate is exposed to different reactants while remaining stationary.

[0303] In some implementations, the apparatus for processing substrate includes the following features. The apparatus may include a process chamber, a pedestal, one or more gas inlets for flowing gases into the processing chamber, and a controller comprising machine-readable instructions for: (a) providing the substrate to a first station in the process chamber; (b) in the first station, introducing a phosphorus-containing precursor to form a phosphorus- and metalcontaining layer; (c) transferring the substrate to a second station in the process chamber; and (d) in the second station, converting the phosphorus- and metal-containing layer to a metal layer. In some embodiments, such an apparatus may be used to perform a spatial ALD where a substrate is moved between different operations. In some embodiments, an apparatus may be configured to perform ALD processes that incorporates both timing and positional control of different operations.

[0304] The foregoing describes implementations of disclosed embodiments in a single or multi-chamber semiconductor processing tool. The apparatus and process described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such tools / processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following steps, each step provided with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

Claims

Docket No. LAM1P069WOCLAIMSWhat is claimed is:

1. A method comprising :(a) exposing a substrate to a phosphorus-containing metal precursor to form a phosphorus- and metal-containing layer on the substrate; and(b) converting the phosphorus- and metal-containing layer to a metal layer.

2. The method of claim 1, wherein the phosphorus-containing metal precursor is a homoleptic complex having one or more phosphorus-containing ligands.

3. The method of claim 1, wherein the phosphorus-containing metal precursor is a heteroleptic complex having two or more different ligands, wherein at least one ligand is a phosphorus-containing ligand.

4. The method of claim 1, wherein the phosphorus-containing metal precursor is characterized by a formula:MaLb,wherein:M is a metal selected from the group consisting of Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, and Au;L is a phosphorus-containing ligand;a > 1 ; and b > 1.

5. The method of claim 4, wherein the phosphorus-containing ligand is one of PF3, P(CF3)3, PFI.2(CF3)2-3, OPF3, and OP(CF3)3.

6. The method of claim 1, wherein the phosphorus-containing metal precursor is characterized by a formula:MaLbYc,wherein:M is a metal selected group consisting of Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, and Au; L is a phosphorus-containing ligand;Y is an organic ligand different from L;Docket No. LAM1P069WOa > 1 ; b > 1 ; and c > 1.

7. The method of claim 6, wherein the phosphorus-containing ligand is one of: PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3.

8. The method of claim 6, wherein the organic ligand comprises optionally substituted carbonyl, optionally substituted isocyanide, optionally substituted nitriles, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted silyl, halo, optionally substituted aliphatic, 1,4-diazadiene (DAD), and a second phosphorus-containing ligand different from L.

9. The method of claim 6, wherein the organic ligand is selected from the group consisting of CO, -CNRa, -NCRa, tetrahydrofuran, pyridine, cyclopentadienyl, benzene, 1,4-diazadiene (DAD), -PRb3, halo, and CH2=CHSiMe3,wherein Racomprises methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl, cyclohexyl, phenyl, benzyl, xylyl, mesityl; andRbcomprises methyl, ethyl, n-propyl, n-butyl, phenyl.

10. The method of claim 1, wherein the phosphorus-containing metal precursor is characterized by a formula:MaLbYcZd,wherein:M is a metal selected group consisting of Cu, Co, Ni, Pt, Cr, Mo, W, Fe, Ru, and Au; L is a phosphorus-containing ligand;Y is an organic ligand different from L;Z is a halo;a > 1; b > 1; c > 1, and d > 1.

11. The method of claim 10, wherein the phosphorus-containing ligand is one of PF3, P(CF3)3, PFI-2(CF3)2-3, OPF3, and OP(CF3)3.

12. The method of claim 10, wherein the organic ligand comprises optionally substituted carbonyl, optionally substituted isocyanide, optionally substituted nitriles, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted silyl,Docket No. LAM1P069WOhalo, optionally substituted aliphatic, 1,4-diazadiene (DAD), and a second phosphorus-containing ligand different from L.

13. The method of claim 10, wherein the organic ligand is selected from a group consisting of CO, -CNRa, -NCRa, tetrahydrofuran, pyridine, cyclopentadienyl, benzene, 1,4-diazadiene (DAD), -PRb3, halo, and CH2=CHSiMe3,wherein Racomprises methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, sec-butyl, cyclohexyl, phenyl, benzyl, xylyl, mesityl; andRbcomprises methyl, ethyl, n-propyl, n-butyl, phenyl.

14. The method of claim 1, wherein (b) comprises introducing a co-reactant to a chamber containing the substrate.

15. The method of claim 14, wherein introducing the co-reactant comprises introducing a halide gas to the chamber.

16. The method of claim 15, further comprising generating a plasma from the halide gas.

17. The method of claim 15, wherein the halide gas is one of fluorine-containing gas, chlorine-containing gas, bromine-containing gas, and iodine-containing gas.

18. The method of claim 14, wherein introducing the co-reactant comprises introducing plasma formed from a halide gas to the chamber.

19. The method of claim 14, wherein the co-reactant reacts with the phosphorus-and metal-containing layer to form a metal halide.

20. The method of claim 19, wherein (b) further comprises exposing the metal halide to a reducing agent to form the metal layer.

21. The method of claim 14, wherein the co-reactant is a hydrogen-containing gas.Docket No. LAM1P069WO22. The method of claim 21, wherein the hydrogen-containing gas is one of H2 gas, a silicon-containing gas, a boron-containing gas, and a phosphorus-containing gas.

23. The method of claim 22, wherein the hydrogen-containing gas is one of S1H4 gas, B2H6 gas, and PH3 gas.

24. The method of claim 14, wherein the co-reactant is co-flowed with the phosphorus-containing metal precursor.

25. The method of claim 14, wherein the co-reactant and the phosphorus-containing metal precursor are introduced sequentially to a chamber containing the substrate.

26. The method of claim 1, wherein (b) comprises reducing the phosphorus- and metal-containing layer to form the metal layer.

27. The method of claim 1, wherein (b) comprises forming a phosphorus-containing compound wherein the phosphorus in the phosphorus-containing compound has an oxidation state +5.

28. The method of claim 1, wherein (b) comprises a thermal decomposition of the phosphorus- and metal-containing layer.

29. The method of claim 28, wherein temperature of the substrate in (b) is between 100°C and 450°C.

30. The method of claim 1, wherein the phosphorus- and metal-containing layer is a metal phosphide (MxPy).

31. The method of claim 1, wherein the substrate comprises an exposed metal surface.

32. The method of claim 31, wherein the substrate further comprises an exposed dielectric surface.Docket No. LAM1P069WO33. The method of claim 31, wherein the phosphorus- and metal-containing layer is selectively deposited on the exposed metal surface.

34. A method comprising:(a) providing a substrate comprising an exposed metal-containing surface and an exposed dielectric surface;(b) exposing the substrate to a first phosphorus-containing metal precursor;(c) selectively depositing a first phosphorus- and metal-containing layer on the exposed metal surface and forming an adsorbate on the exposed dielectric surface; and(d) converting the first phosphorus- and metal-containing layer to a first metal layer.

35. A method comprising:(a) providing a substrate having an exposed metal-containing material;(b) introducing phosphine-containing gas; and(c) binding phosphine-containing gas to form a monolayer on a surface of the exposed metal-containing material to thereby inhibit deposition on the metal-containing material.

36. A method comprising:providing a substrate comprising a first exposed material and a second exposed material;introducing phosphine-containing gas; andelevating the temperature and selectively etching the first exposed material, wherein the first exposed material is a metal-containing material.

37. A method of processing a substrate, the method comprising:providing a substrate comprising a first material and a second material; introducing a phosphine-containing gas;igniting a plasma to generate fluorine radicals from the phosphine-containing gas; and selectively etching the first material, wherein the first material is a silicon-containing material.Docket No. LAM1P069WO38. An apparatus for processing a substrate, the apparatus comprises:a process chamber;a pedestal;one or more gas inlets for flowing gases into the processing chamber; anda controller comprising machine-readable instructions for:providing the substrate;introducing a phosphorus-containing precursor to form a phosphorus- and metal-containing layer; andconverting the phosphorus- and metal-containing layer to a metal layer.

39. An apparatus for processing a substrate, the apparatus comprises:a process chamber having one or more stations;a pedestal;one or more gas inlets for flowing gases into the processing chamber; anda controller comprising machine-readable instructions for:providing the substrate to a first station in the process chamber;in the first station, introducing a phosphorus-containing precursor to form a phosphorus- and metal-containing layer;transferring the substrate to a second station in the process chamber; and in the second station, converting the phosphorus- and metal-containing layer to a metal layer.

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