Highly selective doped hardmask films

Abstract

The present disclosure relates to highly selective doped hardmask films and methods of providing and using such films. In certain examples, the highly selective doped hardmask films can be employed as a hardmask, an intermediate layer, or an overlayer.

Description

[Technical field]

[0001] <CROSS REFERENCE TO RELATED APPLICATIONS> A PCT application has been filed contemporaneously herewith as a part of this application. Each application identified in the contemporaneously filed PCT application to which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes.

[0002] The present disclosure relates to highly selective doped hardmask films and methods of providing and using such films. In certain examples, the highly selective doped hardmask films can be employed as a hardmask, an intermediate layer, or a capping layer. [Background technology]

[0003] The background description provided herein is intended to provide a general overview of the present technology. Work by the currently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be considered prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present technology.

[0004] Certain technology nodes require advanced semiconductor processing to implement desired features. In particular, films can be used as hard masks for etching high aspect ratio features during substrate processing. For three-dimensional (3D) memory applications, hard mask films must have high etch selectivity. Summary of the Invention

[0005] The present disclosure relates to molybdenum (Mo)-containing layers (e.g., Mo-doped layers, etc.) and methods of providing and using such layers. In certain non-limiting embodiments, the Mo-containing layers are provided by a plasma enhanced chemical vapor deposition (PECVD) process. In use, such Mo-containing layers can function as at least one of a hard mask, an intermediate layer (e.g., an etch stop layer), or a capping layer (e.g., a conformal layer or a step coverage layer) in a stack. In certain embodiments, the Mo-containing layers can improve etch selectivity in the stack, which can further extend the scaling of the technology.

[0006] In a first aspect, the present disclosure encompasses a method of providing a metal-containing layer (e.g., a Mo-containing layer). In some embodiments, the method includes providing a substrate on a substrate holder in a process chamber, exposing a top surface portion of the substrate to a metal-containing precursor (e.g., a Mo-containing precursor) and one or more optional deposition precursors, and depositing the metal-containing layer (e.g., a Mo-containing layer) on the top surface portion of the substrate in the process chamber with or without a plasma. In some embodiments, the depositing includes the use of a plasma. As used herein, the terms "Mo-containing layer", "molybdenum-containing layer", and "metal-containing layer" may be used interchangeably.

[0007] In some embodiments, the processing chamber comprises a plasma enhanced chemical vapor deposition (PECVD) chamber, a chemical vapor deposition (CVD) chamber, a plasma enhanced atomic layer deposition (PEALD) chamber, or an atomic layer deposition (ALD) chamber.

[0008] In certain embodiments, the exposing step comprises sequentially or simultaneously delivering a Mo-containing precursor and one or more deposition precursors, while in other embodiments, the exposing step further comprises delivering a reactive gas, a reducing agent, or a carrier gas to the process chamber.

[0009] In further embodiments, the method includes providing an interfacial layer on a top surface portion of the substrate (e.g., prior to said depositing). In some embodiments, said providing places an interfacial layer between the substrate and the Mo-containing layer after said depositing. In other embodiments, the interfacial layer includes an adhesion layer, an initiation layer, or a growth layer. In still other embodiments, the interfacial layer includes boron (B), carbon (C), titanium (Ti), tungsten (W), tantalum (Ta), nickel (Ni), molybdenum (Mo), nitrides thereof, silicides thereof, oxynitrides thereof, carbides thereof, or carbonitrides thereof.

[0010] In some embodiments, the method further comprises pre-treating a top surface portion of the substrate (e.g., prior to said depositing), which in certain embodiments provides a pre-treated surface disposed between the substrate and the Mo-containing layer after said depositing.

[0011] In other embodiments, the substrate further includes a material layer disposed on a top surface portion of the substrate, and the depositing includes depositing a Mo-containing layer on the top surface portion of the material layer, hi some embodiments, the material layer includes at least one of an oxide or a nitride (e.g., any of those described herein).

[0012] In some embodiments, the depositing comprises applying at least one of a low frequency (LF) radio frequency component or a high frequency (HF) radio frequency component.

[0013] In a second aspect, the present disclosure encompasses a method of providing a Mo-containing layer. In some embodiments, the method includes providing a substrate in a processing chamber and depositing a Mo-containing layer on a surface portion of the substrate by a plasma enhanced chemical vapor deposition (PECVD) process.

[0014] In a third aspect, the present disclosure encompasses a method of processing a substrate. In some embodiments, the method includes depositing a Mo-containing layer on a top surface portion of the substrate, forming a pattern defined in the Mo-containing layer, and transferring the pattern defined in a material layer disposed below the Mo-containing layer.

[0015] In some embodiments, the depositing comprises exposing a top surface portion of the substrate to a Mo-containing precursor and one or more optional deposition precursors to form a Mo-containing layer. In other embodiments, the exposing comprises sequentially delivering the Mo-containing precursor and one or more deposition precursors. Optionally, the method may comprise purging at least one of after delivery of the Mo-containing precursor or after delivery of the one or more deposition precursors. In yet other embodiments, the exposing comprises simultaneously delivering the Mo-containing precursor and one or more deposition precursors. In some embodiments, the depositing comprises chemical vapor deposition, atomic layer deposition, or plasma-assisted forms thereof.

[0016] In some embodiments, the exposing further comprises delivering a reactive gas, a reducing agent, or an inert gas.

[0017] In some embodiments, forming the defined pattern includes depositing a resist layer on a top surface portion of the Mo-containing layer to form a resist mask having a pattern, and transferring the pattern of the resist mask to the top surface portion of the Mo-containing layer. In certain embodiments, the transferring forms a hard mask having one or more openings to provide the defined pattern. In other embodiments, transferring the defined pattern includes etching the material layer through the one or more openings in the hard mask. In yet other embodiments, transferring the defined pattern includes etching the material layer through the defined pattern in the Mo-containing layer.

[0018] In a further embodiment, the method includes disposing an interfacial layer between the substrate and the Mo-containing layer by providing an interfacial layer on a top surface portion of the substrate (e.g., prior to depositing the Mo-containing layer).

[0019] In any embodiment herein, the interfacial layer is present on the top surface portion of the substrate. In certain embodiments, the deposition of the Mo-containing layer provides a stack in which the interfacial layer is disposed between the substrate and the Mo-containing layer. In some embodiments, the interfacial layer comprises an adhesion layer, an initiation layer, or a growth layer. In other embodiments, the interfacial layer comprises boron (B), carbon (C), titanium (Ti), tungsten (W), tantalum (Ta), nickel (Ni), molybdenum (Mo), a nitride thereof, a silicide thereof, an oxynitride thereof, a carbide thereof, or a carbonitride thereof.

[0020] In some embodiments, the method further includes etching the interfacial layer through the pattern defined in the Mo-containing layer (eg, prior to transferring the pattern defined in the material layer).

[0021] In other embodiments, the method further includes pre-treating a top surface portion of the substrate (e.g., prior to depositing the Mo-containing layer) to provide a pre-treated surface disposed between the substrate and the Mo-containing layer.

[0022] In yet other embodiments, the method further includes etching the pre-treated surface through the pattern defined in the Mo-containing layer (e.g., prior to transferring the pattern defined in the material layer).

[0023] In a fourth aspect, the present disclosure encompasses a method of processing a substrate. In some embodiments, the method includes providing a substrate having a material layer disposed on a top surface portion of the substrate, depositing a Mo-containing layer on the top surface portion of the material layer, the depositing including delivering a Mo-containing precursor and one or more optional deposition precursors, forming a patterned mask over the Mo-containing layer, transferring a pattern of the patterned mask to the Mo-containing layer to form a pattern defined in the Mo-containing layer, and transferring the pattern defined to the material layer.

[0024] In a fifth aspect, the present disclosure encompasses an apparatus for processing a substrate. In some embodiments, the apparatus includes a processing chamber including a substrate holder, a process gas source coupled to the processing chamber and associated flow control hardware, and substrate processing hardware coupled to the processing chamber.

[0025] In some embodiments, the apparatus further includes a controller having a processor and a memory, the processor and memory being communicatively coupled to each other. In certain embodiments, the processor is operatively coupled to at least the flow control hardware and the substrate processing hardware. In other embodiments, the memory stores computer-executable instructions for performing operations in any of the methods described herein.

[0026] In yet another embodiment, the computer-executable instructions include instructions configured to expose a top surface portion of a substrate to a Mo-containing precursor and one or more deposition precursors in a process chamber, and deposit a Mo-containing layer on the top surface portion of the substrate.

[0027] In a further embodiment, the apparatus includes a plasma source connected to the processing chamber.

[0028] In another embodiment, the computer-executable instructions include instructions configured to expose a top surface portion of a substrate to a Mo-containing precursor and one or more deposition precursors in a processing chamber, provide a plasma to the processing chamber, and deposit a Mo-containing layer on the top surface portion of the substrate.

[0029] In any embodiment herein, the Mo-containing precursor comprises an organo-molybdenum compound, a molybdenum halide compound, a molybdenum oxyhalide compound, an inorganic molybdenum compound, or a compound comprising a structure having one of formulas (I)-(V) or a salt thereof.

[0030] In any embodiment herein, the one or more deposition precursors are selected from the group consisting of carbon-containing precursors, silicon-containing precursors, and boron-containing precursors.

[0031] In any embodiment herein, the carbon-containing precursor is a hydrocarbon, methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), propyne (C3H4), allene (C3H4), cyclopropene (C3H4), butane (C4H 10 ), Cyclohexane (CH 12 ), benzene (C6H6), or toluene (C7H8).

[0032] In any embodiment herein, the silicon-containing precursor comprises a silane compound, an organosilane compound, an alkylsilane compound, an alkoxysilane compound, a silanol compound, a siloxane compound, an aminosilane compound, a cyclic azasilane compound, a halosilane compound, or an inorganic silane compound.

[0033] In any embodiment herein, the boron-containing precursor comprises an organoborane compound, a boron halide compound, a borate compound, or an inorganic boron compound.

[0034] In any embodiment herein, the Mo-containing layer is x C y , Mox S y , Mo x B y , Mo x C y O z , Mo x S y B z , Mo x C y N z , Mo x S y C z , Mo x B y C z , Mo x N y , or Mo x O y N z , as well as combinations thereof.

[0035] In any embodiment herein, the Mo-containing layer is a hard mask, an etch stop layer, a conformal layer, or a step coverage layer.

[0036] In any embodiment herein, the Mo-containing layer has a low fluorine (F) content. Non-limiting examples of the fluorine content include about 0 to 2 atomic %, or less than about 2 atomic %.

[0037] In any embodiment herein, the Mo-containing layer has a low hydrogen (H) content. Non-limiting examples of the hydrogen content include about 0 to 5 atomic %, or less than about 5 atomic %.

[0038] In any embodiment herein, the Mo-containing layer has a high molybdenum (Mo) content. Non-limiting examples of the Mo content include about 5-65 atomic %, about 3-60 atomic %, or greater than about 3 atomic %.

[0039] In any embodiment herein, the Mo-containing layer has low stress, non-limiting examples of which can include ±100 MPa, ±500 MPa, or a range therebetween, as determined by measuring the bow of the wafer before and after deposition of the Mo-containing layer.

[0040] In any embodiment herein, the Mo-containing layer has high etch selectivity. Non-limiting high etch selectivity can be determined by evaluating the blanket etch rate, which can be collected by measuring the amount of etching after a certain period of etching. Additional embodiments are described herein.

[0041] definition As used herein, the term "about" means ±10% of any recited value. As used herein, the term modifies any recited value, range of values, or one or more of the endpoints of a range.

[0042] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. Use of these terms does not indicate or require that a particular structure must be located in a particular location within the device.

[0043] As used herein, the term "surface portion" may include the entire surface or a portion of the surface.

[0044] The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to linear, branched, or cyclic configurations of groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen attached to the parent molecular group through a carbonyl group, as defined herein. This group is exemplified by formyl, acetyl, propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0045] "Acyl halide" means -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0046] "Aldehyde" refers to a -C(O)H group or a compound containing such a group. An example of an aldehyde is RC(O)H, where R is selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0047] "Aldehydoalkyl" means an aldehyde group, as defined herein, attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the aldehyde alkyl group is -LC(O)H, where L is an alkyl group, as defined herein.

[0048] "Aliphatic" refers to a group consisting of at least one carbon atom and at least 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), and includes alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, as well as straight-chain and branched-chain configurations, and all stereoisomers and positional isomers.

[0049] "Aliphatic-aryl" refers to an aryl group that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled via an aliphatic group, as defined herein. In some embodiments, the aliphatic-aryl group is -LR, where L is an aliphatic group, as defined herein, and R is an aryl group, as defined herein.

[0050] "Aliphatic-heteroaryl" refers to a heteroaryl group that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled via an aliphatic group, as defined herein. In some embodiments, the aliphatic-heteroaryl group is -LR, where L is an aliphatic group, as defined herein, and R is a heteroaryl group, as defined herein.

[0051] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" refer to an aryl group, as defined herein, that is coupled (or bonded) or can be coupled to a parent molecular group via an alkyl group, an alkenyl group, or an alkynyl group, as defined herein, respectively. The alkyl-aryl group, the alkenyl-aryl group, or the alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl group, the alkenyl-aryl group, or the alkynyl-aryl group can be substituted with one or more substituents, as described herein for alkyl, alkenyl, alkynyl, or aryl. Exemplary unsubstituted alkyl-aryl groups are those containing 7 to 16 carbon atoms (C 7-16 alkyl-aryl), and those having an alkyl group having 1 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups are those containing 7 to 16 carbon atoms (C 7-16alkenyl-aryl), and those having an alkenyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups are those containing 7 to 16 carbon atoms (C 7-16 alkynyl-aryl), and those having an alkynyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, the alkyl-aryl group is -LR, where L is an alkyl group as defined herein and R is an aryl group as defined herein. In some embodiments, the alkenyl-aryl group is -LR, where L is an alkenyl group as defined herein and R is an aryl group as defined herein. In some embodiments, the alkynyl-aryl group is -LR, where L is an alkynyl group as defined herein and R is an aryl group as defined herein. In some embodiments, the alkynyl-aryl group is -LR, where L is an alkynyl group as defined herein and R is an aryl group as defined herein.

[0052] "Alkyl-cycloalkyl" means a cycloalkyl group, as defined herein, attached to the parent molecular group via an alkyl group, as defined herein. The alkyl-cycloalkyl group can be substituted or unsubstituted. For example, the alkyl-cycloalkyl group can be substituted with one or more substituents, as described herein for alkyl. In some embodiments, the alkyl-cycloalkyl group is -LR, where L is an alkyl group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0053] "Alkenyl" refers to an alkyl group consisting of at least 2 carbon atoms and at least 50 carbon atoms (C 2-50 ), e.g., 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10), and at least one carbon-carbon double bond, which may be derived by removing one hydrogen atom from one carbon atom of a parent alkene. Alkenyl groups may be branched, straight-chained, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C alkyl groups having one or more double bonds. 2-24 Alkyl groups include. Alkenyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents as described herein for alkyl.

[0054] "Alkyl-heteroaryl" means a heteroaryl group, as defined herein, attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the alkyl-heteroaryl group is -LR, where L is an alkyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0055] "Alkyl-heterocyclyl", "alkenyl-heterocyclyl", and "alkynyl-heterocyclyl" refer to a heterocyclyl group, as defined herein, that is coupled (or attached) to a parent molecular group, or that can be coupled, via an alkyl, alkenyl, or alkynyl group, as defined herein, respectively. The alkyl-heterocyclyl group, the alkenyl-heterocyclyl group, or the alkynyl-heterocyclyl group can be substituted or unsubstituted. For example, the alkyl-heterocyclyl group, the alkenyl-heterocyclyl group, or the alkynyl-heterocyclyl group can be substituted with one or more substituents, as described herein for alkyl, alkenyl, alkynyl, or heterocyclyl. Exemplary unsubstituted alkyl-heterocyclyl groups are those containing 2 to 16 carbon atoms (C 2-16alkyl-heterocyclyl), and those having an alkyl group having 1 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 1-6 Alkyl-C 1-18 Exemplary unsubstituted alkenyl-heterocyclyl groups are those containing 3 to 16 carbon atoms (C 3-16 alkenyl-heterocyclyl), and those having an alkenyl group having 2 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 2-6 Alkenyl-C 1-18 Exemplary unsubstituted alkynyl-heterocyclyl groups are those containing 3 to 16 carbon atoms (C 3-16 alkynyl-heterocyclyl), and those having an alkynyl group having 2 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 2-6 Alkynyl-C 1-18 In some embodiments, the alkyl-heterocyclyl group is -LR, where L is an alkyl group as defined herein and R is a heterocyclyl group as defined herein. In some embodiments, the alkenyl-heterocyclyl group is -LR, where L is an alkenyl group as defined herein and R is a heterocyclyl group as defined herein. In some embodiments, the alkynyl-heterocyclyl group is -LR, where L is an alkynyl group as defined herein and R is a heterocyclyl group as defined herein.

[0056] "Alkoxy" refers to -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples of the alkyl group include alkoxy groups.

[0057] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include those having 2 to 12 carbon atoms (C 2-12 alkoxyalkyl), and those having an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl group is -LOR, where each of L and R is independently an alkyl group, as defined herein.

[0058] "Alkyl" refers to an alkyl group consisting of at least one carbon atom and at least 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10), which may be derived by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). The alkyl group may be branched, linear, or cyclic (e.g., cycloalkyl). Exemplary alkyls include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. Additionally, the alkyl group may be substituted or unsubstituted. The alkyl group may be made monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group may be substituted with one, two, three, or, in the case of alkyl groups having two or more carbon atoms, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (2) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 alkyl), (4) amines (e.g., -C(O)NR 1 R 2 or -NHCOR 1 , where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2may form a heterocyclyl group together with the nitrogen atom to which each is attached, as defined herein), (5) aryl, (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl), (7) aryloyl (e.g., -C(O)-R, where R is aryl), (8) azido (e.g., -N), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11) C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein), (15) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO), (19) oxo (e.g., =O), (20) C 1-6 Thioalkoxy (e.g., -SR, where R is alkyl), (21) thiol (e.g., -SH), (22) -COR 1 , where R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (23) -C(O)NR aryl 1 R 2 , where R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18(24) -SO2R 1 , where R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (25)-SONR 1 R 2 , where R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), and (26) -NR 1 R 2 , where R 1 and R 2 each independently represents (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl, (e) C 2-6 Alkynyl, (f) C 4-18 Aryl, (g) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8In one embodiment, there are no two groups attached to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl groups can be primary, secondary, or tertiary alkyl groups substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl groups are selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0059] The term "alkylamino," as used herein, refers to the group -NR1R2, where R1 is an optionally substituted alkyl and R2 is H or an optionally substituted alkyl. Examples of alkylamino substituents include dimethylamino and diethylamino substituents.

[0060] "Alkylene" refers to a polyvalent (e.g., divalent) form of an alkyl, alkenyl, or alkynyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, ethenylene, ethynylene, propylene, propenylene, propynylene, butylene, butenylene, butynylene, and the like. In some embodiments, an alkylene group is selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 It is an alkylene group. The alkylene group can be branched or unbranched. Also, the alkylene group can be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substituents as described herein for alkyl.

[0061] The term "alkylsilyl" as used herein refers to the group -SiR1R2R3, where R1 is an optionally substituted alkyl and each of R2 and R3 is independently selected from H and an optionally substituted alkyl. Alkylsilyl includes mono-, bis-, and tris-alkylsilyl. Examples of alkylsilyl include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, ethylsilyl, and the like.

[0062] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is 1-6 Or C 1-12 In another embodiment, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0063] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is C 2-12 Or C 2-24 Alkyl sulfinyl alkyl groups (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In another embodiment, the alkylsulfinylalkyl group is -LS(O)-R, where each of L and R is independently an alkyl group, as defined herein.

[0064] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO- group. In some embodiments, an unsubstituted alkylsulfonyl group is 1-6 Or C 1-12In other embodiments, the alkylsulfonyl group is -SO-R, where R is an optionally substituted alkyl (e.g., C, which is optionally substituted as described herein). 1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0065] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is a C 2-12 Or C 2-24 Alkylsulfonylalkyl groups (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In another embodiment, the alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group, as defined herein.

[0066] "Alkynyl" refers to an alkyl group consisting of at least 2 carbon atoms and at least 50 carbon atoms (C 2-50 ), e.g., 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10 ) and at least one carbon-carbon triple bond, which may be derived by removing one hydrogen atom from one carbon atom of a parent alkyne. The alkynyl group may be branched, straight-chained, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include optionally substituted C alkyl groups having one or more triple bonds. 2-24Examples of alkynyl groups include alkyl groups. Alkynyl groups can be cyclic or non-cyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents as described herein for alkyl.

[0067] "Ambient temperature" means a temperature in the range of 16°C to 26°C, such as, for example, 19°C to 25°C or 20°C to 25°C.

[0068] "Amide" is -C(O)NR 1 R 2 or -NHCOR 1 where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 can form a heterocyclyl group, as defined herein, together with the nitrogen atom to which they are attached.

[0069] "Amine" is -NR 1 R 2 where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 can form a heterocyclyl group, as defined herein, together with the nitrogen atom to which they are attached.

[0070] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amine group, as defined herein. In some embodiments, an aminoalkyl group is -L-NR 1 R 2 where L is an alkyl group as defined herein and R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 may form a heterocyclyl group, as defined herein, together with the nitrogen atom to which each is attached. In other embodiments, an aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 can form a heterocyclyl group together with the nitrogen atom to which each is attached, as defined herein, R 3 and R 4 Each of is independently H or alkyl as defined herein.

[0071] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5-15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings (e.g., naphthyl, indolyl, or pyrazolopyridinyl) in which at least one ring is aromatic, i.e., at least one ring, and optionally multiple fused rings, have a contiguous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Huckel's rule (4n+2). The point of attachment to the parent structure is usually through the aromatic portion of the fused ring system.

[0072] "Aryl" refers to an alkyl group having at least 5 carbon atoms and up to 15 carbon atoms (C 5-15 ), e.g., 5 to 10 carbon atoms (C 5-10 ), and the like, refers to an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also encompasses heteroaryl, which is defined as a group that contains an aromatic group having at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl is also encompassed by the term aryl, defining a group that contains an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 (2) C 1-6 Alkyl, (3) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, where L and R are each independently 1-6 (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, where L and R are each independently 1-6 (7) C 1-6Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently 1-6 (9) aryl; (10) amine (e.g., -NR 1 R 2 , where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 may form a heterocyclyl group together with the nitrogen atom to which each is attached, as defined herein; (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 Or -L 2 -C(NR 1 R 2 )R 3 )-R 4 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 is alkyl, R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 can form a heterocyclyl group together with the nitrogen atom to which each is attached, as defined herein, R 3 and R 4 Each of is independently H or C 1-6 (12) heteroaryl, (13) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18aryl), (14) aryloyl (e.g., -C(O)-R, where R is aryl), (15) azido (e.g., -N), (16) cyano (e.g., -CN), (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 (18) aldehyde (e.g., —C(O)H), (19) aldehyde-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 (20) C 3-8 Cycloalkyl, (21)C 1-6 Alkyl-C 3-8 Cycloalkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8 (22) halo, (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 alkyl, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is independently H or C 1-6 (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (25) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein), (26) heterocyclyloyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (27) hydroxyl (-OH), (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein. 1-6 (29) nitro, (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein. 1-6 (31) N-protected amino, (32) N-protected amino-C 1-6 Alkyl, (33) oxo (e.g., =O), (34) C 1-6 Thioalkoxy (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, where L and R are each independently 1-6 (36)-(CH2) r CO2R 1 where r is an integer from 0 to 4, and R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (37)-(CH2) r CONR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (38)-(CH2) r SO2R 1 where r is an integer from 0 to 4, and R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (39)-(CH2) r SO2NR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (40)-(CH2) r NR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently represents (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl, (e) C 2-6 Alkynyl, (f) C 4-18 Aryl, (g) C 1-6 Alkyl-C 4-18 Aryl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 1-6 Alkyl-C 3-8Cycloalkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8 (41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2) n CF3, where n is an integer from 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, where n is an integer from 0 to 10), (44) aryloxy (e.g., -OR, where R is aryl), (45) cycloalkoxy (e.g., -OR, where R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -OLR, where L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 It is an aryl group.

[0073] "Arylalkoxy" means an alkyl-aryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0074] "Aryloxy" refers to -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is C 4-18 Or C 6-18 It is an aryloxy group.

[0075] "Aryloxycarbonyl" means an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is 5-19 In another embodiment, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group, as defined herein.

[0076] "Aryloyl" refers to an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is C 7-11 Aryloyl or C 5-19 In another embodiment, the aryloyl group is -C(O)-R, where R is an aryl group, as defined herein.

[0077] "Azido" refers to the group --N3.

[0078] "Azidoalkyl" means an azido group attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group, as defined herein.

[0079] "Azo" means the -N=N- group.

[0080] "Carbonyl" means the group -C(O)-, which also can be represented as >C=O.

[0081] "Carboxyl" means the -CO2H group or the anion thereof.

[0082] "Cyano" refers to the radical -CN.

[0083] "Cycloaliphatic" means an aliphatic group, as defined herein, that is cyclic.

[0084] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group, as defined herein.

[0085] "Cycloalkylalkoxy" refers to an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0086] "Cycloalkyl", unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical having 3 to 8 carbon atoms and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups including those described herein for alkyl.

[0087] "Cycloheteroaliphatic" means a heteroaliphatic group, as defined herein, that is cyclic.

[0088] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0089] "Ester" means -C(O)OR or -OC(O)R, where R is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0090] "Halo" means F, Cl, Br, or I.

[0091] "Haloaliphatic" means an aliphatic group, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0092] "Haloaliphatic-aryl" refers to an aryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled via a haloaliphatic group, as defined herein. In some embodiments, the haloaliphatic-aryl group is -LR, where L is a haloaliphatic group, as defined herein, and R is an aryl group, as defined herein.

[0093] "Haloaliphatic-heteroaryl" means a heteroaryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled via a haloaliphatic group, as defined herein. In some embodiments, the haloaliphatic-heteroaryl group is -LR, where L is a haloaliphatic group, as defined herein, and R is a heteroaryl group, as defined herein.

[0094] "Haloalkyl" means an alkyl group, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In one independent embodiment, a haloalkyl can be a -CX group, where each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, a haloalkyl group is -LX, where L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, a haloalkyl group is -LC(X)(R 1 )-R2 where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0095] "Haloheteroaliphatic" means heteroaliphatic, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0096] "Heteroaliphatic" means an aliphatic group, as defined herein, containing at least one heteroatom to 20 heteroatoms, such as 1-15 heteroatoms or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, within the group.

[0097] "Heteroaliphatic-aryl" means an aryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled via a heteroaliphatic group, as defined herein. In some embodiments, the heteroaliphatic-aryl group is -LR, where L is a heteroaliphatic group, as defined herein, and R is an aryl group, as defined herein.

[0098] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" mean an alkyl, alkenyl, or alkynyl group, as defined herein, which may be branched, straight-chained, or cyclic, containing at least one heteroatom to 20 heteroatoms, such as, for example, 1 to 15 heteroatoms or 1 to 5 heteroatoms, and the heteroatoms may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, within the group.

[0099] "Heteroalkylene" refers to a polyvalent (e.g., divalent) form of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, as described herein. A heteroalkylene group can be branched or unbranched. Also, a heteroalkylene group can be substituted or unsubstituted. For example, a heteroalkylene group can be substituted with one or more substituents, as described herein for alkyl.

[0100] "Heteroalkyl-aryl", "heteroalkenyl-aryl", and "heteroalkynyl-aryl" refer to an aryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled via a heteroalkyl group, a heteroalkenyl group, or a heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-aryl group is -LR, where L is a heteroalkyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkenyl-aryl group is -LR, where L is a heteroalkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkynyl-aryl group is -LR, where L is a heteroalkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0101] "Heteroalkyl-heteroaryl", "heteroalkenyl-heteroaryl", and "heteroalkynyl-heteroaryl" refer to a heteroaryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled via a heteroalkyl group, a heteroalkenyl group, or a heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-heteroaryl group is -LR, where L is a heteroalkyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkenyl-heteroaryl group is -LR, where L is a heteroalkenyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkynyl-heteroaryl group is -LR, where L is a heteroalkynyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0102] "Heteroaromatic" means an aromatic group as defined herein containing at least one heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms or 1 to 5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0103] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms, such as 1 to 4 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof in the ring. Such heteroaryl groups may have a single ring or multiple fused rings, which may or may not be aromatic or may contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. The heteroaryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryls include a subset of heterocyclyl groups as defined herein that are aromatic, i.e., contain 4n+2 pi-electrons in a monocyclic or polycyclic ring system.

[0104] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, heteroatoms do not include halogen atoms, such as when not permitted by valence constraints.

[0105] "Heterocyclyl" means, unless otherwise specified, a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Five-membered rings have 0 to 2 double bonds, and 6- and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles are fused to 1, 2, or 3 rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and other monocyclic heterocycles, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, nyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, urisyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0106] "Heterocyclyloxy" means a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group, as defined herein.

[0107] "Heterocyclyl" means a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group, as defined herein.

[0108] "Hydroxyl" means --OH.

[0109] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, provided that only one hydroxyl group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, a hydroxyalkyl group is -L-OH, where L is an alkyl group, as defined herein. In other embodiments, a hydroxyalkyl group is -LC(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0110] "Imide" means a =NR group, where R is selected from H, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0111] "Ketone" means a compound containing -C(O)R or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. An example of a ketone is R 1C(O)R, where R and R 1 Each of is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0112] "Nitro" refers to the radical --NO2.

[0113] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with one to three nitro groups. In some embodiments, a nitroalkyl group is -L-NO, where L is an alkyl group, as defined herein. In other embodiments, a nitroalkyl group is -LC(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0114] "Oxo" or "oxide" refers to the group =O.

[0115] "Oxy" means --O--.

[0116] "Perfluoroalkyl" means an alkyl group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer from 0 to 10.

[0117] "Perfluoroalkoxy" refers to an alkoxy group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group, as defined herein.

[0118] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein), including cationic or anionic compounds to form electrically neutral compounds or structures. Salts are well known in the art. For example, non-toxic salts are described in "Pharmaceutical salts" by Berge SM et al., J.Pharm.Sci. January 1977; 66(1):1-19, and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use", Wiley-VCH, April 2011 (2nd revised edition, edited by P.H. Stahl and C.G. Wermuth). Salts can be prepared in situ during the final isolation and purification of the compounds of the present invention, or separately by reacting the free base with a suitable organic acid (thereby producing an anionic salt) or by reacting an acidic group with a suitable metal or organic acid salt (thereby producing a cationic salt).Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobisulfate, and the like. Examples of the salts include acetate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, basic acetate, succinate, sulfate, tannate, tartrate, theophylline, thiocyanate, triethiodide, toluenesulfonate, undecanoate, and valerate. Representative cationic salts include metal salts such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts such as aluminum, bismuth, iron, and zinc; as well as non-toxic ammonium, quaternary ammonium, and amine cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, substituted and optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prenium).

[0119] "Silyl ether" means a functional group comprising a silicon atom covalently bonded to an alkoxy group, as defined herein. In some embodiments, the silyl ether is -Si-OR or Si-OR, where R is an alkyl group, as defined herein.

[0120] "Sulfinyl" means the group -S(O)-.

[0121] "Sulfo" refers to the group -S(O)2OH.

[0122] "Sulfonyl" or "sulfonate" means a -S(O)- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0123] "Thioalkoxy" means an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkoxy groups include, 1-6 In some embodiments, the thioalkoxy group is -SR, where R is an alkyl group, as defined herein.

[0124] "Thioalkoxyalkyl" means an alkyl group, as defined herein, that is substituted with a thioalkoxy group, as defined herein. Exemplary unsubstituted thioalkoxyalkyl groups include those having 2 to 12 carbon atoms (C 2-12 thioalkoxyalkyl), and those having an alkyl group having 1 to 6 carbon atoms and a thioalkoxy group having 1 to 6 carbon atoms (i.e., C 1-6 Thioalkoxy-C 1-6 In some embodiments, a thioalkoxyalkyl group is -LSR, where each of L and R is independently an alkyl group, as defined herein.

[0125] "Thiol" refers to a -SH group.

[0126] Any of the functional groups or chemical moieties described herein can be employed within the ligand (eg, for Mo-containing precursors, C-containing precursors, Si-containing precursors, or B-containing precursors).

[0127] Those skilled in the art will recognize that the above definitions are not intended to include impermissible substitution patterns (e.g., methyl substituted with five different groups). Such impermissible substitution patterns are readily recognized by those skilled in the art. Any functional group disclosed herein or defined above may be substituted or unsubstituted unless otherwise indicated.

[0128] Other features and advantages of the invention will become apparent from the following description and from the claims. [Brief description of the drawings]

[0129] [Figure 1] FIG. 1 provides a schematic diagram of a stack undergoing patterning and etching operations.

[0130] [Diagram 2] FIG. 2 is a process flow diagram illustrating operations performed in accordance with certain disclosed embodiments to provide a Mo-containing layer.

[0131] [Figure 3A] 3A shows a process flow diagram illustrating operations performed in accordance with certain disclosed embodiments. A non-limiting illustration of operations for processing a substrate is provided. [Figure 3B] 3B shows a process flow diagram illustrating operations performed in accordance with certain disclosed embodiments. Still other non-limiting operations for processing a substrate are provided.

[0132] [Figure 4] FIG. 4 is a schematic diagram of an example processing chamber for carrying out certain disclosed embodiments.

[0133] [Diagram 5] FIG. 5 is a schematic diagram of an example of a process apparatus for practicing certain disclosed embodiments.

[0134] [Figure 6] FIG. 6 is a block diagram of a processing system suitable for performing thin film deposition processes in accordance with certain embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0135] Reference will be made in detail herein to specific embodiments of the present disclosure. Examples of specific embodiments are illustrated in the accompanying drawings. Although the present disclosure will be described in conjunction with these specific embodiments, it will be understood that it is not intended to limit the present disclosure to such specific embodiments. Rather, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. The present disclosure may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the present disclosure.

[0136] Certain technology nodes require advanced semiconductor processing that can provide more selective patterning or etching operations. The present disclosure relates, in part, to Mo-containing layers that can provide enhanced selectivity. Such layers can be useful for extending technology scaling, such as by providing selective hardmask materials. Thus, in certain embodiments, the Mo-containing layers exhibit certain properties (e.g., density, etch selectivity, hydrogen content, fluorine content, etc., and combinations thereof) that exhibit desired film behavior for use as a hardmask.

[0137] Conventional molybdenum deposition may include the use of fluorine-containing precursors such as MoF6. However, the use of MoF6 may introduce significant amounts of fluorine into the deposited Mo-containing film. The presence of fluorine may cause electromigration or diffusion of fluorine to adjacent components, damaging contacts and degrading device performance. As devices scale, features become smaller and the adverse effects of electromigration and ion diffusion become more pronounced, causing device failure. Mo films containing significant amounts of fluorine may thereby cause integration and reliability issues as well as device performance issues associated with underlying films or device structures such as vias and gates. Processes having minimal fluorine content are described herein. As an example, fluorine-free Mo-containing precursors may be employed. In another example, fluorine-containing Mo precursors are employed, but the deposition process can minimize fluorine content in the grown film.

[0138] FIG. 1 provides a non-limiting use of a stack with a hard mask. For example, the stack may include a resist layer 114, a Mo-containing layer 113, a material layer 112, and a substrate layer 111. In some cases, the term "substrate" is used for a general surface on which the Mo-containing layer may be deposited. Thus, in FIG. 1, the substrate may include a material layer 112 and a substrate layer 111. Such a substrate may, in some cases, be considered a stack.

[0139] As can be seen, material layer 112 can be disposed between Mo-containing layer 113 and substrate layer 111, and resist layer 114 can be disposed on a top portion of Mo-containing layer 113. A method of processing a stack (or substrate, which can be used interchangeably) can include patterning 101 resist layer 114 to form a resist mask having a pattern. As can be seen, the resist mask can include patterned features 114a / b / c / d having openings 105 disposed therein.

[0140] Returning again to Figure 1, the method may further include transferring 102 the pattern of the resist mask to the underlying Mo-containing layer 113. Upon transferring the pattern from the resist mask to the Mo-containing layer, the Mo-containing layer itself has a defined pattern. In some embodiments, the Mo-containing layer functions as a hard mask including patterned features 113a / b / c / d and having one or more openings 106 disposed therein.

[0141] The defined pattern provided by the Mo-containing layer may then be transferred to the material layer. Returning to Figure 1, the method may further include transferring 103 the defined pattern of the Mo-containing layer (acting as a hard mask) to the underlying material layer 112. After patterning, the material layer may have patterned features 112a / b / c / d and have one or more openings 107 disposed therein.

[0142] In addition to using the Mo-containing layer as a hard mask, the Mo-containing layer can also serve other purposes, for example, it can function as an etch stop layer, a conformal layer, a planar layer, a step coverage layer, a barrier layer, an isolation layer, or any other useful layer in a stack.

[0143] The Mo-containing layer can be provided by any useful method. As seen in FIG. 2, one non-limiting method can include providing a substrate 210 and exposing a surface portion of the substrate to one or more Mo-containing precursors 270 with one or more deposition precursors. The non-limiting Mo-containing precursor can be any described herein. The deposition precursor(s) can include any precursor that does not contain Mo. Such non-limiting deposition precursors can include a C-containing precursor, a Si-containing precursor, or a B-containing precursor.

[0144] The providing and exposing operations may include using a process chamber having a substrate holder. The providing operation may include providing a substrate to the substrate holder, which may be a pedestal.

[0145] The exposure operation may include sequential or simultaneous delivery of the Mo-containing precursor(s) and one or more deposition precursors, which may include atomic layer deposition (ALD), chemical vapor deposition (CVD), and plasma-assisted forms thereof.

[0146] 2, the method may optionally include depositing 290 the Mo-containing layer in the presence of a plasma. In some embodiments, the deposition may include a plasma enhanced chemical vapor deposition (PECVD) process. Processing conditions for providing the plasma are described herein.

[0147] The exposure or deposition operation may include the use of another reagent, such as a reactive gas, a reducing agent, a carrier gas, or a combination thereof. Non-limiting reagents may include gaseous forms such as hydrogen (H2), argon (Ar), nitrogen (N2), helium (He), and combinations thereof.

[0148] Optionally, the stack may include an interfacial layer disposed between the Mo-containing layer and the substrate. The interfacial layer may provide an adhesion layer, an initiation layer, or a growth layer, as the case may be. As seen in FIG. 2, the method may include an optional operation 230 of providing an interfacial layer on a top surface portion of the substrate. Thus, exposing the substrate to a Mo-containing precursor provides a Mo-containing layer on a top surface portion of the interfacial layer.

[0149] In yet another option, the top surface portion of the substrate may be pretreated. As seen in FIG. 2, the method may include an optional operation 250 of pretreating the top surface portion of the substrate. Thus, exposing the substrate to a Mo-containing precursor provides a Mo-containing layer on the top surface portion of the pretreated surface. Without wishing to be limited by mechanism, such pretreatment may enhance adhesion of the Mo-containing layer to the interface layer or top surface portion of the substrate. Non-limiting pretreatment conditions may include the use of helium (He), argon (Ar), nitrogen (N2), or hydrogen (H2), as well as combinations thereof, which may be used to pretreat the substrate (e.g., prior to introducing the Mo-containing precursor or other deposition precursors described herein).

[0150] Operations 230, 250 can be performed sequentially in any order. In one example, the method includes providing an interface layer and then pre-treating a top surface portion of the interface layer to provide a pre-treated surface on the interface layer. In another example, the method includes pre-treating a top surface portion of the substrate to provide a pre-treated surface and then providing an interface layer on the pre-treated surface. In yet other examples, only one of operations 230 or 250 is performed.

[0151] The present disclosure also relates to a method for processing a substrate, which may include transferring a pattern to a portion of the substrate. As employed herein, the term substrate may refer to a particular material or layer, a combination of materials or layers, a stack, or any other useful combination of materials and devices. Thus, a pattern may be transferred to any material, layer, stack, device, or portion thereof.

[0152] Semiconductor manufacturing processes involve the fabrication of memory and logic devices. Examples include 3D NAND and Dynamic Random Access Memory (DRAM) applications, as well as logic applications for mid-end-of-line (MEOL) and back-end-of-line (BEOL) processes. Fabrication of memory and logic devices often involves etching features, such as contact holes, on a substrate, which may include one material or multiple layers of materials, some of which may be semiconductor materials. A "feature," such as a via or contact hole, may be characterized by one or more of a narrow or reentrant opening, a constriction inside the feature, and a high aspect ratio. The term "feature" as described herein refers to a negative feature, such as a hole or a via. Etching a feature often involves deposition and patterning of a hard mask on the material to be etched, and etching the material using the hard mask as a pattern. The patterned hard mask may eventually be removed from the substrate. As described herein, a Mo-containing layer may be employed as a hard mask or etch stop layer.

[0153] In other embodiments, the Mo-containing layers provided herein can be used as components in interconnect metallization (e.g., to fill recessed features to form contacts), in logic gate applications in FinFETs, as adhesion layers or diffusion barriers, and in 3D NAND manufacturing. For example, the Mo-containing layers can be employed as liners for subsequent deposition of different metal layers, metallization layers, or different metal-containing layers (e.g., cobalt-containing layers, or pure molybdenum metal layers). Examples of applications include logic and memory contact filling, DRAM buried wordline filling, vertically integrated memory gates, wordline filling, and 3D integration using through-silicon vias (TSVs). Without wishing to be limited by mechanism, the resistivity of molybdenum scales better than tungsten, and in some embodiments, molybdenum is a particularly advantageous metal for filling narrow recessed features, e.g., features having a width less than about 20 nm. In one exemplary application, molybdenum metal is used to manufacture barrierless contacts. In this application, molybdenum metal is deposited directly into a recessed feature (contact hole) having a width of about 5-100 nm, e.g., about 5-20 nm, formed in a dielectric layer and including exposed dielectric such as silicon oxide, silicon nitride, or low-k material, such as silicon oxycarbide, on the sidewalls and exposed silicon or silicon germanium, etc., on the bottom. In an alternative embodiment, the contact hole prior to deposition may be lined with an interfacial layer (such as tungsten nitride, molybdenum nitride, molybdenum carbide, or titanium nitride) on which the molybdenum metal is deposited.

[0154] In certain embodiments, such processing may include using the Mo-containing layer as a hard mask to pattern the material layer. As seen in FIG. 3A, the method may include providing 310 a substrate having a material layer, depositing 330 a Mo-containing layer on a top portion of the material layer, forming 350 a defined pattern in the Mo-containing layer, and transferring 370 the defined pattern to a material layer underlying the Mo-containing layer. Optionally, the method may include providing an interface layer or pre-treating a surface of the substrate prior to deposition of the Mo-containing layer. The process may also include other operations, such as removing the Mo-containing layer, the interface layer, or the pre-treated surface.

[0155] The processing of the substrate may include further operations to transfer the pattern. As seen in FIG. 3B, the method may include providing a substrate having a material layer 310. Optional operations may include providing an interface layer on a top surface portion of the substrate to place an interface layer between the substrate and the Mo-containing layer, or pre-treating the surface to provide a pre-treated surface 320. The process may also include other operations, such as removing the Mo-containing layer, the interface layer, or the pre-treated surface.

[0156] The method may further include depositing 330 a Mo-containing layer on a top portion of the material layer and depositing 351 a resist layer to form a resist mask having a pattern. The resist layer may be further patterned (e.g., photopatterned) to form a resist mask. In addition to resist masks, any useful patterning mask may be employed and disposed over the Mo-containing layer.

[0157] The resist mask can be used to pattern the Mo-containing layer. For example, the method may further include transferring 352 the pattern of the resist mask onto the Mo-containing layer. Upon transferring this pattern, the Mo-containing layer can be used as a hard mask, the hard mask now having a defined pattern provided by the resist mask. The defined pattern may include one or more patterned features and one or more openings in the Mo-containing layer. Finally, the method may include transferring 371 the defined pattern of the Mo-containing layer (employed as a hard mask) to a material layer disposed below the Mo-containing layer.

[0158] Such a transfer operation may include etching a resist layer, a Mo-containing layer, an interface layer, a pre-treated surface, or a material layer. Etching can define openings in a particular layer and transfer the pattern by etching material through the exposed openings. Non-limiting etch chemistries include nitrogen trifluoride (NF3), boron trifluoride (BF3), sulfur hexafluoride (SF6), chlorine gas (Cl2), bromine gas (Br2), C, fluorine gas (HF), fluorine-containing gas (F4), fluorine-containing fluoride (HF ... x F y a halogen-containing gas such as a halogen-containing gas (wherein x is 1 to 10 and y is 2 to 20), an oxygen-containing gas such as oxygen (O2), or a C x F y Fluorine-containing gases such as fluorine-containing gases can be mentioned.

[0159] If an interfacial layer is present, the transfer of the pattern may include etching the interfacial layer through a defined pattern (or openings) in the Mo-containing layer. If a pre-treated surface is present, then the transfer of the pattern may include etching the pre-treated surface through a defined pattern in the Mo-containing layer.

[0160] Deposition process Deposition may include delivering one or more precursors to a process chamber. Such precursors may include Mo-containing precursors, which are deposited in the presence of one or more deposition precursors to provide a Mo-containing layer. The precursors herein may be delivered to a process chamber in the presence of a gas (e.g., a reactive gas, a reducing agent, or a carrier gas, as well as combinations thereof). The carrier gas may be, for example, an inert gas. Non-limiting gases include hydrogen (H2), nitrogen (N2), helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and the like.

[0161] In certain embodiments, a reducing agent is used during deposition. In one example, the reducing agent is used to reduce metal atoms (e.g., Mo atoms) in the film to a lower oxidation state. In another example, the reducing agent can remove halides or other impurities in the growing film. Non-limiting reducing agents can include hydrogen (H2), methane (CH4), ammonia (NH3), other nitrogen-containing gases or reducing agents such as hydrazine (N2H4), carbon monoxide (CO), boron-containing or silicon-containing reducing agents such as B2H6 or SiH4, and the like. Still other reducing agents include water, alcohols, H2S, hydrocarbons (e.g., any of those described herein, including methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), and the like), and thiols, optionally using plasma activation.

[0162] In some embodiments, the deposition includes the use of a Mo-containing precursor, a deposition precursor, and a reducing agent. In certain embodiments, the deposition precursor is a C-containing precursor, a Si-containing precursor, or a B-containing precursor. The reducing agent can be any of those described herein, including but not limited to hydrogen (H2) gas.

[0163] The Mo-containing layer can be disposed on top of a substrate, on top of an interfacial layer (which is then provided on top of the substrate), or on top of a pre-treated surface. The use of an interfacial layer or a pre-treated surface can enhance adhesion of the Mo-containing layer to the substrate.

[0164] Prior to deposition of the Mo-containing layer, the surface may include an interfacial layer. The interfacial layer may be provided by ALD, CVD, or plasma-assisted forms thereof. Non-limiting precursors and deposition conditions for providing the interfacial layer are described herein.

[0165] Prior to deposition of the Mo-containing layer, the surface may be pretreated. Such pretreatment may include treating a surface portion of the substrate or a surface portion of the interface layer, if present. In one example, the surface may be pretreated with a soak gas. Non-limiting soak gases include oxygen-containing gases, nitrogen-containing gases, or other suitable gases that can modify the interface between the substrate and the subsequently deposited material to reduce tunneling of electrons from the substrate. Examples of soak gases include oxygen (O2), ammonia (NH3), nitrogen (N2), silane (SiH4), disilane (Si2H6), trisilane (Si3H8), germane (GeH4), argon (Ar), diborane (B2H6), hydrogen (H2), nitrogen (N2) gas, or combinations thereof.

[0166] In some embodiments, the substrate may be soaked using one or more gases. For example, in some embodiments, the substrate may be exposed to silane for a first duration and then to diborane for a second duration. Such operations may also be repeated periodically. In any of the disclosed embodiments, the chamber housing the substrate may be purged between one or more cycles of the soak operation. Purging may be performed by flowing an inert gas, such as argon, into the chamber.

[0167] Pre-treatment may optionally include modifying the substrate or interface layer to provide a rough surface. In some embodiments, the modification may include sputtering the surface by non-reactive ion bombardment to provide a rough surface. Non-limiting non-reactive ions may include argon (Ar), helium, (He), krypton (Kr), or other non-reactive species. In other embodiments, the modification may include exposing the surface to an oxygen-containing plasma to provide an oxygen-containing surface. Non-limiting oxygen-containing plasmas may include carbon dioxide (CO2), oxygen (O2), or water (as H2O or as a mixture of H2 and O2).

[0168] In other embodiments, the pre-treatment may optionally include exposing the interface layer substrate to ultraviolet radiation, which may be emitted at a wavelength between about 180-600 nm for a duration between about 60-600 seconds.

[0169] Deposition of the Mo-containing layer may include ALD processes, CVD processes, and plasma-assisted forms thereof. In some embodiments, deposition includes exposure of the precursor to a plasma. Deposition may also include various types of plasma processes, such as using inductively coupled plasma, capacitively coupled plasma, microwave plasma CVD, remote plasma CVD, and other similar processes.

[0170] ALD is a technique for depositing thin layers of materials using sequential self-limiting reactions. Typically, an ALD cycle includes delivering and adsorbing at least one reactant to a substrate surface, and then reacting the adsorbed reactant with one or more reactants to form a sublayer of a film. As an example, a deposition cycle may include the following operations: (i) delivery / adsorption of a Mo-containing precursor, (ii) purging the Mo-containing precursor from the chamber, (iii) delivery of a deposition precursor (e.g., a C-containing precursor, a Si-containing precursor, a B-containing precursor, optionally in the presence of a reactive gas, a reducing agent, and a carrier gas), and (iv) purging the deposition precursor from the chamber.

[0171] In an ALD process, the substrate may be exposed in a cyclical manner. For example, the substrate may be first exposed to a pulse of a Mo-containing precursor, then the precursor is optionally purged, and then the substrate is exposed to a pulse of another reagent (e.g., a reducing agent or a deposition precursor), and then the reagent is optionally purged. Such cycles may be repeated until a layer of a desired thickness is formed on the substrate. It will be understood that the sequence of the Mo-containing precursor, the deposition precursor, and the reducing agent may be any useful sequence. Purging may be performed by flowing an inert gas, such as argon. In some embodiments, the inert gas may also be used as a carrier gas to deliver one or more gases, including but not limited to, a soak gas, a precursor gas, a reactant gas, a reducing agent, and a carrier gas, to the substrate. Although ALD is described herein as an example, it will be understood that the films deposited by ALD herein may also be deposited by CVD or other techniques.

[0172] During any of the above exposures, the gas may be pulsed or continuously flowed. Similarly, in some embodiments, during purging, the inert gas may be pulsed for one or more times during a single purge operation. During deposition, one or more changes to one or more parameters, such as pressure, flow rate, and temperature, may be used. In some embodiments, the pedestal may be moved during deposition, so that the gap between the substrate and the showerhead above the pedestal may be adjusted. The movement of the pedestal may be used in combination with a change in one or more parameters, such as pressure, temperature, or flow rate. Adjusting the gap between the substrate and the showerhead may affect the pressure, temperature, or flow rate that may be used according to certain disclosed embodiments.

[0173] The flow rates of the Mo-containing precursor, deposition precursor, and other optional gases (e.g., reactive gas, reducing agent, or carrier gas) can be adjusted to provide the desired Mo-containing layer. Typical gas pressures and flow rates can include any of those described herein. In other embodiments, the flow rate of the Mo-containing precursor can be between about 20-1000 sccm, and the flow rate of the optional deposition precursor(s) can be between about 100-5000 sccm. The flow rate of the carrier gas(es) can be between about 1500-15000 sccm. If present, the reducing agent can be provided at a flow rate between about 100-1000 sccm. During deposition, one or more of the gases can be provided to the process chamber at the flow rates herein. Optionally, a plasma can be used to deposit the Mo-containing layer, such as by remote delivery to the process chamber or generation within the chamber. The exposure time can vary (e.g., from about 1 to 5000 seconds) depending on the desired thickness of the layer or layers, or the desired thickness during each cycle of deposition of the Mo-containing precursor and other deposition precursor(s).

[0174] Plasma may be employed during deposition, patterning, pattern transfer, or etching. Various types of plasma sources may be used, including RF, direct current (DC), and microwave-based plasma sources. In some embodiments, an RF plasma source is used. Typically, RF plasma power for a 300 mm wafer ranges between about 500-10,000 watts (W), or between about 3,000-10,000 W. In some embodiments, the power is about 7,000 W per station. Depending on the process chamber being used, in some embodiments, each station has its own dedicated power source. In various embodiments, the plasma is generated as an inductively coupled plasma upstream of the showerhead.

[0175] The generation of the plasma may include the use of one or more radio frequency (RF) power sources. In one example, the RF power sources provide about 100-5000 W of power at frequencies of about 50 kHz to about 100 MHz (e.g., 50 kHz to 13.6 MHz, 50 kHz to 27 MHz, 13.6 MHz to 100 MHz, and ranges therebetween). In another example, the RF power sources provide about 500-5000 W of power at frequencies of about 50 kHz to about 100 MHz (e.g., 50 kHz to 13.6 MHz, 50 kHz to 27 MHz, 13.6 MHz to 100 MHz, and ranges therebetween). In general, the plasma may be generated directly in the process chamber housing the substrate (direct plasma or in situ plasma) or may be generated remotely in a separate compartment and the resulting plasma activated species delivered to the process chamber (remote plasma).

[0176] The power used to generate the plasma may be between about 10-3000 W per station (e.g., 100-1000 W, 200-1000 W, 200-800 W, 200-500 W, 500-3000 W, or 800-3000 W). The RF frequency used to generate the plasma may be between about 0.3-600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 40 MHz, 100 MHz, 400 kHz, or combinations thereof). The RF bias power may be between about 0-1000 W using pulsed or continuous wave plasma. The processing chamber may be an inductively coupled plasma (ICP) chamber or a capacitively coupled plasma (CCP) chamber. In some embodiments of an ICP chamber, the frequency of both the top ICP generator and the bias generator is 13.5 MHz. Depending on the underlying layer, in some embodiments, the pressure can be about 10-400 mTorr and the transformer coupled plasma (TCP) power can be about 200-500 W.

[0177] The RF frequency used to generate the plasma may be between about 0.3 and 600 MHz (e.g., 13.56 MHz, 60 MHz, 27 MHz, 2 MHz, 400 kHz, or a combination thereof). The RF bias power may be between about 10 and 1000 W, with the plasma pulsed at between 1 and 100% DC, where 100% indicates CW (e.g., 1 to 99%). In some cases, the pulse duration of the plasma is between about 0.02 and 5 ms. The RF bias power may be pulsed at less than 5000 Hz, such as at a frequency between about 5 and 2000 Hz (e.g., between about 5 and 100 Hz). The TCCT parameter may be between 0.1 and 1.5. In some non-limiting processes, the plasma exposure can include a high frequency (HF) RF component (e.g., typically between about 1-100 MHz, such as about 13.56 MHz) and a low frequency (LF) RF component (e.g., less than about 1 MHz, or typically between about 100 kHz and 2 MHz, such as about 100 kHz). Such HF and LF RF components can be provided at any useful plasma condition, such as any useful power range (e.g., 100-1000 W or 100-5000 W) or frequency range (e.g., 50 kHz to 100 MHz).

[0178] In certain embodiments, the deposition involves a PECVD process. This process may include transformer coupled plasma (TCP), inductively coupled plasma (ICP), or capacitively coupled plasma (CCP). In certain embodiments, the TCP or ICP power is about 100-1000 W without bias. In certain embodiments, the generation of plasma (e.g., TCP or ICP) can be controlled by power in a continuous wave (CW) mode.

[0179] In various embodiments, no bias is applied to the pedestal during deposition or etching of the Mo-containing layer. However, in some embodiments, an RF bias is used. An RF bias may be used in some embodiments. Various types of RF bias may be used, for example, the RF bias may be generated at a frequency of 13.56 MHz or less, including but not limited to 400 MHz, 2 MHz, and 1 MHz.

[0180] In some cases, a high bias may be employed. For example, the etch may be performed using a high bias in pulses to effectively remove the Mo-containing layer. One example of a high bias is a bias having a power of at least about 1000V applied to the pedestal during the etch. The use of a bias depends on the chemistry and whether directional etching is used in the application using the particular disclosed embodiment. If a bias is applied, the power applied to the bias may be between about 10-3000V, such as about 10V. It will be understood that the terms "bias power" and "bias voltage" are used interchangeably herein to describe the voltage set on the pedestal when a bias is applied to the pedestal. The bias power or bias voltage described herein is measured in watts with respect to the power applied to the pedestal.

[0181] The bias can be applied using an applied pulsed bias (e.g., about 10-1000 W of power) or an applied continuous wave bias (e.g., about 10-500 W of power). In further embodiments, deposition (e.g., using TCP or ICP power in CW mode) can include an applied bias (regardless of frequency) that is pulsed (e.g., in the range of about 1 Hz to about 10 kHz, such as 10-2000 Hz) with a duty cycle between about 1-99%. Additional pulse frequencies and duty cycles are described herein. In some embodiments, an applied pulsed bias can be provided to control ion energy. Non-limiting applied pulsed bias power can be about 10-1000 W, as well as other ranges described herein.

[0182] For example, the pulsed plasma may be pulsed between a low bias and a high bias, or between an on-state bias and an off-state (0V) bias. Pulsing between a low bias and a high bias includes pulsing between a low bias of between about 100-300V and a high bias of between about 1000-2500V.

[0183] Pulsing may be performed using a duty cycle (DC) between about 3% to about 40%, or about 3% to about 99%, or 100% (continuous bias). Duty cycle refers to the duration that a pulse is on during a period. It will be understood that bias pulsing may include a repetition of periods, each of which may last for a duration T. Duration T includes the duration for pulse on time (duration that bias is on) and duration for bias off time (duration that bias is off) of a given period. Pulse frequency is understood as 1 / T. For example, for a bias pulsing period T=100 μs, the frequency is 1 / T=1 / 100 μs or 10 kHz. Duty cycle or duty ratio is the fraction or percentage of the period T that the bias is on, i.e., duty cycle or duty ratio is the pulse on time divided by T. For example, for a bias pulsing period T=100 μs, if the pulse on time is 70 μs (the duration of a period that the bias is in the on state is 70 μs) and the pulse off time is 30 μs (the duration of a period that the bias is in the off state is 30 μs), then the duty cycle is 70%.

[0184] Pulsed or continuous bias can be used to fine-tune the film properties. In one embodiment, pulsed bias can provide a denser film compared to a less dense film prepared with a bias power of 0 W. Such denser films can, in some cases, increase etch resistance compared to a less dense film. In another example, such denser films can reduce undercut compared to a less dense film prepared with a bias power of 0 W.

[0185] In other embodiments, the deposition may include an applied CW bias. The CW bias may also be used to control the ion energy. In some embodiments, the applied CW bias power may be 10-1000 W (e.g., 10-500 W, 10-400 W, as well as other ranges described herein).

[0186] Other non-limiting process conditions include pressures >1 milliTorr (mTorr) (e.g., about 5-1000 mTorr or 1-10 Torr), power levels <5000 W (e.g., about 10-3000 W), or temperatures <200° C. (e.g., about 0-100° C.) or >200° C. (e.g., about 200-700° C.). The plasma can be generated with an RF source operating at 0.3-600 MHz, with a power between about 10-3000 W.

[0187] Other process conditions may include those to provide a useful Mo-containing layer. The substrate temperature for deposition may be, for example, in the range of about 20-700°C (e.g., 300-650°C, 250-650°C, 250-550°C, or 150-350°C). In some embodiments, lower temperatures may be used. Such temperatures may be less than 500°C, less than 550°C, less than 450°C, less than 400°C, or less than 350°C. Low temperatures may be used for improved step coverage. In addition, low temperatures may increase the amount of impurities in the deposited layer and increase the amorphous character, which in turn may increase the grain size of the subsequently deposited layer. In various embodiments, it may be advantageous to deposit the layer at a low temperature. The chamber pressure may be between about 0.2-90 Torr, or between about 5-50 Torr, or between about 20-40 Torr, or about 30 Torr.

[0188] Further non-limiting deposition conditions include control of precursor flow rate(s), gas flow rate(s), process pressure, temperature (e.g., electrostatic chuck (ESC) temperature), plasma (e.g., TCP) power, bias power, and duty cycle (DC) in the process chamber. The flow rate of the precursor(s) may be between about 1-2500 standard cubic centimeters per minute (sccm) (e.g., about 20-5000 sccm, 100-5000 sccm, 20-1000 sccm, or 100-1000 sccm). The flow rate of the carrier gas(s) may be between about 0-20000 sccm (e.g., 0-15000 sccm, 1000-2000 sccm, or 1000-15000 sccm). The chamber pressure may be between about 5-1000 mTorr (e.g., 5-800 mTorr, 10-500 mTorr, 10-400 mTorr, 30-500 mTorr, 10-1000 mTorr, or 30-1000 mTorr) or between about 0.2-20 Torr. The ESC temperature may be between about 20-700°C and the process chamber temperature may be between 200-650°C.

[0189] After deposition, the Mo-containing layer may be optionally annealed. The annealing may be performed by increasing the temperature. For example, if the reaction is performed at a relatively low temperature, e.g., less than about 450°C, such as less than about 400°C, the temperature may be increased by, e.g., 50-200°C during the annealing. In some embodiments, the annealing is performed at a temperature between about 300-500°C.

[0190] Pattern Formation and Transfer Process In the semiconductor stack, patterning can be achieved using a mask. In one example, a resist mask is employed by using a resist layer, which can be fabricated using a lithography process that optically injects a pattern into the photoresist and then develops the photoresist to remove portions, thereby forming openings in the resist. Non-limiting resists can include positive photoresist, negative photoresist, ultraviolet (UV) photoresist, i-line photoresist, electron beam (e-beam) photoresist, and the like. Non-limiting materials for patterning the Mo-containing layer can include, for example, silicon dioxide, amorphous carbon, silicon-containing precursors, carbon-containing precursors, and materials that include or are formed from any of these.

[0191] A resist mask can be formed by depositing (e.g., by spin coating) a layer of resist material onto a surface to a desired thickness. A pattern can be introduced into the resist material by exposing the resist to patterning radiation (e.g., UV radiation) and then developing the resist material. After development, a pattern with openings is provided in the resist layer to produce a resist mask.

[0192] The resist mask can then be used to provide a defined pattern in the Mo-containing layer. In some cases, the Mo-containing layer can be used as a hard mask. The hard mask can optionally include feature openings having widths between about 16-120 nm. In use, the defined pattern in the Mo-containing layer can be transferred to a material layer disposed below the Mo-containing layer.

[0193] The transfer of the pattern may include providing a mask with openings and then etching the underlying material layer using the mask. The etching may include aligning the mask over the material layer, where the openings in the mask define the exposed portions of the material layer. The etching may then include exposing the open areas of the material layer to an etchant chemical, resulting in removal of the material layer through the open areas. The etching may include wet or dry processes, as well as combinations thereof.

[0194] Non-limiting etchant chemistries may include the use of an etchant gas with or without the presence of a plasma. The etchant gas may include a fluorine-containing gas (e.g., a fluorocarbon gas or a perfluorocarbon gas), an oxygen-containing gas, a nitrogen-containing gas, a chlorine-containing gas, a carbon-containing gas, a halogen-containing gas, and mixtures thereof. The etchant gas may optionally include an inert gas, such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and the like.

[0195] Non-limiting etchant gases are as follows: Fluorine-containing gases include tetrafluoromethane (CF4), perfluoroethane (C2F6), hexafluorocyclopropane or hexafluoropropene (C3F6), perfluoropropane (C3F8), hexafluoro-1,3-butadiene or hexafluorocyclobutene (C4F6), perfluoroisobutene or octafluorocyclobutane (C4F8), octafluorocyclopentene (C5F8), decafluorocyclopentane or perfluoropent-1-ene (C5F 10), 1,2,3,3,4,5,6,6-octafluorocyclohexa-1,4-diene, or 3-(trifluorovinyl)pentafluorocyclobutene (C6F8), or combinations thereof. The oxygen-containing gas may include oxygen (O2), carbon dioxide (CO2), carbon monoxide (CO), nitrous oxide (N2O), nitrogen dioxide (NO2), ozone (O3), water (H2O), and the like. The nitrogen-containing gas may include nitrogen (N2), ammonia (NH3), N2O, NO2, and the like. The chlorine-containing gas may include hydrogen chloride (HCl), chlorine gas (Cl2), tetrachloromethane (CCl4), trichloromethane (CHCl3), dichloromethane (CH2Cl2), chloromethane (CH3Cl), and the like. The carbon-containing gas can be a hydrocarbon or any C-containing precursor herein, as well as methane (CH4), ethane (C2H6), ethylene (C2H4), etc. The halogen-containing gas can be nitrogen trifluoride (NF3), boron trifluoride (BF3), sulfur hexafluoride (SF6), chlorine gas (Cl2), bromine gas (Br2), hydrogen chloride (HCl), tetrafluoromethane (CF4), etc.

[0196] After transferring the defined pattern to the material layer, the Mo-containing layer may be optionally stripped. The method of stripping the Mo-containing layer may include any of the etchant chemistries described herein. The strip chemistries may include the use of hydrogen peroxide, sulfuric acid, and a combination of oxygen-containing gas and halogen-containing gas.

[0197] In any of the processes herein, a purge operation may be employed between deposition, patterning, and pattern transfer processes. The purge operation may include the use of a purge gas (e.g., any inert gas herein) to remove gases or by-products from the processing chamber. Each purge may be performed for a duration between about 0.25 to 30 seconds.

[0198] Molybdenum-Containing Precursors The use of dopants can improve etch resistance in some cases. Thus, the processes, layers, and films herein can include the use of Mo-containing precursors to provide Mo-containing layers. Any of the process conditions herein can be modified to incorporate Mo into the Mo-containing layer. For example, deposition can include the use of Mo-containing precursors alone or in combination with another deposition precursor (e.g., C-containing, Si-containing, or B-containing precursors) within the process conditions described herein (e.g., any of the flow rates, pressures, temperatures, plasma powers, bias powers, pulse frequencies, duty cycles, TCCTs, etc. described herein).

[0199] Non-limiting Mo-containing precursors can include organo-molybdenum compounds (e.g., having one or more organic ligands), molybdenum halide compounds (e.g., having one or more halos), molybdenum oxyhalide compounds (e.g., having an oxide and a halo), inorganic molybdenum compounds, and the like.

[0200] In one embodiment, the Mo-containing precursor comprises a structure having formula (I): MoL n (I) In the formula, each L is hydrogen (H), halo, oxide (=O), imide (=NR 1 ), carbonyl (CO), amine (NR 1 R 2 ), an organic ligand, a monodentate ligand, or a bidentate ligand, and n is selected from 2 to 6. 1 and R 2 Each of can be any functional group described herein, such as aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein. Each L can be any ligand described herein.

[0201] In some embodiments, one or more L can be aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein. In other embodiments, one or more L can be alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. In certain disclosed embodiments, L may be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, hydroxyl, thiol, acyloxy, silyl, alicyclic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl, where the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0202] In another embodiment, the Mo-containing precursor comprises a structure having the formula (II): Mo(X) m (L) n (II) wherein each X is independently selected from halo (e.g., F, Cl, Br, and I), oxide (=O), imide (=NR 1 ), or carbonyl (CO), each L is an organic ligand (e.g., any of those described herein), m is selected from 0 to 6, and n is selected from 0 to 6, and at least one of m and n is not 0. In certain embodiments, L further comprises an element selected from the group consisting of N, O, and S.

[0203] In some embodiments, the organic ligand(s) are independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, ester, amine, amidinate, amidate, iminopyrrolidinate, diazabutadiene, β-iminoamide, α-iminoalkoxide, β-diketiminate, β-ketoiminate, β-diketonate, pyrazolate, β-aminoalkoxide, guanidinate, amide, imide, thioether, thiolate, dithiolene, α-iminothiolene, α-dithiolate, and β-dithiolate, each of which may be substituted or unsubstituted.

[0204] In another embodiment, the Mo-containing precursor comprises a structure having formula (III): Mo2L n (III) wherein each L is a bidentate ligand and n is selected from 2 to 5. In certain embodiments, the Mo-containing precursor comprises multiple Mo-Mo bonds. The bidentate ligand can be any of those described herein, for example, an amidinate, amidate, or guanidinate ligand.

[0205] In yet another embodiment, the Mo-containing precursor comprises a structure having formula (IV): Mo(L1) m (L2) n (X) p (IV) wherein each L1 is independently a bidentate ligand, each L2 is independently a neutral ligand, each X is independently an anionic ligand, m is selected from 1 to 3, n is selected from 0 to 4, and p is selected from 0 to 4. In some embodiments, n and p are not simultaneously 0. Examples of bidentate, neutral, and anionic ligands are described herein.

[0206] Non-limiting bidentate ligands include amidinates, amidates, iminopyrrolidinates, diazobutadienes, β-iminoamides, α-iminoalkoxides, β-diketiminates, β-ketoiminates, β-diketonates, pyrazolates, β-aminoalkoxides, guanidinates, dithiolenes, α-iminothiolenes, α-dithiolates, and β-dithiolates. Bidentate ligands can be neutral or anionic. Still other bidentate ligands include NR 1 -Ak-NR 2 , N.R. 1 -Ak-O, NR 1 Examples of the substituents include -Ak-S, S-Ak-O, O-Ak-O, and S-Ak-S, where Ak is an optionally substituted alkylene or an optionally substituted heteroalkylene. Ak groups can be unsubstituted or substituted, such as with alkyl, amine, hydroxyl, halo, aminoalkyl, hydroxyalkyl, haloalkyl, or other substituents described herein for alkyl. Ak groups can be saturated or unsaturated (e.g., having one or more double or triple bonds).

[0207] The ligands can be neutral or anionic (e.g., monoanionic or dianionic), and the molybdenum can be in various oxidation states, such as +1, +2, +3, +4, +5, and +6. In some embodiments, the ligands can be neutral ligands. Non-limiting neutral ligands can include CO, amines, phosphines, nitriles, isonitriles, and thioethers. In other embodiments, the ligands can be anionic ligands. Non-limiting anionic ligands can include halides, alkyls, allyls, cyclopentadienyls, alkoxides, amides, and imides.

[0208] Further examples include heteroleptic molybdenum halide compounds (i.e., compounds with different types of ligands). A specific example of such a precursor is a compound that includes molybdenum, at least one halide that forms a bond with the molybdenum, and at least one organic ligand (e.g., the organic ligand includes any of the elements N, O, and S, where an atom of any of these elements forms a bond with the molybdenum). In one embodiment, the Mo-containing precursor includes a structure having the formula (V): Mo(X) m (L) n (V) wherein each X is independently halo, each L is an organic ligand, m is selected from 1 to 6, and n is selected from 1 to 4. In certain embodiments, L comprises an element selected from the group consisting of N, O, and S.

[0209] In any embodiment herein, the ligand is an organic ligand having any of N, O, and S elements, and any atom of these elements forms a bond with molybdenum.In any embodiment herein, the ligand can be amine, amidinate, amidate, iminopyrrolidinate, diazabutadiene, β-iminoamide, α-iminoalkoxide, β-diketiminate, β-ketoiminate, β-diketonate, pyrazolate, β-aminoalkoxide, guanidinate, amide, and imide.Non-limiting N-containing and O-containing ligands include those in Scheme I. Scheme I: [ka]

[0210] In some embodiments, the ligands can be thioethers, thiolates, dithiolenes, α-iminothiolenes, α-dithiolates, and β-thiolates. Thioethers can include both monodentate and polydentate (e.g., bidentate or tridentate) thioethers, as well as ligands that include both thioether and thiolate (or other) moieties. An example of a monodentate thioether is dialkylsulfide SR 1 R 2 where R 1 and R 2 Each of the is independently an alkyl, such as dimethylsulfide, diethylsulfide, diisobutylsulfide, etc. An example of a polydentate thioether ligand containing a thiolate moiety is (SCH2CH2SCH2CH2S). 2- Further non-limiting S-containing ligands include those in Scheme II. Scheme II: [ka]

[0211] In Scheme I and Scheme II, R 1 , R 2 , and R 3 Each of R is independently hydrogen (H), aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. 1 , R 2 , and R 3is independently alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. 1 , R 2 , and R 3 Each of may be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, hydroxyl, thiol, acyloxy, silyl, alicyclic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl, where the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0212] In yet another embodiment of the ligand in Scheme I or Scheme II, R 1 , R 2 , and R 3 Each of R is independently H, alkyl, amine, haloalkyl, alkylsilyl, alkylamino, and alkoxy. 1 , R 2 , and R 3 is independently H, methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, and cyclobutylethyl. 1 , R2 , and R 3 Each of is independently an optionally substituted alkyl. In yet other embodiments, branched alkyl substituents (e.g., C 1 -C 2 -C 3 -C 4 -C 5 -C 6 -C 7 -C 8 -C 9 -C 10 -C 11 -C 12 -C 13 -C 14 -C 15 -C 16 -C 17 -C 18 -C 19 -C 20 -C 21 -C 22 -C 33 -C 44 -C 55 -C 66 -C 77 -C 88 -C 99 -C 100 -C 111 -C 120 -C 132 -C 140 -C 152 -C 162 -C 173 -C 184 -C 195 -C 196 -C 197 -C 198 -C 199 -C 200 -C 2 3-6 Ligands with branched alkyl groups are employed because such ligands may provide more volatile molybdenum precursors.

[0213] Any of the ligands herein may be substituted or unsubstituted. In some embodiments, these ligands comprise one or more substituents independently selected from the group consisting of H, alkyl, halo, hydroxyl, amine, haloalkyl, alkylsilyl, alkylamino, and alkoxy substituents.

[0214] In certain embodiments, the organomolybdenum compound is selected from the group consisting of molybdenum carbonyl (Mo[CO]), molybdenum acetate (Mo2[OCCH3]4), pentamethylmolybdenum (MoMe5), molybdocene dihydride (MoCp2H2, where Cp is cyclopentadienyl), bis(cyclopentadienyl)molybdenum(IV) dichloride (MoCp2Cl2 or Cp2H3). 10 H 10 Cl2Mo), cyclopentadienylmolybdenum(II) tricarbonyl dimer (Cp2Mo2[CO]6 or C 16 H 10 Mo2O6), bis(ethylbenzene)molybdenum ([(Et x C6H 6-x]2Mo, where x is 0, 1, 2, 3, or 4), cycloheptatriene molybdenum tricarbonyl (C7H8Mo[CO]3), molybdenum bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Mo[thd]3, where thd is 2,2,6,6-tetramethylheptan-3,5-dionate), molybdenum(VI) dioxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (MoO2[thd]2), molybdenum Molybdenum(VI) dioxide bis(acetylacetonate) (MoO2[acac]2, where acac is acetylacetonate), (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum ([nbd]Mo[CO]4), (mesitylene)molybdenum tricarbonyl ([Me3C6H3]Mo[CO]3), (trimethylsilylcyclopentadienyl)molybdenum dicarbonyl 2-methylallyl ([CpSiMe3]Mo[CO]2[η 3 -2-methylallyl]).

[0215] The organomolybdenum compound may contain an amine group. Such compounds include bis(t-butylimido)bis(dimethylamino)molybdenum(VI) ([tBuN]Mo[NMe]), bis(t-butylimido)bis(N,N-di(i-propyl)acetamidinato)molybdenum(VI) ([tBuN]Mo[iPrAMD], where AMD is acetamide), bis(N,N-di(cyclohexyl)acetamidinato)molybdenum dioxide ( MoO2[(CyN)2CMe]2, where Cy is cyclohexyl), bis(N,N-di(i-propyl)acetamidinato)molybdenum dioxide (MoO2[iPr2AMD]2 or MoO2[(iPrN)2CMe]2), bis(N,N-di(t-butyl)acetamidinato)molybdenum dioxide (MoO2[tBu2AMD]2 or MoO2[(tBuN)2CMe]2), and the like.

[0216] The molybdenum halide compound can be a molybdenum fluoride (e.g., MoF6 or MoF5 or MoF4), a molybdenum chloride (e.g., [MoCl5]2 or MoCl5 or MoCl4 or MoCl3 or MoCl2), a molybdenum bromide (e.g., MoBr4 or MoBr3 or MoBr2), or a molybdenum iodide (e.g., MoI3).

[0217] In some embodiments, the molybdenum halide is selected from the group consisting of molybdenum dioxide dichloride (e.g., MoO2Cl2), molybdenum dioxide dibromide (e.g., MoO2Br2), molybdenum dioxide diiodide (e.g., MoO2I2), molybdenum oxytetrachloride (MoOCl4), molybdenum oxytetrafluoride (MoOF4), molybdenum oxyiodide (e.g., Mo4O 11 I) and other molybdenum oxyhalide compounds.

[0218] Still other Mo-containing precursors may include molybdenum oxide (MoO3), ammonium molybdate (MoO4[NH4]2), etc. In some embodiments, the Mo-containing precursors provided herein have a vaporization temperature of 200° C. or less.

[0219] Carbon-Containing Precursors In combination with the Mo-containing precursor, one or more C-containing precursors can be used to provide a molybdenum carbide-containing material. Such materials may include ternary or quaternary materials such as molybdenum silicide carbide, molybdenum boride carbide, etc. Non-limiting C-containing precursors may include hydrocarbon compounds, halocarbon compounds, etc. In some cases, the C-containing precursor is employed with a reducing agent (e.g., H2), an inert gas, or a combination thereof.

[0220] The hydrocarbon precursor generally includes a carbon-containing precursor. In some cases, the hydrocarbon precursor includes only C and H atoms. The hydrocarbon compound includes C x H ywhere x is an integer from 1 to 10 and y is an integer from 2 to 24. Further non-limiting hydrocarbons include methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), propyne (C3H4), allene (C3H4), cyclopropene (C3H4), butane (C4H 10 ), Cyclohexane (CH 12 ), benzene (C6H6), toluene (C7H8), etc. Still other hydrocarbon compounds include alkenes, alkynes, aromatic, and cyclic hydrocarbons.

[0221] Hydrocarbon precursors are aliphatic compounds (e.g., C 1-10 Alkane, C 2-10 Alkenes, C 2-10 alkynes, including their linear or cyclic forms), alicyclic compounds (e.g., C 3-12 Cycloalkane, C 3-12 Cycloalkene, or C 3-12 The hydrocarbon precursor may be an aliphatic, cyclic, or aromatic compound (e.g., benzene, toluene, naphthalene, phenanthrene, as well as other polycyclic forms thereof). The hydrocarbon precursor may contain saturated bonds (single bonds, e.g., C-C or C-H bonds), unsaturated bonds (double or triple bonds, e.g., C=C, C≡C, or C≡N bonds), or combinations thereof. The aliphatic, cyclic, or aromatic compounds may be substituted with one or more functional groups, such as halo, alkyl, alkenyl, alkynyl, alkoxy, cyano, hydroxyl, etc.

[0222] Among the hydrocarbon precursors, a variety of compounds can be employed. For example, the hydrocarbon precursors can include aliphatic and aromatic compounds (e.g., alkanes, alkenes, alkynes, benzene, etc.) including their substituted forms. By using different hydrocarbon precursors, the type and amount of specific chemical bonds in the Mo-containing layer can be modified. For example, by using unsaturated hydrocarbon precursors, the unsaturated bond content can be increased (e.g., increased C=C or C≡C bond content), sp 2 The carbon content is increased, the sp carbon content is increased, the saturated bond content is decreased (e.g., decreased C-C bond content), and the sp3 Layers can be provided that have reduced carbon content or reduced C-H bond content (e.g., as compared to films formed with increased amounts of saturated hydrocarbon precursors or reduced amounts of unsaturated hydrocarbon precursors).

[0223] The selection of the hydrocarbon precursor may depend on various factors. In one non-limiting example, the hydrocarbon precursor includes a saturated precursor (e.g., an increased C-H bond content compared to a C-C, C=C, or C≡C content), which can provide sufficient H atoms. In yet another non-limiting example, the hydrocarbon precursor includes an unsaturated precursor (e.g., an increased C-C, C=C, or C≡C content compared to a C-H bond content). Without wishing to be limited by mechanism, the selection of such a precursor can provide enhanced etch resistance.

[0224] Non-limiting examples of halocarbon compounds include haloalkanes, haloalkenes, or haloaromatics. In yet other embodiments, the halocarbon compound is carbon tetrabromide (CBr4) or carbon tetrachloride (CCl4).

[0225] In some embodiments, the hydrocarbon compounds may be fluorine-containing, halogen-containing, oxygen-containing, silicon-containing, hydroxyl-containing, and boron-containing derivatives of hydrocarbon compounds.

[0226] In another embodiment, the hydrocarbon compound is a cyclic hydrocarbon (e.g., methylcyclohexane), a substituted aromatic hydrocarbon (e.g., halo-substituted benzene, amine-substituted benzene, C 2-8 Alkyl- or halo- and alkyl-substituted benzenes, such as cumene, aniline, N,N-dimethylaniline, etc., and halocarbons (e.g., C 2-12In some instances, the hydrocarbon is unsubstituted benzene or a C1 alkyl substituted benzene (e.g., toluene, o-xylene, m-xylene, p-xylene). In other instances, the hydrocarbon is a halo-substituted C1 hydrocarbon (e.g., chloroform, methylene chloride). In yet other instances, the hydrocarbon is acetonitrile.

[0227] In some embodiments, the hydrocarbon is an unsaturated hydrocarbon having one or more double or triple bonds. In other embodiments, the hydrocarbon is an unsaturated cyclic hydrocarbon (e.g., cyclopentene, cyclohexene, cycloheptene, fluorene, etc.). In certain embodiments, the hydrocarbon is an alkene having one or more double bonds or an alkyne having one or more triple bonds, and the alkene or alkyne can be linear or cyclic. Exemplary alkenes include ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-nonene, as well as dienes of any of these, and positional isomers, where available, in which the position of the double bond is changed (e.g., a positional isomer of 1-butene can be 2-butene, etc.). Exemplary alkynes include ethyne, propyne, 1-butyne, 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, and 1-nonyne, as well as positional isomers, where available, in which the position of the triple bond is altered (e.g., a positional isomer of 1-butyne can be 2-butyne, etc.).

[0228] Silicon-Containing Precursors In addition, one or more Si-containing precursors can be used to provide molybdenum silicide-containing materials. Such materials may include ternary or quaternary materials such as molybdenum silicide carbide, molybdenum boride silicide, etc. Non-limiting Si-containing precursors may include silane compounds, organosilane compounds, alkylsilane compounds, alkoxysilane compounds, silanol compounds, siloxane compounds, aminosilane compounds, cyclic azasilane compounds, halosilane compounds, inorganic silane compounds, etc. In certain embodiments, the Si-containing precursor may be employed as a reducing agent. In some cases, the Si-containing precursor is employed with a reducing agent, an inert gas, or a combination thereof.

[0229] A common Si-containing precursor is SiR 1 R 2 R 3 R 4 and R 1 , R 2 , R 3 , and R 4 each is independently hydrogen (H), hydroxyl, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0230] In certain embodiments, R 1 , R 2 , R 3 , and R 4is independently alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. 1 , R 2 , R 3 , and R 4 Each of may be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, hydroxyl, thiol, acyloxy, silyl, alicyclic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl, where the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0231] In one example, a non-limiting Si-containing precursor is polysilane (H3Si-(SiH2) n —SiH3), where n ≧ 0. Examples of silanes include silane (SiH4), disilane (Si2H6), trisilane (Si3H8), tetrasilane (Si4H 10 ).

[0232] Organosilanes are SiR 1 R 2 R 3 R 4 where R 1 , R 2 , R 3 , and R 4is independently hydrogen (H), hydroxyl, halo, amine, aminoalkyl, alkoxy, ester, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; and R 1 , R 2 , R 3 , and R 4 At least one of is an organic ligand. Non-limiting organic ligands can include aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. In other embodiments, the organic ligand includes alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, or heteroalkynyl-heteroaryl.

[0233] Non-limiting examples of organosilanes include methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane (SiMe2H2), trimethylsilane (SiMe3H), tetramethylsilane (SiMe4), diethylsilane (SiEt2H2), triethylsilane (SiEt3H), tetraethylsilane (SiEt4), di-t-butylsilane, tributylsilane (SiBu3H), allylsilane, tetraallylsilane (Si[CH2CH=CH2]4), sec-butylsilane, thexylsilane, isoamylsilane, t-butyldisilane, di-t-butyldisilane, cyclopentadienyltrimethylsilane (SiCpMe3), hexamethyldisilane (Si2Me6), silicon acetate (Si[OAc]4, where Ac is acetyl), and the like.

[0234] Alkoxysilanes contain at least one O atom bonded to a Si atom, but may also contain H, N, halogen, or C atoms. Non-limiting alkoxysilanes include R 1 OSiR 2 R 3 R 4 where R 1 is optionally substituted aliphatic or optionally substituted alkyl, and R 2 , R 3 , and R 4 each is independently hydrogen (H), hydroxyl, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0235] Examples of alkoxysilanes include monoalkoxysilanes, dialkoxysilanes, trialkoxysilanes, and tetraalkoxysilanes (H3Si[OR], H2Si[OR]2, HSi[OR]3, and Si[OR]4, respectively, where each R can be independently an alkyl or aryl, which may be substituted), as well as substituted monoalkoxysilanes, dialkoxysilanes, trialkoxysilanes, and tetraalkoxysilanes, such as trimethoxymethylsilane (MeSi[OMe]3), (3-aminomethylsilane (3-aminoethyl ... Examples of silanes include (3-aminopropyl)trimethoxysilane (NH2(CH2)3Si[OMe]3), (3-aminopropyl)triethoxysilane (NH2(CH2)3Si[OEt]3), triethoxyvinylsilane (CH2=CHSi[OEt]3), triethoxyethylsilane (EtSi[OEt]3), trimethoxyphenylsilane (PhSi[OMe]3), isobutyltriethoxysilane (i-BuSi(OCH2CH3)3), diacetoxydimethylsilane (Me2Si(OCOMe)2), etc. Still other examples include trimethoxysilane (HSi[OMe]3), tetramethoxysilane (Si[OMe]4), triethoxysilane (HSi[OEt]3), tetraethoxysilane (TEOS or Si[OEt]4), and tetrabutoxysilane (Si[OBu]4).

[0236] Non-limiting examples of silanols include HOSiR 2 R 3 R 4 where R 2 , R 3 , and R 4 Each of is independently hydrogen (H), hydroxyl, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Non-limiting silanol compounds include tri-t-butoxysilanol ([tBuO]SiOH), tri-t-pentoxysilanol ([EtMeCO]SiOH), and the like.

[0237] Non-limiting examples of siloxanes include R 1 R 2 R 3 Si-O-SiR 4 R 5 R 6 where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 Each of is independently hydrogen (H), hydroxyl, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Non-limiting siloxane compounds include hexachlorodisiloxane (Cl3SiOSiCl3), hexamethylsiloxane (Me3SiOSiMe3), 1,1,3,3-tetramethyldisiloxane (HMe2SiOSiMe2H), and the like.

[0238] Aminosilanes contain at least one N atom bonded to a Si atom, but may also contain H, O, halogen, or C atoms. Non-limiting aminosilanes include R 1 R 2 NSiR 3 R 4 R 5 where R 1 and R2 is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted aromatic, or optionally substituted aryl, and R 3 , R 4 , and R 5 Each of is independently H, hydroxyl, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0239] Examples of aminosilanes are mono-, di-, tri-, and tetraaminosilanes (H3Si[NH2], H2Si[NH2]2, HSi[NH2]3, and Si[NH2]4, respectively), as well as substituted mono-, di-, tri-, and tetraaminosilanes, such as t-butylaminosilane, methylaminosilane, di-sec-butylaminosilane (DSBAS or [(s-Bu)2N]SiH3), H2Si(NR')2 (where R is tBu or Et and R' is H or Et), bis(t-butylamino)silane ([H(t Examples of aminosilanes include bis(diethylamino)silane ([EtN]SiH2), bis(dimethylamino)dimethylsilane ([MeN]SiMe2), hexakis(ethylamino)disilane ([HEtN]Si2), tris(dimethylamino)silane ([MeN]SiH), tetrakis(ethylmethylamino)silane ([MeEtN]Si), 2,2,4,4,6,6-hexamethylcyclotrisilazane (MeH3N3Si3), t-butylsilylcarbamate, SiHMe-(NMe2)2, SiHCl-(NMe2)2, (SiMe2NH)3, etc. A further example of an aminosilane is trisilylamine (N[SiH3]).

[0240] A halosilane contains at least one halogen group and may or may not contain H or C atoms. Non-limiting examples of halosilanes include XSiR 1 R 2 R 3where X is halo and R 1 , R 2 , and R 3 Each of is independently H, hydrogen, halo, amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0241] Examples of halosilanes include iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include tetrachlorosilane (SiCl4), trichlorosilane (SiHCl3), dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, hexyldimethylchlorosilane, hexachlorosilane (Si2Cl6), and benzyltrichlorosilane (SiBzCl3). Specific bromosilanes include tetrabromosilane (SiBr4). Specific iodosilanes include tetraiodosilane, triiodosilane, diiodosilane, monoiodosilane, and trimethylsilyl iodide.

[0242] Boron-Containing Precursors One or more B-containing precursors can be used to provide molybdenum boride-containing materials. Such materials may include ternary or quaternary materials such as molybdenum boride carbide, molybdenum boride silicide, etc. Non-limiting B-containing precursors can include organoborane compounds, boron halide compounds, borate compounds, inorganic boron compounds, etc. In certain embodiments, the B-containing precursor can be employed as a reducing agent.

[0243] Non-limiting examples of organoboranes include BR 1 R 2 R 3 where R 1 , R 2 , and R3 is independently H, hydroxyl, halo, amine, aminoalkyl, alkylamino, alkoxy, ester, amino, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; and R 1 , R 2 , and R 3 At least one of is an organic ligand (e.g., any of those described herein). In certain embodiments, the organic ligand is an optionally substituted alkyl, an optionally substituted aliphatic, an optionally substituted aryl, or an optionally substituted aromatic.

[0244] The organoborane compound can be trimethylborane (BMe3), 1,2-dimethyldiborane ((BH2Me)2), triethylborane (BEt3), triphenylborane (BPh3, where Ph is phenyl), tris(pentafluorophenyl)borane, tetrakis(dimethylamino)diboron (B2[NMe2]4), and the like.

[0245] Non-limiting examples of boron halide compounds include XBR 1 R 2 where X is halo and R 1 and R 2 Each of is independently H, hydroxyl, halo, oxide (=O), amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. The boron halide compound can be boron bromide (e.g., BBr3), boron chloride (e.g., BCl3 or B2Cl4), boron fluoride (e.g., BF or BF3 or B2F4), boron iodide (e.g., BI3), boron monoxide monofluoride (BFO), and the like.

[0246] Non-limiting borate compounds include R 1 OBR 2 R 3 where R 1is H, optionally substituted aliphatic, or optionally substituted aromatic, and R 2 and R 3 Each of is independently H, hydroxyl, halo, oxide (=O), amine, aminoalkyl, alkoxy, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, heteroaromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. The borate compound can be trimethyl borate (B[OMe]3), triethyl borate (B[OEt]3), triisopropyl borate (B[OiPr]3), and the like.

[0247] Non-limiting inorganic boron compounds include BR 1 R 2 R 3 and R 1 , R 2 , and R 3 Each of is independently H, hydroxyl, halo, oxide (=O), NH2, NH, etc. The inorganic boron compound can be borane (BH3), diborane (e.g., B2H6 or B2H4), borazine (H3NBH3), etc.

[0248] Molybdenum-containing layer The Mo-containing layer may include one or more other heteroatoms (e.g., carbon, nitrogen, silicon, boron, oxygen, etc.). In certain embodiments, the layer is a Mo-containing carbon layer, a Mo-containing silicon layer, a Mo-containing boron layer, a Mo-containing carbon-silicon layer, a Mo-containing carbon-boron layer, or a Mo-containing silicon-boron layer, as well as doped forms of any of these. Such Mo-containing layers may include alloys or hybrid forms thereof. Furthermore, the Mo-containing layer may include binary materials (e.g., including Mo and one of C, Si, or B) or ternary materials (e.g., including Mo and two of C, Si, or B). In some embodiments, the Mo-containing layer is amorphous. In other embodiments, the Mo-containing layer is crystalline with a grain size between about 1-3 nm.

[0249] Yet another Mo-containing layer is molybdenum carbide (e.g., MoC y , Mo2C, MoC, or Mox C y ), molybdenum disilicide (e.g., MoSi y , MoSi2, Mo5Si3, Mo3Si, or Mo x S y ), molybdenum borides (e.g., MoB y , MoB2, Mo2B4, or Mo x B y ), molybdenum oxycarbide (e.g., Mo2C y O z Or Mo x C y O z ), molybdenum boride silicide (e.g., Mo5SiB2, MoSi2B, or Mo x S y B z ), molybdenum carbonitride (e.g., MoC y N z Or Mo x C y N z ), molybdenum silicide carbide (e.g., MoSi y C z Or Mo x S y C z ), molybdenum boride carbide (e.g., MoB y C z Or Mo x B y C z ), Molybdenum nitride (MoN y Or Mo x N y ), molybdenum oxynitride (e.g., Mo x O y N z ), where x, y, and z indicate that the stoichiometric ratio of these compounds may vary. In some embodiments, each of x, y, and z may be 0.1 to 10, including whole numbers and decimals therebetween.

[0250] The Mo-containing layer can be employed as a hard mask, an etch stop layer, a conformal layer, or a step coverage layer. The hard mask can include use in a variety of applications such as deep oxide contact etches, DRAM capacitor mold etches, and line or space etches, including etches to form shallow trench isolation structures, gates, and bitlines.

[0251] In certain embodiments, the Mo-containing layer provides a hardmask film where increasing doping with Mo atoms increases cross-linking, which in turn can provide a harder or denser film that provides enhanced etch resistance while remaining removable for semiconductor hardmask applications.

[0252] In another embodiment, the Mo-containing layer provides a conformal film. The degree of conformality of the film may be measured by step coverage. In one embodiment, step coverage is calculated by dividing the average thickness of the deposited film on the sidewalls by the average thickness of the deposited film on the top of the feature and multiplying by 100 to obtain a percentage.

[0253] The Mo-containing layer may also have other useful properties. For example, the Mo-containing layer may be characterized by having a low fluorine content (e.g., about 0-2 atomic %). In another example, the Mo-containing layer may be characterized by having a Mo content of about 5-60 atomic %. In yet another example, the Mo-containing layer may be characterized by having a low hydrogen content (e.g., about 5-12 atomic %).

[0254] The Mo-containing layer may have a reduced compressive film stress. In one example, the stress may be about 10-20 MPa. In certain embodiments, the overall tensile stress of the Mo-containing layer may be less than about 1 GPa.

[0255] The Mo-containing layer can have any useful thickness, such as from about 10 Å to 10 μm. In other embodiments, the thickness is from about 10 to 30 Å. In other embodiments, the thickness is from about 200 Å to 10 μm. In yet other embodiments, the thickness is from about 100 Å to 2 μm. In various embodiments, the Mo-containing layer is between about 150 to 300 Å thick.

[0256] Mo-containing layers may be characterized by high etch selectivity, which may, for example, allow for thinner masks with improved etch margins.

[0257] interfacial layer The interface layer may comprise any useful material, including, but not limited to, pure boron (B), pure carbon (C), titanium (Ti), titanium nitride (TiN), titanium aluminide (TiAl), titanium silicide (TiSi), titanium carbide (TiC), tungsten (W), tungsten nitride (WN), tungsten carbonitride (WCN), tantalum nitride (TaN), nickel (Ni), nickel silicide (NiSi), nickel nitride (NiN), molybdenum carbide (MoC), molybdenum nitride (MoN), and the like. x ), molybdenum oxynitride layer (MoO x N y ), and the like, as well as combinations thereof. Still other materials can include dielectric and conductive layers, such as silicon oxides, silicon nitrides, silicon carbides, metal oxides, metal nitrides, metal carbides, and metal layers.

[0258] The interfacial layer may comprise any useful thickness, such as from about 10 Å to 100 nm. In use, the interfacial layer may be employed as a diffusion barrier, an adhesion layer, a barrier layer, a nucleation layer, or a combination thereof.

[0259] The method of providing the interfacial layer includes vapor deposition of a precursor for providing the interfacial layer. The interfacial layer can be deposited on the surface portion or the pre-treated surface of the substrate. In one example, the interfacial layer includes a metal nitride, where the deposition includes the use of a suitable metal (M)-containing precursor with a suitable nitrogen (N)-containing precursor. For other compositions in the interfacial layer, other precursors can be employed, such as a C-containing precursor with an M-containing precursor for a metal carbide, an O-containing precursor with an M-containing precursor for a metal oxide, an O-containing precursor and an N-containing precursor with an M-containing precursor for a metal oxynitride, an O-containing precursor with an Si-containing precursor for a silicon oxide, etc. In other embodiments, the pure boron layer includes deposition of any B-containing precursor described herein, and the pure carbon layer includes deposition of any C-containing precursor described herein.

[0260] Non-limiting examples of M-containing precursors include MX n and the like, where M is a metal, each X is independently halo, and n is selected from 2 to 6. Still other non-limiting metal-containing precursors include metal halides such as ML n and the like, where M is a metal and each L is independently hydrogen (H), halo, oxide (=O), imide, (=NR 1 ), carbonyl (CO), amine (NR 1 R 2 ), an organic ligand, a monodentate ligand, or a bidentate ligand (e.g., any of those described herein), and n is selected from 2 to 6. M can be any metal atom in the interfacial layer, such as titanium (Ti), tungsten (W), tantalum (Ta), nickel (Ni), and molybdenum (Mo).

[0261] Non-limiting Si-containing precursors include any of those described herein, such as tetraethoxysilane (Si(OEt)4 or TEOS). Non-limiting C-containing precursors include any of those described herein, including acetylene (C2H2).

[0262] Non-limiting N-containing precursors include any of those described herein, including ammonia (NH3), nitrogen (N2), hydrazine (N2H4), amines, and aminosilanes. Non-limiting amines include methylamine, dimethylamine, ethylmethylamine, ethylamine, isopropylamine, t-butylamine, di-t-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-t-butylhydrazine, and aromatics containing amines such as aniline, pyridine, and benzylamine. Still other N-containing precursors can include nitriles (e.g., acetonitrile), amides, N-containing heterocyclic compounds, or aminoalcohols (e.g., ethanolamine). The amines can be primary, secondary, tertiary, or quaternary (e.g., tetraalkylammonium compounds). The N-containing precursor may contain heteroatoms other than N, for example, hydroxylamine, t-butyloxycarbonylamine, and Nt-butylhydroxylamine are N-containing precursors.

[0263] Non-limiting O-containing precursors include any of those described herein, including oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), water (H2O), hydrogen peroxide (H2O2), alcohols (e.g., t-amyl alcohol, ethanol, propanol, etc.), polyols (e.g., diols such as ethylene glycol), ketones, aldehydes, ethers, esters, carboxylic acids, alkoxysilanes, oxolanes, or furans.

[0264] Material layers and substrates (including stacks thereof) The material layer can include any useful material, including oxide materials, nitride materials, dielectric materials, metal layers, semiconductor materials, and combinations thereof, that can be used to form semiconductor devices (e.g., metal contacts, trench isolation, gates, bitlines, or any other interconnect features).

[0265] Non-limiting materials may include dielectric materials such as silicon oxide (e.g., SiO), silicon nitride (e.g., Si3N4), silicon oxynitride, silicon carbide, silicon oxycarbide, titanium nitride, hafnium dioxide (HfO2), zirconium dioxide (ZrO2), hafnium silicon oxide (HfSiO2), hafnium aluminum oxide (HfAlO), zirconium silicon oxide (ZrSiO2), tantalum dioxide (TaO2), aluminum oxide, aluminum doped hafnium dioxide, bismuth strontium titanium (BST), platinum zirconium titanium (PZT), as well as composites, alloys, or doped forms thereof. In other embodiments, the material is a high-k material, e.g., one having a dielectric constant greater than 4.

[0266] Still other non-limiting materials include conductive materials such as materials containing silicon (e.g., polysilicon, doped silicon such as n-type or p-type doped silicon, tungsten silicide (WSi), tungsten polysilicon (W / poly), etc. Other materials include those having titanium (Ti), hafnium (Hf), vanadium (V), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), iron (Fe), ruthenium (Ru), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), gold (Ag), silver (Au), aluminum (Al), alloys thereof, nitride compounds thereof, combinations thereof, and the like.

[0267] The methods and layers herein can be employed for any useful stack. In one embodiment, the stack includes a stair-like structure in a three-dimensional (3D) stack. In another embodiment, the stack includes one or more high aspect ratio (HAR) features, for example, greater than 20:1, disposed on a substrate. Other features may be present in the stack, such as trenches, vias, etc. In some cases, the features are formed by the use of the Mo-containing layers described herein.

[0268] The Mo-containing layers herein can be employed to provide any useful stack, film, or device. For example, etch selectivity may be important for the patterning of new generation NAND and dynamic random access memory (DRAM) devices, and the present disclosure encompasses the use of Mo-containing layers to form such devices. Still other devices may include those for VNAND or vertically integrated memory (VIM) applications, as well as magnetic random access memory (MRAM) and phase change random access memory (PCRAM) applications.

[0269] The material layers can have any useful thickness. In some embodiments, the material layers can include one type of material, or two or more different types of materials. In certain embodiments, the material layers can include alternating sublayers. The material layers or sublayers of material can have any useful thickness, such as 10 Å to 2000 Å for each layer or sublayer, or for the total thickness of all layers / sublayers.

[0270] In various embodiments, the material layer is between about 50-500 nm thick for 3D NAND applications. The critical dimension of the features etched into the material layer depends on the application. In some embodiments, the features have a critical dimension between about 50-120 nm for 3D NAND applications. In some embodiments, the features have a critical dimension between about 16-22 nm for DRAM applications. In other embodiments, the features include constrictions, pillars, trenches, voids, etc., which can be optionally filled later (e.g., to provide wordlines, etc.).

[0271] The substrate can include any useful material. In various embodiments, the substrate has a dielectric layer thereon that includes an oxide surface. The substrate can be a silicon wafer, such as a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, including a wafer having one or more layers of materials, such as dielectric, conductive, or semiconductive materials, deposited thereon. Non-limiting examples of layers include dielectric and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0272] In various embodiments, the substrate is patterned. The patterned substrate may have "features" such as pillars, poles, trenches, vias, or contact holes, and the features may be characterized by one or more of a narrow or reentrant opening, a constriction inside the feature, and a high aspect ratio. The feature(s) may be formed in one or more of the layers above. For example, the feature may be formed at least partially in a dielectric layer. In some embodiments, the 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 more. One example of a feature is a hole or via in a semiconductor substrate or a layer on the substrate.

[0273] In some embodiments, features may be formed in one or more of the top layers of the substrate such that the bottom of the feature is an exposed underlying layer. One example of a feature is a pillar or pole in a semiconductor substrate or a layer on the substrate. Another example is a trench in the substrate or layer. In various embodiments, the feature may have an underlying layer such as a barrier layer or an adhesion layer. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0274] Device The methods and layers herein can be formed, deposited, and processed using an apparatus. In one example, an apparatus for providing a Mo-containing layer includes a process chamber including a substrate holder, a process gas source coupled to the process chamber and associated flow control hardware, and substrate processing hardware connected to the process chamber.

[0275] The processing chamber and substrate holder can be configured for any useful deposition process. Such deposition processes can include ALD, CVD, and plasma-assisted forms thereof. Optionally, the processing chamber can be an ICP chamber or a CCP chamber. The substrate holder can be, for example, an electrostatic chuck (ESC) having at least one clamping electrode for holding a substrate under a showerhead assembly within the processing chamber. The ESC can be configured for use as a cathode. The substrate holder can be optionally heated.

[0276] Additionally, the process gas source can be configured to provide any of the precursors herein as a gas, such as a Mo-containing precursor, a C-containing precursor, a Si-containing precursor, a B-containing precursor, or combinations thereof. The gas source can optionally be connected to the processing chamber via a showerhead assembly.

[0277] The apparatus can further include a plasma source that can be connected to the processing chamber and / or associated flow control hardware. The plasma source can be configured to deliver plasma to the processing chamber. The plasma can optionally be a remote plasma source coupled to the processing chamber or showerhead assembly via a matching network.

[0278] In certain embodiments, the apparatus further includes a controller having a processor and a memory, the processor and the memory being communicatively connected to each other, the processor being at least operatively connected to the flow control and substrate processing hardware, and the memory storing computer-executable instructions for performing the operations described in any of the methods described herein. For example, the controller can be configured to control the flow control hardware and the plasma source, the control providing instructions for exposing the substrate to a Mo-containing precursor and one or more deposition precursors in the processing chamber, exposing the substrate to the precursor, providing a plasma to the processing chamber, and causing deposition of a Mo-containing layer on a top surface portion of the substrate.

[0279] 4 illustrates generally one embodiment of a process station 400 that may be used to deposit material using ALD and / or CVD, either of which may be plasma-assisted. For simplicity, the process station 400 is depicted as a stand-alone process station having a processing chamber body 402 for maintaining a low pressure environment. However, it will be understood that multiple process stations 400 may be included in a common process tool environment. Additionally, it will be understood that in some embodiments, one or more hardware parameters of the process station 400, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers.

[0280] The process station 400 is in fluid communication with a reactant delivery system 401 for delivering process gases to a distribution showerhead 406. The reactant delivery system 401 includes a mixing vessel 404 for combining and / or conditioning the process gases for delivery to the showerhead 406. One or more mixing vessel inlet valves 420 may control the introduction of process gases to the mixing vessel 404. Similarly, a showerhead inlet valve 405 may control the introduction of process gases to the showerhead 406.

[0281] Some reactants, such as BTBAS, may be stored in liquid form prior to vaporization at the process station and subsequent delivery to the process station. For example, the embodiment of FIG. 4 includes a vaporization point 403 for vaporizing the liquid reactant to be delivered to the mixing vessel 404. In some embodiments, the vaporization point 403 may be a heated vaporizer. The reactant vapor generated from such a vaporizer may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may also generate small particles. These small particles may clog piping, interfere with valve operation, contaminate the substrate, etc. Some approaches to address such issues include cleaning and / or evacuating the delivery piping to remove residual reactants. However, cleaning the delivery piping may increase the cycle time of the process station and reduce the throughput of the process station. Thus, in some embodiments, the delivery piping downstream of the vaporization point 403 may be heat traced. In some examples, the mixing vessel 404 may also be heat traced. In one non-limiting example, the piping downstream of the vaporization point 403 has an increasing temperature profile extending from about 100° C. to about 150° C. at the mixing vessel 404 .

[0282] In some embodiments, the reactant liquid may be vaporized in a liquid injector. For example, the liquid injector may inject a pulse of liquid reactant into the carrier gas stream upstream of the mixing vessel. In one scenario, the liquid injector may vaporize the reactant by rapidly depressurizing the liquid from a higher pressure to a lower pressure. In another scenario, the liquid injector may atomize the liquid into dispersed microdroplets that are then vaporized in a heated delivery tubing. It will be appreciated that smaller droplets may vaporize faster than larger droplets, reducing the delay between injection and complete vaporization of the liquid. Faster vaporization may reduce the length of tubing downstream from the vaporization point 403. In one scenario, the liquid injector may be attached directly to the mixing vessel 404. In another scenario, the liquid injector may be attached directly to the showerhead 406.

[0283] In some embodiments, a liquid flow controller may be provided upstream of the vaporization point 403 to control the mass flow rate of the liquid for vaporization and delivery to the process station 400. For example, the liquid flow controller (LFC) may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take more than a second to stabilize the liquid flow using feedback control. This may extend the time to add the 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, the LFC may be dynamically switched from the feedback control mode to the direct control mode by disabling the sense tubes of the LFC and the PID controller.

[0284] 4, the substrate 412 is shown as being located below the showerhead 406 and resting on a pedestal 408. It will be understood that the showerhead 406 may have any suitable shape and any suitable number and arrangement of ports for delivering process gases to the substrate 412.

[0285] In some embodiments, a microvolume 407 is located under the showerhead 406. Performing ALD and / or CVD processes in a microvolume rather than in the full volume of the process station may reduce reactant exposure and sweep times, reduce the time to change process conditions (e.g., pressure, temperature, etc.), limit exposure of the process station robot to process gases, etc. Example sizes of the microvolume include, but are not limited to, volumes between 0.1 liters and 2 liters. This microvolume also impacts productivity throughput. While the deposition rate per cycle is reduced, the cycle time is simultaneously reduced. In certain cases, the latter effect is dramatic enough to improve the overall throughput of the module for a given target film thickness.

[0286] In some embodiments, the substrate holder (e.g., pedestal 408) may be raised and lowered to expose the substrate 412 to the microvolume 407 and / or to change the volume of the microvolume 407. For example, during a substrate transfer phase, the pedestal 408 may be lowered to allow the substrate 412 to be loaded onto the pedestal 408. During a deposition process phase, the pedestal 408 may be raised to position the substrate 412 within the microvolume 407. In some embodiments, the microvolume 407 may completely surround not only the substrate 412, but also a portion of the pedestal 408, forming an area of ​​high flow impedance during the deposition process.

[0287] Optionally, the pedestal 408 may be lowered and / or raised during portions of the deposition process to adjust the process pressure, reactant concentration, etc., in the microvolume 407. In one scenario where the processing chamber body 402 remains at base pressure during the deposition process, lowering the pedestal 408 may allow the microvolume 407 to be evacuated. Example ratios of the microvolume to the processing chamber volume include, but are not limited to, volume ratios between 1:500 and 1:10. It will be appreciated that in some embodiments, the height of the pedestal may be adjusted programmatically by a suitable computer controller.

[0288] In another scenario, the plasma density may be varied during plasma activation and / or treatment cycles involved in the deposition process by adjusting the height of the pedestal 408. At the end of the deposition process stage, the pedestal 408 may be lowered during another substrate transfer stage to allow removal of the substrate 412 from the pedestal 408.

[0289] While the examples of microvolume variation described herein refer to a height adjustable pedestal, it will be understood that in some embodiments, the position of the showerhead 406 may be adjusted relative to the pedestal 408 to vary the volume of the microvolume 407. Further, it will be understood that the vertical position of the pedestal 408 and / or the showerhead 406 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 408 may include a rotation axis for rotating the orientation of the substrate 412. It will be understood that in some embodiments, one or more of these examples of adjustments may be performed programmatically by one or more suitable computer controllers.

[0290] Returning to the embodiment shown in FIG. 4, the showerhead 406 and pedestal 408 are in electrical communication with an RF power source 414 and a matching network 416 to provide power to the plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 414 and the matching network 416 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers are included above. Similarly, the RF power source 414 may provide RF power of any suitable frequency. In some embodiments, the RF power source 414 may be configured to control high and low frequency RF power sources independently of each other. Examples of low frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 1000 kHz. Examples of high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be adjusted discretely or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be pulsed intermittently to reduce ion bombardment with the substrate surface compared to a continuously powered plasma.

[0291] In some embodiments, the plasma may be monitored in situ by one or more plasma monitors. In one scenario, the plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, the 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 to provide programmatic control of the 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.

[0292] In some embodiments, the plasma may be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting plasma conditions for a plasma process stage may be included in a corresponding plasma activation recipe stage of a deposition process recipe. In some cases, the process recipe stages may be sequentially arranged such that all instructions for a deposition process stage are executed simultaneously with that process stage. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe stage preceding the plasma process stage. For example, a first recipe stage may include instructions for setting flow rates of an inert gas and / or a reactive gas, instructions for setting a plasma generator to a power set point, and a time delay instruction for the first recipe stage. A second subsequent recipe stage may include instructions for enabling the plasma generator and a time delay instruction for the second recipe stage. A third recipe stage may include instructions for disabling the plasma generator and a time delay instruction for the third recipe stage. It will be understood that these recipe stages may be further subdivided and / or repeated in any suitable manner within the scope of the present disclosure.

[0293] In some deposition processes, the plasma strike lasts for a duration of approximately several seconds or more. In certain implementations, much shorter plasma strikes may be used. These may be on the order of 10 ms to 1 second, typically about 20-80 ms, with a specific example being 50 ms. Such very short RF plasma strikes require the plasma to stabilize very quickly. To achieve this, the plasma generator may be configured to allow the frequency to float while the impedance match is preset to a particular voltage. Conventionally, high frequency plasmas are generated at an RF frequency of approximately 13.56 MHz. In various embodiments disclosed herein, the frequency can float to values ​​different from this standard value. By floating the frequency while fixing the impedance match to a predetermined voltage, the plasma can be stabilized much more quickly, which may be important when using the very short plasma strikes associated with some types of deposition cycles.

[0294] In some embodiments, the pedestal 408 may be temperature controlled via a heater 410. Additionally, in some embodiments, pressure control of the deposition process station 400 may be provided by a butterfly valve 418. As shown in the embodiment of FIG. 4, the butterfly valve 418 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the process station 400 may also be adjusted by varying the flow rate of one or more gases introduced to the process station 400.

[0295] FIG. 5 shows a schematic diagram of an embodiment of a multi-station processing tool 500 having an inbound load lock 502 and an outbound load lock 504, either or both of which may include a remote plasma source. A robot 506 is configured to move a wafer from a cassette loaded via a pod 508 to the inbound load lock 502 via an atmospheric port 510 at atmospheric pressure. The wafer is placed on a pedestal 512 in the inbound load lock 502 by the robot 506, the atmospheric port 510 is closed, and the load lock is pumped down. If the inbound load lock 502 includes a remote plasma source, the wafer may be exposed to a remote plasma process in the load lock before being introduced to the process chamber 514. Additionally, the wafer may also be heated in the inbound load lock 502 as well, for example, to remove moisture and adsorbed gases. The chamber transfer port 516 to the processing chamber 514 is then opened and another robot (not shown) places the wafer into the reactor and places it on the pedestal of the first station shown in the reactor for processing. Although the embodiment depicted in Figure 5 includes a load lock, it will be understood that in some embodiments the wafer may enter the process station directly.

[0296] The depicted processing chamber 514 includes four process stations, numbered 1 through 4 in the embodiment shown in FIG. 5. Each station has a heated pedestal (shown at 518 for station 1) and a gas line inlet. It will be understood that in some embodiments, each process station may have different or multiple purposes. Although the depicted processing chamber 514 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments, a processing chamber may have three or fewer stations.

[0297] FIG. 5 also illustrates an embodiment of a wafer processing system 590 for transporting wafers within the processing chamber 514. In some embodiments, the wafer processing system 590 may transport wafers between various process stations and / or between process stations and load locks. It will be understood that any suitable wafer processing system may be employed. Non-limiting examples include a wafer carousel and a wafer handling robot. FIG. 5 also illustrates an embodiment of a system controller 550 employed to control process conditions and hardware states of the process tool 500. The system controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0298] In some embodiments, the system controller 550 controls all of the activity of the process tool 500. The system controller 550 executes system control software 558 stored in the mass storage device 554, loaded into the memory device 556, and executed on the processor 552. The system control software 558 may include instructions for controlling the timing, mixture of gases, chamber and / or station pressure, chamber and / or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequency, substrate, pedestal, chuck and / or susceptor position, and other parameters of a particular process performed by the process tool 500. The system control software 558 may be configured in any suitable manner. For example, subroutines or control objects of the various process tool components may be written to control the operation of the process tool components necessary to perform the processes of the various process tools in accordance with the disclosed methods. The system control software 558 may be coded in any suitable computer readable programming language.

[0299] In some embodiments, the system control software 558 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each step of a plasma-assisted process (e.g., a plasma enhanced atomic layer deposition (PEALD) process) may include one or more instructions for execution by the system controller 550. Instructions for setting process conditions for a PEALD process step may be included in a corresponding PEALD recipe step. In some embodiments, the PEALD recipe steps may be arranged sequentially, such that all instructions for a PEALD process step are executed simultaneously with that process step.

[0300] Other computer software and / or programs stored on the mass storage device 554 and / or memory device 556 associated with the system controller 550 may also be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0301] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal 518 and control the spacing between the substrate and other parts of the process tool 500 .

[0302] The process gas control program may include code for controlling gas composition and flow rates, and optionally flowing gases into one or more process stations prior to deposition to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rates within any of the disclosed ranges. The pressure control program may include code for controlling pressure within the process station, for example, by adjusting a throttle valve in the exhaust system of the process station, gas flow into the process station, etc. The pressure control program may include code for maintaining pressure within the process station within any of the disclosed pressure ranges.

[0303] The heater control program may include code for controlling current to a heating unit used to heat the substrate. Alternatively, the heater control program may control the delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions for maintaining the temperature of the substrate within any of the disclosed ranges.

[0304] The plasma control program may include code for setting the RF power levels and frequencies applied to the process electrodes of one or more process stations, for example, using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure.

[0305] In some embodiments, there may be a user interface associated with the system controller 550. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0306] In some embodiments, the parameters adjusted by the system controller 550 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (RF power levels, frequency, and exposure time), etc. These parameters may be provided to a user in the form of a recipe or may be entered using a user interface.

[0307] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 550 from various process tool sensors. Signals for controlling the process may be output at analog and digital output connections of the process tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

[0308] Any suitable chamber may be used to carry out the disclosed embodiments. Examples of deposition equipment include, but are not limited to, equipment from the ALTUS® product family, VECTOR® product family, and / or SPEED® product family, each available from Lam Research Corp., Fremont, Calif., or any of a variety of other commercially available processing systems. Two or more stations may perform the same function. Similarly, two or more stations may perform different functions. Each station may be designed / configured to perform a specific function / method as desired.

[0309] FIG. 6 is a block diagram of a processing system suitable for performing thin film deposition processes according to certain embodiments. System 600 includes a transfer module 603. The transfer module 603 provides a clean, pressurized environment to minimize the risk of contamination of the substrate being processed as it moves between various reactor modules. Two multi-station reactors 609 and 610 are mounted on the transfer module 603, each capable of performing atomic layer deposition (ALD) and / or chemical vapor deposition (CVD) according to certain embodiments. The reactors 609 and 610 may include multiple stations 611, 613, 615, and 617 that may perform operations sequentially or non-sequentially according to the disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets, or a showerhead or distribution plate.

[0310] The transfer module 603 may also be fitted with one or more single or multi-station modules 607 capable of performing plasma or chemical (non-plasma) pre-cleaning or any other process described in connection with the disclosed method. The modules 607 may be used for various processes, in some cases, for example to prepare the substrate for a deposition process. The modules 607 may also be designed / configured to perform various other processes, such as etching or polishing. The system 600 also includes one or more wafer source modules 601 that store wafers before and after processing. An atmospheric robot (not shown) in the atmospheric transfer chamber 619 may first retrieve the wafer from the source module 601 to a load lock 621. A wafer transfer device (typically a robot arm unit) in the transfer module 603 moves the wafer from the load lock 621 to and between modules mounted in the transfer module 603.

[0311] In various embodiments, a system controller 629 is employed to control process conditions during deposition. The controller 629 typically includes one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0312] The controller 629 may control all of the deposition apparatus activities. The system controller 629 executes system control software that includes sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored in memory devices associated with the controller 629 may also be employed in some embodiments.

[0313] Typically, there is a user interface associated with the controller 629. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0314] The system control logic may be configured in any suitable manner. In general, logic may be designed or configured in hardware and / or software. Instructions for controlling the drive circuits may be hard-coded or provided as software. Instructions may be provided by "programming." Such programming is understood to include any form of logic, including hard-coded logic in digital signal processors, application specific integrated circuits, and other devices that implement specific algorithms as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. The system control software may be coded in any suitable computer readable programming language.

[0315] Computer program code for controlling the Mo-containing precursor flows, deposition precursor(s), reactant gas flows, reducing agent flows, carrier gas flows, and other processes in the process sequence can be written in any conventional computer readable programming language, such as assembly language, C, C++, Pascal, Fortran, etc. Compiled object code or scripts are executed by a processor to perform the tasks specified in the program. Also, as shown, the program code may be hard coded.

[0316] The controller parameters relate to process conditions such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters may be provided to a user in the form of a recipe and entered using a user interface. Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 629. Signals for controlling the process are output at analog and digital output connections of the deposition apparatus 600.

[0317] The system software may be designed or configured in many different ways. For example, various chamber component subroutines or control objects may be written to control the operation of the chamber components necessary to perform a deposition process (and possibly other 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.

[0318] In some implementations, the controller 629 is part of a system, which may be part of the examples described above. Such a system may include semiconductor processing equipment including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as a "controller" and may control various components or subparts of one or more systems. Depending on the processing requirements and / or type of system, the controller 629 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow settings, liquid delivery settings, position and motion settings, loading and unloading of wafers into and out of the tool, and loading and unloading of wafers into and out of other transport tools and / or load locks connected or interlocked with the particular system.

[0319] Broadly speaking, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps during the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0320] The controller may be part of or connected to a computer that is integrated into the system, connected to the system, otherwise networked to the system, or a combination thereof, in some embodiments. For example, the controller may be all or part of a "cloud", i.e., fab host computer system, which allows remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, examine trends or performance criteria from multiple manufacturing operations, change parameters of a current process, set processing steps to track a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows for entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool the controller is configured to interface with or control. Thus, as discussed above, the controller may be distributed, such as by including one or more individual controllers networked together and operating toward a common purpose, such as the processes and controls described herein. One example of a distributed controller for such purposes is one or more integrated circuits on the chamber that are located remotely (e.g., at the platform level or as part of a remote computer) and communicate with one or more integrated circuits that cooperatively control the processes in the chamber.

[0321] Examples of systems may include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0322] As described above, depending on the process step or steps being performed by the tool, the controller may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used to transport materials to and from containers of wafers to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0323] conclusion Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be implemented within the scope of the appended claims. The embodiments disclosed herein may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. Furthermore, while the disclosed embodiments are described in conjunction with specific embodiments, it will be understood that it is not intended to limit the specific embodiments to the disclosed embodiments. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Thus, the present embodiments are considered to be illustrative and not restrictive, and the present embodiments are not limited to the details given herein.

Claims

1. 1. A method for providing a metal-containing layer, comprising the steps of: Providing a substrate on a substrate holder in a processing chamber; exposing a top surface portion of the substrate to a molybdenum-containing precursor and one or more optional deposition precursors; depositing a metal-containing layer on the top surface portion of the substrate in the processing chamber with or without a plasma; Including, The method, wherein the metal-containing layer optionally comprises a molybdenum-containing layer or a molybdenum-doped layer.

2. 10. The method of claim 1, wherein the exposing further comprises delivering a reactive gas, a reducing agent, or a carrier gas to the processing chamber; The method, wherein the reducing agent optionally comprises water, an alcohol, H2S, a hydrocarbon, a thiol, or a combination thereof.

3. 10. The method of claim 1 , further comprising, prior to said depositing: providing an interfacial layer on the top surface portion of the substrate, whereby after said depositing, said interfacial layer is disposed between the substrate and the metal-containing layer. Further comprising: the interface layer comprises an adhesion layer, an initiation layer, or a growth layer; The interfacial layer optionally comprises boron (B), carbon (C), titanium (Ti), tungsten (W), tantalum (Ta), nickel (Ni), molybdenum (Mo), a nitride thereof, a silicide thereof, an oxynitride thereof, a carbide thereof, or a carbonitride thereof. ,method.

4. 10. The method of claim 1 , further comprising, prior to said depositing: pre-treating the top surface portion of the substrate to provide a pre-treated surface disposed between the substrate and the metal-containing layer after the depositing. The method further comprising:

5. 2. The method of claim 1 , wherein the substrate further comprises a material layer disposed on the top surface portion of the substrate, and the depositing comprises depositing the metal-containing layer on the top surface portion of the material layer; Optionally, the method wherein the material layer comprises at least one of an oxide or a nitride.

6. 1. A method for providing a metal-containing layer, comprising the steps of: Providing a substrate in a processing chamber; depositing a molybdenum-containing layer on a surface portion of the substrate by a plasma enhanced chemical vapor deposition (PECVD) process; A method comprising:

7. 1. A method for processing a substrate, comprising: depositing a molybdenum-containing layer on an upper surface portion of a substrate; forming a defined pattern in the molybdenum-containing layer; transferring the defined pattern to a material layer disposed below the molybdenum-containing layer; A method comprising:

8. 8. The method of claim 7, wherein the depositing comprises: forming the molybdenum-containing layer by exposing the top surface portion of the substrate to a molybdenum-containing precursor and one or more optional deposition precursors. Including, Additionally, optionally, (i) the exposing comprises sequentially delivering the molybdenum-containing precursor and the one or more optional deposition precursors, and optionally further comprising at least one of purging after delivery of the molybdenum-containing precursor or after delivery of the one or more optional deposition precursors; (ii) said exposing comprises simultaneously delivering said molybdenum-containing precursor and said one or more optional deposition precursors; (iii) the exposing step further comprises delivering a reactive gas, a reducing agent, or an inert gas, comprising one of (i) to (iii).

9. 8. The method of claim 7, wherein forming the defined pattern comprises: depositing a resist layer on an upper surface portion of the molybdenum-containing layer to form a patterned resist mask; transferring the pattern of the resist mask onto the top surface portion of the molybdenum-containing layer to form a hard mask having one or more openings to provide the defined pattern; Including, Optionally, transferring the defined pattern comprises: etching the layer of material through the one or more openings in the hard mask.

10. 8. The method of claim 7, further comprising the steps of: providing an interfacial layer on the top surface portion of the substrate, thereby disposing the interfacial layer between the substrate and the molybdenum-containing layer; Further comprising: the interface layer comprises an adhesion layer, an initiation layer, or a growth layer; Optionally, the interfacial layer comprises boron (B), carbon (C), titanium (Ti), tungsten (W), tantalum (Ta), nickel (Ni), molybdenum (Mo), a nitride thereof, a silicide thereof, an oxynitride thereof, a carbide thereof, or a carbonitride thereof. ,method.

11. 11. The method of claim 10, further comprising the steps of: prior to transferring the defined pattern to the material layer; Etching the interfacial layer through the defined pattern in the molybdenum-containing layer. The method further comprising:

12. 8. The method of claim 7, further comprising the steps of: pre-treating the top surface portion of the substrate to provide a pre-treated surface disposed between the substrate and the molybdenum-containing layer. Further comprising: Optionally, prior to transferring the defined pattern into the material layer, and etching the pre-treated surface through the defined pattern in the molybdenum-containing layer. ,method.

13. 1. A method for processing a substrate, comprising: providing a substrate having a layer of material disposed on a top surface portion of the substrate; depositing a molybdenum-containing layer on an upper surface portion of the material layer, the depositing comprising delivering a molybdenum-containing precursor and one or more optional deposition precursors; forming a patterned mask over the molybdenum-containing layer; forming a defined pattern in the molybdenum-containing layer by transferring a pattern of the patterned mask to the molybdenum-containing layer; transferring the defined pattern into the layer of material; A method comprising:

14. 14. The method of claim 13, wherein the one or more optional deposition precursors are: (i) a carbon-containing precursor, optionally comprising at least one of a hydrocarbon, methane (CH4), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), propyne (C3H4), allene (C3H4), cyclopropene (C3H4), butane (C4H10), cyclohexane (C6H12), benzene (C6H6), or toluene (C7H8); (ii) a silicon-containing precursor, optionally comprising a silane compound, an organosilane compound, an alkylsilane compound, an alkoxysilane compound, a silanol compound, a siloxane compound, an aminosilane compound, a cyclic azasilane compound, a halosilane compound, or an inorganic silane compound; and (iii) a boron-containing precursor, optionally wherein the boron-containing precursor is selected from the group comprising an organoborane compound, a boron halide compound, a borate compound, or an inorganic boron compound.

15. 14. The method of claim 13, wherein the molybdenum-containing precursor comprises an organo-molybdenum compound, a molybdenum halide compound, a molybdenum oxyhalide compound, an inorganic molybdenum compound, or a compound comprising a structure having one of formulas (I)-(V) or a salt thereof. MoL n (I) wherein each L is independently hydrogen (H), halo, oxide (=O), imide (=NR 1 ), carbonyl (CO), amine (NR 1 R 2 ), an organic ligand, a monodentate ligand, or a bidentate ligand; n is selected from 2 to 6; and R 1 and R 2 are each independently aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. Mo(X) m (L) n (II) wherein each X is independently halo, oxide (=O), imide (=NR 1 ), or carbonyl (CO); Each L is an organic ligand; R 1 is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic; m is selected from 0 to 6; and n is selected from 0 to 6, and at least one of m and n is not 0. Mo 2 L n (III) wherein each L is a bidentate ligand, and n is selected from 2 to 5. Mo(L1) m () n () p () wherein each L1 is independently a bidentate ligand; each L2 is independently a neutral ligand; Each X is independently an anionic ligand; m is selected from 1 to 3; n is selected from 0 to 4; and p is selected from 0 to 4. Mo(X) m (L) n (V) wherein each X is independently halo; Each L is an organic ligand; m is selected from 1 to 6; and n is selected from 1 to 4.

16. 14. The method of claim 13, wherein the molybdenum-containing layer is Mo x C y , Mo x S y , Mo x B y , Mo x C y O z , Mo x S y B z , Mo x C y N z , Mo x S y C z , Mo x B y C z , Mo x N y , or Mo x O y N z Including, The molybdenum-containing layer is a hard mask, an etch stop layer, a conformal layer, or a step coverage layer. ,method.

17. 14. The method of claim 13, comprising at least one of: (i) the molybdenum-containing layer having a low fluorine content; (ii) the molybdenum-containing layer having a low stress; and (iii) the molybdenum-containing layer comprising a high etch selectivity.

18. 1. An apparatus for processing a substrate, comprising: a processing chamber including a substrate holder; a process gas source connected to the processing chamber and associated flow control hardware; substrate processing hardware coupled to the processing chamber; a controller having a processor and a memory; Including, the processor and the memory are communicatively coupled to each other, the processor is operatively coupled to at least the flow control hardware and the substrate processing hardware, and the memory stores computer-executable instructions for performing the operations recited in the method of claim 1; The computer executable instructions further comprising: exposing a top surface portion of a substrate to a molybdenum-containing precursor and one or more deposition precursors in the processing chamber; and depositing a metal-containing layer or a molybdenum-containing layer on the top surface portion of the substrate; comprising instructions configured to: Device.

19. 20. The apparatus of claim 18, a plasma source coupled to the processing chamber Further comprising: The computer executable instructions further comprising: exposing a top surface portion of a substrate to a molybdenum-containing precursor and one or more deposition precursors in the processing chamber; providing a plasma to the processing chamber; and depositing a metal-containing layer or a molybdenum-containing layer on the top surface portion of the substrate; comprising instructions configured to: Device.

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