Attorney Docket No. LAM1P018WO-11683-1WO CONVERSION OF ORGANOMETAL FILMS USING OXIDANTS FOR BEOL METALLIZATION INCORPORATION BY REFERENCE [0000] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in its entirety and for all purposes. BACKGROUND [0001] Semiconductor fabrication processes involve metallization during back-end-of-line (“BEOL”) processing for logic. Contacts may be formed by depositing conductive interconnect material in an opening on the surface of insulating material disposed between two spaced apart conductive layers. Interconnect materials may be made of aluminum, copper or other metals. Copper may provide a lower electrical resistivity than aluminum. However, copper suffers from diffusion, resulting in the formation of undesirable intermetallic alloys, which can negatively affect resistivity. [0002] In part, copper diffusion may occur when processes for metal deposition using chlorine- containing metal precursors are employed under certain conditions, as such processes may lead to the formation of leachable copper chloride byproducts, thus potentially damaging the copper layer on the substrate. In some circumstances a solution may be to utilize a barrier material such as tantalum nitride to shield the copper layer. However, conventional tantalum nitride barrier layer deposition processes are non-selective and can potentially result in elevated resistance. An alternative to chlorine-containing metal precursors is the use of metal precursors having direct carbon-metal and/or carbon-nitrogen bonds. Yet the highly stable carbides or nitrides deposited present certain challenges during post-processing reduction to metal. Therefore, a selective and efficient metal deposition process which can minimize or prevent negative interactions associated with use of some types of chlorine-free metal precursors on interconnects, would be advantageous. [0003] The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as art against the present disclosure. SUMMARY [0004] The present disclosure relates to apparatuses and methods for depositing metals on
Attorney Docket No. LAM1P018WO-11683-1WO interconnects for dual damascene structures in back-end-of-line substrates. The methods include deposition of an organometal-containing film by a chlorine-free organometal precursor on an interconnect, and conversion of the organometal-containing film to a metal oxide with an oxidant. The metal oxide is then reduced to form diffusion layer over the interconnect. The method also includes further metal deposition over the diffusion layer formed by the conversion. The method is useful for atomic layer deposition of transition metals such as molybdenum over copper interconnects; and avoids deleterious effects of chlorine-containing metal precursors to the interconnect. The techniques described can reduce costs, simplify BEOL manufacturing processes and increase performance of semiconductor manufacture. [0005] One aspect of the disclosure relates to a method of depositing a metal film on a substrate. In some embodiments, the method includes providing a substrate in a process chamber, exposing the substrate to a chlorine-free metal precursor to deposit a first metal, oxidizing the first metal with a halogen-free oxidant comprising a second metal to form a metal oxide, where the metal oxide includes the first metal and the second metal, and reducing the metal oxide with a reducing agent to form a metal film. In some embodiments, the metal film includes the first metal and the second metal. [0006] In some embodiments, the first metal comprises a transition metal and the second metal comprises a noble metal. In some embodiments, exposing the substrate to the chlorine-free metal precursor to deposit the first metal occurs via an atomic layer deposition (ALD) operation or a chemical vapor deposition (CVD) operation. [0007] In some embodiments, the substrate comprises an interconnect. In some embodiments, the metal film forms a diffusion barrier over the interconnect. In some embodiments, the interconnect comprises a metal, such as aluminum, copper, or ruthenium. In some embodiments, the interconnect is a copper interconnect, a molybdenum-aluminum interconnect, or a molybdenum-ruthenium-aluminum interconnect. [0008] In some embodiments, the method further comprises depositing a metal-containing film over the diffusion barrier by electrodeposition. In some embodiments, the metal-containing film comprises a third metal. In some embodiments, the first metal and the third metal are the same metal. In some embodiments, the first metal and the third metal are two different metals. [0009] In some embodiments, the chlorine-free metal precursor comprises a structure of the formula: M1CxNyHalz, where Hal comprises Br, I or F, M1 is a first metal, and where z, y and z are each independently an integer of from 0 to 6. [0010] In some embodiments, the chlorine-free metal precursor comprises at least one carbon- metal bond, at least one nitrogen-metal bond, and/or at least one oxygen-metal bond. [0011] In some embodiments, the halogen-free oxidant comprises a structure of the formula:
Attorney Docket No. LAM1P018WO-11683-1WO M2On, where M2 is a second metal, and n is an integer of 2 to 4. [0012] Another aspect of the disclosure relates to a method of depositing the metal film on the substrate. In some embodiments, the method includes providing the substrate including the interconnect in the process chamber, exposing the substrate to the chlorine-free transition metal- containing precursor to deposit the transition metal-containing film, and oxidizing the transition metal-containing film with the noble metal-containing oxidant to form the metal oxide. In some embodiments, the metal oxide includes the transition metal and the noble metal. In some embodiments, the method further includes reducing the metal oxide with the reducing agent to form the transition metal and noble metal-containing film. In some embodiments, the chlorine- free transition metal-containing precursor includes the first transition metal and at least one carbon-metal bond and/or at least one nitrogen-metal bond. [0013] In some embodiments, the first transition metal includes molybdenum, tantalum or tungsten. In some embodiments, the noble metal-containing oxidant includes RuO4, MeReO3, or OsO4. [0014] In some embodiments, the reducing agent is a reducing agent plasma. In some embodiments, the reducing agent plasma is hydrogen (H2), ammonia (NH3), hydrazine (N2H4), an amine, diborane (B2H6), silane (SiH4), disilane (Si2H6), an alcohol, hydrogen sulfide (H2S), or a thiol. [0015] In some embodiments, the reducing agent is trimethylaluminum (Al(CH3)3), methylaluminum hydride (HAl(CH3)2), triethylaluminum (Al(CH2CH3)3), or aluminum ethyl hydride (HAl(CH2CH3)2). [0016] In some embodiments, the method further comprises exposing the transition metal and noble metal-containing film to the transition metal-containing precursor to deposit the transition metal-containing film on the transition metal and noble metal-containing film. In some embodiments, the transition metal-containing precursor includes the second transition metal. In some embodiments, the second transition metal includes molybdenum, rhenium, rhodium, iridium, tungsten, copper, cobalt, or tantalum. [0017] In some embodiments, the interconnect is a copper interconnect, a molybdenum- aluminum interconnect, or a molybdenum-ruthenium-aluminum interconnect. [0018] Another aspect of the disclosure relates to a method for conversion of a molybdenum- containing film. In some embodiments, the method includes providing the substrate comprising the copper interconnect in the process chamber, exposing the substrate to the chlorine-free molybdenum-containing precursor to deposit the molybdenum-containing film, oxidizing the molybdenum-containing film with the ruthenium-containing oxidant to form the metal oxide, where the metal oxide includes molybdenum and ruthenium, and reducing the metal oxide with
Attorney Docket No. LAM1P018WO-11683-1WO the reducing agent to form the molybdenum- and ruthenium-containing film. In some embodiments, the chlorine-free molybdenum precursor comprises at least one carbon- molybdenum bond and/or at least one nitrogen-molybdenum bond. [0019] In some embodiments, the substrate further comprises a cobalt layer or a tantalum nitride layer on the copper interconnect. [0020] In some embodiments, the chlorine-free molybdenum-containing precursor comprises a low valent chlorine-free molybdenum precursor. In some embodiments, the low valent chlorine- free molybdenum precursor has an oxidation state of zero, one, two, or three. [0021] In some embodiments, the low valent chlorine-free molybdenum precursor comprises a structure of Formula (I), Formula (II), or Formula (III): MoLn (I), Mo2Ln (II), or LnMo(L’)mMoLn (III), where: each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3. [0022] In some embodiments, the low valent chlorine-free molybdenum precursor comprises the structure of Formula (I), Formula (II), or Formula (III), and each L is independently a monodentate ligand. In some embodiments, the monodentate ligand is hydrogen, halo, hydroxy, alkyl silyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, imido, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, acetylacetonato, fluorinated acetylacetonato, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, haloalkyl, alkylcarbonyl, CO, =O, =S, N, NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, fluorinated carboxyl, acetylacetonato, fluorinated acetylacetonato, carboxy, - C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanoaryl, isocyanohaloalkyl, isocyanohaloaryl, or cyclyl, with the proviso that halo, haloalkyl, isocyanohaloalkyl, and isocyanohaloaryl monodentate ligands do not include chlorine. [0023] In some embodiments, the chlorine-free molybdenum-containing precursor comprises a
Attorney Docket No. LAM1P018WO-11683-1WO structure of Formula (IV) or Formula (V): Mon(OnC-Y-PPhn)m(ML)m (IV), or Mon(ZN-C(H)-NZ)m (V), where: each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand; n is 2; m is 4; M is selected from the group consisting of Rh, Ir, Ru, and Au; and Y and Z are each independently an aryl group. [0024] In some embodiments, the chlorine-free molybdenum-containing precursor comprises a structure of Formula (IV) or Formula (V), Y is phenyl, and Z is p-(MeO)C6H4. [0025] In some embodiments, the reducing agent is a reducing agent plasma. [0026] In some embodiments, the chlorine-free molybdenum-containing precursor is bis(ethylbenzene)Mo, Mo(CO)6, MoO2(acac)2, bis(tert- butylimido)bis(dimethylamido)molybdenum, bis(tert-butylimido)bis(tert-butoxy)molybdenum, MoO(OiPr)4, or a complex. In some embodiments, the chlorine-free molybdenum-containing precursor is the complex and the complex is benzene molybdenum tricarbonyl ((C6H6)Mo(CO)3), or molybdenum tricarbonyl mesitylene ((C6H3Me3)Mo(CO)3). In some embodiments, the chlorine-free molybdenum-containing precursor is the complex and the complex includes molybdenum bonded to a tri-tert-butylphenylazide ligand (e.g., (Ph[tBu]N)3Mo). In some embodiments, the chlorine-free molybdenum-containing precursor is the complex and the complex includes molybdenum coordinated to four allyl ligands (e.g., Mo(allyl)4). In some embodiments, the chlorine-free molybdenum-containing precursor is the complex and the complex is a diphenylphosphino benzoic acid complex. In some embodiments, the chlorine-free molybdenum-containing precursor is the complex, the complex is a dimolybdenum complex, and the dimolybdenum complex is a Mo-Mo dinuclear paddlewheel compound. [0027] In some embodiments, the method further comprises exposing the molybdenum- and ruthenium-containing film to the transition metal-containing precursor to deposit the transition metal-containing film on the molybdenum- and ruthenium-containing film. In some embodiments, the transition metal-containing precursor comprises molybdenum, rhenium, rhodium, iridium, tungsten, copper, cobalt, or tantalum. [0028] Another aspect of the disclosure relates to an apparatus for processing substrates. In some embodiments, the apparatus includes one or more process chambers, where each process chamber includes a chuck. In some embodiments, the apparatus further includes an ampoule for
Attorney Docket No. LAM1P018WO-11683-1WO precursor delivery having an inlet and an outlet, a plasma source, one or more gas inlets into the process chambers and associated flow-control hardware, and a controller. In some embodiments, the controller has at least one processor and a memory. In some embodiments, the at least one processor and the memory are communicatively connected with one another. In some embodiments, the at least one processor is at least operatively connected with the flow-control hardware. In some embodiments, the memory stores computer-executable instructions for controlling the at least one processor to at least control the flow-control hardware to: cause introduction of a substrate to a chlorine-free metal precursor to deposit a first metal, cause oxidation of the first metal with a halogen-free oxidant comprising a second metal to form a metal oxide, where the metal oxide includes the first metal and the second metal, and cause reduction of the metal oxide with a reducing agent to form a metal film, the metal film comprising the first metal and the second metal. [0029] These and other aspects are described further below with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS [0030] FIG 1 illustrates a cross-sectional view of a substrate during deposition of metal- containing films in accordance with certain disclosed embodiments. [0031] FIG.2A depicts a flowchart for a method of depositing a metal film in accordance with certain disclosed embodiments. [0032] FIG.2B depicts a flowchart for another method in accordance with certain disclosed embodiments. [0033] FIG.2C depicts a flowchart for another method in accordance with certain disclosed embodiments. [0034] FIG.2D depicts a flowchart for another method in accordance with certain disclosed embodiments. [0035] FIG.2E depicts a flowchart for another method in accordance with certain disclosed embodiments. [0036] FIG.3A provides Mo3d high resolution X-ray photoelectron spectroscopic data for the metal films deposited in accordance with certain disclosed embodiments. [0037] FIG.3B provides Ru3d high resolution X-ray photoelectron spectroscopic data for the metal films deposited in accordance with certain disclosed embodiments. [0038] FIG.4 provides examples of general structures for molybdenum precursors in accordance with certain disclosed embodiments. [0039] FIG.5 provides examples of low valent molybdenum precursors of the formula Mo(L)6 in accordance with certain disclosed embodiments.
Attorney Docket No. LAM1P018WO-11683-1WO [0040] FIG.6 provides examples of low valent dimolybdenum precursors in accordance with certain disclosed embodiments. [0041] FIG.7 is a schematic presentation of an apparatus that is suitable for depositing metals in accordance with certain disclosed embodiments. [0042] FIG.8 shows a schematic view of a multi-station processing system in accordance with certain disclosed embodiments. [0043] FIG.9 shows a schematic view of a multi-station processing system in accordance with certain disclosed embodiments. DETAILED DESCRIPTION [0044] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments. Introduction & Context [0045] ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. ALD processes use surface-mediated deposition reactions to deposit films on a layer by-layer basis in cycles. As an example, an ALD cycle may include the following operations: (i) delivery/adsorption of a precursor, (ii) purging of precursor from the chamber, (iii) delivery of a second reactant and optionally ignite plasma, and (iv) purging of byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of a substrate affects the film composition and properties, such as non-uniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc. [0046] Unlike the CVD technique, ALD processes use surface mediated deposition reactions to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface that includes a population of surface-active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, in a dose provided to a chamber housing a substrate. Molecules of this first precursor are adsorbed onto the substrate surface, including chemisorbed species and/or physi-sorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the
Attorney Docket No. LAM1P018WO-11683-1WO adsorbed layer may include the compound as well as derivatives of the compound. After a first precursor dose, the chamber is then evacuated to remove most or all of first precursor remaining in gas phase so that mostly or only the adsorbed species remain. In some implementations, the chamber may not be fully evacuated. For example, the reactor may be evacuated such that the partial pressure of the first precursor in gas phase is sufficiently low to mitigate a reaction. A second reactant, such as an oxygen-containing gas, is introduced to the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after a source of activation is applied temporally. The chamber may then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness. [0047] In some implementations, the ALD methods include plasma activation. As described herein, the ALD methods and apparatuses described herein may be conformal film deposition (CFD) methods. [0048] When alternatives to chlorine-containing metal precursors, such as the use of metalorganic precursors having direct carbon-metal, nitrogen-metal, and/or oxygen-metal bonds are utilized for BEOL processes, the highly stable carbides or nitrides deposited by the alternative precursors in turn present certain challenges during post-processing reduction to metal film. The processes described herein manage the carbides or nitrides deposited by treatment with certain molecular oxidants to convert them to metal oxides, which then can more readily be removed under less harsh conditions. An illustration of a cross-sectional view 100 of a substrate 101 and various deposited layers using the techniques described herein is provided in FIG.1. In some embodiments, the substrate 101 may have a recessed feature (not shown). In some embodiments, a recessed feature may have sidewalls and a bottom. In general, the substrate 101 may include a variety of materials including dielectrics, metals and metal nitrides. [0049] In some embodiments, the substrate 101 may be, for example, a hardmask, a film, a stack, a partially fabricated semiconductor device film stack, etc., fabricated in any suitable way. In some embodiments, the substrate 101 may include a hardmask disposed on a work piece, such as the partially fabricated semiconductor device film stack. The hardmask, on the uppermost layer of the film stack, may have a variety of compositions, such as SiO2, silicon nitride, an ashable hardmask (AHM) material, and may be formed by CVD, for example PECVD. It should be appreciated that AHMs composed of amorphous carbon films are desirable in some implementations. Amorphous carbon films in this context may be undoped or doped with boron (B) or tungsten (W), for example. Suitable amorphous carbon films may have a composition
Attorney Docket No. LAM1P018WO-11683-1WO including about 50 to 80 atomic % carbon (C), 10 to 20 atomic % hydrogen (H), and 5 to 40 atomic % B or W dopant, for example. [0050] In some embodiments, other substrates can be employed. For instance, the substrate 101 can be or include an amorphous hydrogenated carbon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon boronitride, amorphous silicon, polysilicon, or a combination of any described herein, in any form (e.g., a bulk film, a thin film, another film, a stack, etc.). [0051] In some embodiments, the substrate 101 may include an interconnect. A semiconductor interconnect is a structure in a dual damascene, semi-damascene, or single damascene integration flow, such as a via or trench structure. In some embodiments, the substrate 101 may include the interconnect, and the interconnect may include a material, such as Cu, Ti, TiN, TiSi, TiSiN, Al, Ag, Au, W, Mo, Ru, Co, Sb or Bi, among others. In some embodiments, the interconnect includes a metal, such as aluminum, copper, or ruthenium. In some embodiments, the interconnect is a copper interconnect. In some embodiments, the interconnect is a molybdenum- aluminum interconnect. In some embodiments, the interconnect is a molybdenum-ruthenium- aluminum interconnect. [0052] In some embodiments, a conformal layer of a metal-containing film 103 may be deposited on or over a top surface of the substrate 101 by introduction of a chlorine-free metal precursor including a first metal to a process chamber to deposit the first metal. As used herein, the phrase “chlorine-free metal precursor” refers to a precursor which does not have any chlorines directly bonded to the metal, and also does not have any chlorinated substituents bonded to the metal. [0053] In some embodiments, and as depicted in FIG.1, the chlorine-free metal precursor has a structure of the formula: M1CxNyHalz, where Hal is Br, I or F and where z, y and z are each independently an integer of 0 to 6. Suitable first metals (M1) are transition metals including Mo, W, or Ta. In some embodiments, the deposition of the conformal layer of a metal-containing film 103 occurs via ALD deposition. In some embodiments, more than one of the chlorine-free metal precursor may be utilized. If more than one of the chlorine-free metal precursor is utilized, each one may be dosed cyclically and separately. Process details for deposition are described further below. [0054] In some embodiments, the conformal layer of a metal-containing film 103 is then treated with a molecular halogen-free oxidant including a second metal to form a metal oxide- containing layer 105. As used herein, “halogen-free oxidant” refers to an oxidant which does not have any halogens or any halogenated substituents. In some embodiments, the halogen-free oxidant has a structure of the formula M2On, where n is an integer of 2-4, and the metal oxide- containing layer 105 has a structure of the formula M1M2On, where n is an integer of 2-4. In
Attorney Docket No. LAM1P018WO-11683-1WO some embodiments, suitable second metals (M2) are noble metals including Ru, Re, and Os. In some embodiments, the halogen-free oxidant is RuO4, MeReO3 or OsO4. [0055] In some embodiments, oxidizing conditions may include a temperature of less than about 200°C. In some embodiments, oxidizing conditions may include the temperature of less than about 150°C. In some embodiments, oxidizing conditions may include the temperature of about 100°C. In some embodiments, a pressure during oxidation may range from about 0.1 to about 10 Torr. In some embodiments, the pressure during oxidation may be about 5 Torr. In some embodiments, a duration of the oxidation may range from about 0.1 to about 10 seconds. [0056] In some embodiments, the metal oxide-containing layer 105 may be reduced with a reducing agent to form a metal film 107 of the first metal and the second metal. In some embodiments, the reducing agent is a gas. In some embodiments, the reducing agent is a reducing plasma. In some embodiments, the reducing agent is hydrogen (including hydrogen plasma, hydrogen radicals, or other hydrogen species), ammonia or ammonia plasma, hydrazine (N2H4), an alkylhydrazine, such as t-butyl hydrazine (C4H12N2), an alcohol, an aldehyde, a carboxylic acid, a borane, an amine, a thiol, silane (SiH4), disilane (Si2H6), trisilane (Si3H8), germane (GeH4), digermane (Ge2H6), borane (BH3), diborane (B2H6), methane (CH4), and/or carbon monoxide (CO). In some embodiments, the reducing agent is trimethylaluminum (Al(CH3)3), methylaluminum hydride (HAl(CH3)2), triethylaluminum (Al(CH2CH3)3), and/or aluminum ethyl hydride (HAl(CH2CH3)2). It should be appreciated that the reduction may be either thermal or plasma-based. In some embodiments, the reducing agent may be delivered as either a direct plasma or a remote plasma. In addition to the plasmas mentioned, other reducing agents may be provided by generating plasma from one or more the reducing agents listed. [0057] In some embodiments, exposing the metal oxide-containing layer 105 to the reducing agent may include contacting the substrate with the reducing agent for a duration ranging between about 0.1 seconds and about 180 seconds. In some embodiments, exposing the metal oxide-containing layer 105 to the reducing agent may include contacting the substrate with the reducing agent for a duration ranging between about 0.5 seconds and 60 seconds. In some embodiments, exposing the metal oxide-containing layer 105 to the reducing agent may include contacting the substrate with the reducing agent for a duration ranging between about 0.1 seconds at 10 seconds. [0058] In some embodiments, a flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent may be less than about 30 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent may be less than about 15 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the
Attorney Docket No. LAM1P018WO-11683-1WO reducing agent may be less than about 10 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent may be less than about 5 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent may be less than about 2 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent may be less than about 0.1 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent ranges from about 0.1 to about 30 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide- containing layer 105 to the reducing agent ranges from 5 to about 15 slm. In some embodiments, the flow rate of the reducing agent during exposure of the metal oxide-containing layer 105 to the reducing agent is equal to or greater than about 10 slm. [0059] In some embodiments, a ratio of M1 to M2 in the metal film 107 is tunable, dependent upon the particular precursors and process conditions such as temperature, pressure, dose time and flow rate. In some embodiments, the metal film 107 forms a diffusion barrier over the interconnect, which may prevent leaching of interconnect metals. [0060] In some embodiments, the metal film 107 has a thickness ranging between about 1 to about 50 Angstroms. In some embodiments, the metal film 107 has the thickness ranging between about 3 to about 30 Angstroms. In some embodiments, the metal film 107 has a thickness ranging between about 5 to about 20 Angstroms. [0061] Optionally, after reducing the metal oxide-containing layer 105 to the metal film 107, a metal-containing film 109 of a third metal may deposited on or over the top surface of the metal film 107. In some embodiments, the third metal is Mo, W, Ta, Re, Rh, Ir, Cu or Co. In some embodiments, the first metal and the third metal may be different metals. In some embodiments, the first metal and the third metal may be the same metal. In some embodiments, deposition of the metal film 109 occurs via ALD, electrodeposition, CVD, or electroless deposition. [0062] In some embodiments, the metal-containing film 109 may be deposited by exposing the metal film 107 to either a non-chlorine-containing precursor or a chlorine-containing precursor. [0063] In some embodiments, metal film 107 may be have a thickness less than that of the metal-containing film 109. [0064] Any of the reagents described above (chlorine-free metal precursors, halogen-free oxidants, reducing agents, and chlorine-containing precursor) may be delivered to the process chamber in a carrier gas. In some embodiments, the oxidant is delivered as a liquid in a solvent to the process chamber. [0065] In some embodiments, the temperature range for reduction, oxidation and depositions
Attorney Docket No. LAM1P018WO-11683-1WO may be from about 25 ºC to about 500 ºC. In some embodiments, the pressure during the reduction, oxidation and depositions may be up to about 300 Torr. [0066] FIG.2A depicts a flowchart 200A for a method of depositing a metal film in accordance with certain disclosed embodiments. As shown in FIG.2A, the method begins at an operation 201, where the substrate having an interconnect is provided to the process chamber. Appropriate substrates and interconnects are those described above with reference to FIG.1. [0067] As shown in FIG.2A, an operation 203 follows the operation 201 and includes introducing the chlorine-free transition-metal containing precursor to deposit the transition metal-containing film. In some embodiments, the chlorine-free transition-metal containing precursor has at least one carbon-metal bond and/or at least one nitrogen-metal bond. In some embodiments, suitable transition metals include Mo, W, or Ta. [0068] In some embodiments, tungsten or tantalum can be deposited using a variety of volatile precursors including, but not limited to, tungsten hexacarbonyl, tris(3- hexyne)tricarbonyltungsten, (ethylcyclopentadienyl)tricarbonyltungsten monohydride, methylcyclopentadienyltungstendicarbonylnitrosyl, ethylcyclopentadienyltungstendicarbonylnitrosyl, bis(iso- propylcyclopentadienyl)dihydridotungsten, bis(tert-butylimido)bis(dimethylamido)tungsten, pentakisdimethylamidotantalum, (tert-butylimido)tris(dimethylamido)tantalum, (tert- butylimido)tris(diethylamido)tantalum, (tert-amylimido)tris(dimethylamido)tantalum, and tris(neopentyl)neopentylidenetantalum. Appropriate molybdenum precursors are described below. [0069] As shown in FIG.2A, an operation 205 follows the operation 203 and includes oxidizing the transition metal-containing film with the noble metal-containing oxidant to form the metal oxide. In some embodiments, the metal oxide is a transition metal and noble metal- containing film. In some embodiments, the metal oxide may have a structure of RuxMoyOz, where x, y and z are each independently integers of from 1-4. In some embodiments, the metal oxide may have a structure of RexMoyOz, where x, y and z are each independently integers of from 1-4. Appropriate oxidants are described above with reference to FIG.1. It should be appreciated that in-situ conversion of any Mo-C bonds may occur by using any selective organometallic Mo precursor for Cu to Mo-O. [0070] As shown in FIG.2A, an operation 207 follows the operation 205 and includes reducing the metal oxide with the reducing agent plasma to form the transition metal and noble metal-containing film. Appropriate reducing agents are described above with reference to FIG. 1. [0071] As shown in FIG.2A, an optional operation 209 follows the operation 207 and
Attorney Docket No. LAM1P018WO-11683-1WO includes depositing the transition metal over the transition metal and noble metal-containing film. Appropriate transition metals include the third metals described above with reference to FIG.1. [0072] Returning to FIG.2A, certain steps of the method 200 may be repeated cyclically until the desired thickness and/or metal content is attained. For example, an operation 211 is a process flow path indicating that after the operation 205, the operation 203 can commence again, repeating n1 times. In some embodiments, in the operation 211, n1 is the number of cycles which may be from 0 to 50 or from 20 to 40. In some embodiments, the cycle of operations from the operation 205 back to the operation 203 can be repeated as many times as necessary. As used herein, the term “cycle” refers to a particular set of sequential operations. [0073] Similarly, an operation 213 is a process flow path indicating that after the operation 207, the operation 203 can commence again, repeating n2 times. In some embodiments, in the operation 213, n2 is the number of cycles which may be from 0 to 50 or from 20 to 40. In some embodiments, the cycle of operations from the operation 207 to back to the operation 203 can be repeated as many times as necessary. [0074] It should be appreciated that in some embodiments, the method of FIG.2A concludes after execution of the operation 207. It should be appreciated that in some embodiments, the method of FIG.2A concludes after execution of the operation 209. [0075] FIG.2B depicts a flowchart 200B for a method in accordance with certain disclosed embodiments. The term “metalorganic,” as used herein, refers to a metal which has a direct metal-nitrogen bond, direct metal-oxygen bond, a direct metal-carbon bond, or combinations thereof. In some embodiments, the method of FIG.2B can advantageously result in damage-free Mo metallization, which may be useful for future BEOL applications. Protection of copper interconnects with diffusion barriers (also referred to as “plateable barrier films”) allows replacement of the conventional multistep process of 1) physical vapor deposition of TaN 2) chemical vapor deposition of Co 3) physical vapor deposition of Cu barrier/seed flow; with a single ALD-based process. Moreover, resistivity of the plateable barrier is reduced in comparison with conventional diffusion barriers. [0076] As shown in FIG.2B, the method begins at an operation 215 that includes providing the substrate having the copper interconnect in the process chamber. In some embodiments, the copper interconnect may have a cobalt layer or a tantalum nitride layer on or over the top surface of the copper interconnect. [0077] As shown in FIG.2B, an operation 217 follows the operation 215 and includes introducing the chlorine-free nitrogen and/or the carbon-containing molybdenum precursor to deposit an organometal film. In some embodiments, the chlorine-free molybdenum-containing
Attorney Docket No. LAM1P018WO-11683-1WO precursor includes a structure of Formula (I), Formula (II), Formula (III), Formula (IV), or Formula (V). [0078] In some embodiments, the chlorine-free molybdenum-containing precursor is Mo(CO)6. In some embodiments, the chlorine-free molybdenum-containing precursor is (toluene)Mo(CO)3. In some embodiments, the chlorine-free molybdenum-containing precursor is C16H20Mo. In some embodiments, the chlorine-free molybdenum-containing precursor is bis(ethylbenzene)Mo. In some embodiments, the chlorine-free molybdenum-containing precursor is MoO2(acac)2. In some embodiments, the chlorine-free molybdenum-containing precursor is bis(tert-butylimido)bis(dimethylamido)molybdenum. In some embodiments, the chlorine-free molybdenum-containing precursor is bis(tert-butylimido)bis(tert- butoxy)molybdenum. In some embodiments, the chlorine-free molybdenum-containing precursor is MoO(OiPr)4. In some embodiments, the chlorine-free molybdenum-containing precursor is [Mo(CH3SiCH2)3]2. In some embodiments, the chlorine-free molybdenum-containing precursor is Mo(allyl)4. In some embodiments, the chlorine-free molybdenum-containing precursor is Mo(THD)3. In some embodiments, the chlorine-free molybdenum-containing precursor is Mo(toluene)2. In some embodiments, the chlorine-free molybdenum-containing precursor is (dimethylamido)2Mo(tert-butylimido)2. In some embodiments, the chlorine-free molybdenum- containing precursor is (iPrCp)2MoH2. In some embodiments, the chlorine-free molybdenum- containing precursor is EtCp(CO)2Mo(NO). In some embodiments, the chlorine-free molybdenum-containing precursor is CpMo(CO)2(NO). [0079] A general discussion of molybdenum precursors follows. Any precursors described herein are useful for the operation 217, as will be discussed in further detail below. However, for the purposes of the operation 217, only those molybdenum precursors which are chlorine-free are suitable. [0080] It should be appreciated that the galvanic exchange between copper oxide (CuO or Cu2O) and the chlorine-free molybdenum-containing precursor in the presence of a reducing agent (such as carbon derived from a source such as carbon monoxide (CO) or carbon dioxide (CO2)) involves the reduction of copper oxide by carbon from the chlorine-free molybdenum- containing precursor, leading to the formation of metallic copper (Cu) and gas. This process is driven by the higher electronegativity of copper compared to carbon, making it a favorable redox reaction. In some embodiments, the carbon from the chlorine-free molybdenum-containing precursor reacts with the copper oxide, reducing it to metallic copper, and releasing oxygen as a byproduct. The difference in reduction potential between copper and carbon drives the reaction. It should be appreciated that the galvanic exchange occurs before conversion of the Cu-MoOx to Cu-Mo, Cu-MoxRuy, MoxRuyAlz, or Cu-MoxAlz.
Attorney Docket No. LAM1P018WO-11683-1WO [0081] As shown in FIG.2B, an operation 219 follows the operation 217 and includes oxidizing the organometal film with the ruthenium-containing oxidant to form the molybdenum oxide. In some embodiments, the molybdenum oxide includes both molybdenum and ruthenium. In some embodiments, the ruthenium-containing oxidant is RuO4, and the molybdenum oxide is RuMoOx where x is an integer of 2 to 4. In some embodiments, the oxidant may be in liquid form, delivered in a suitable solvent in certain embodiments. In some embodiments, suitable solvents may include water, or fluorinated solvents. [0082] It should be appreciated that in some embodiments, an aluminum-based precursor may be used to convert molybdenum to a molybdenum-aluminum alloy using a technique such as ALD or CVD. In some embodiments, the aluminum-based precursor is trimethylaluminum (TMAl). In some embodiments, the aluminum-based precursor is bis(2,4-pentanedionato) molybdenum (VI) dioxide. It should be appreciated that the aluminum-based precursor is not limited to those disclosed herein and any suitable aluminum-based precursor may be used. In some embodiments, the aluminum-based precursor may be used in addition to the halogen-free oxidant (such as RuO4) to convert the Mo-C to MoAl or Mo. In some embodiments, the aluminum-based precursor may be used in lieu of the halogen-free oxidant (such as RuO4) to convert the Mo-C to MoAl or Mo. [0083] As shown in FIG.2B, an operation 221 follows the operation 219 and includes reducing the molybdenum oxide with the reducing agent plasma to form the molybdenum and ruthenium-containing film, such as RuMo. [0084] As shown in FIG.2B, an optional operation 223 follows the operation 221 and includes depositing the transition metal over the molybdenum and ruthenium-containing film. In some embodiments, the transition metal is molybdenum. In some embodiments, the transition metal is rhenium. In some embodiments, the transition metal is rhodium. In some embodiments, the transition metal is iridium. In some embodiments, the transition metal is tungsten. In some embodiments, the transition metal is copper. In some embodiments, the transition metal is cobalt. In some embodiments, the transition metal is tantalum. [0085] In some embodiments, any of the molybdenum precursors described above may be utilized for the optional operation 223, including those containing chlorine, as the molybdenum and ruthenium-containing film formed in the operation 221 can act as a diffusion barrier, protecting the copper interconnect beneath it from any potential interaction associated with exposure to the molybdenum precursor in the optional operation 223. In some embodiments, deposition in the optional operation 223 is by electrodeposition. In some embodiments, deposition of the optional operation 223 is by electroless deposition. [0086] It should be appreciated that certain steps of the method of FIG.2B may be repeated
Attorney Docket No. LAM1P018WO-11683-1WO cyclically until the desired thickness and/or metal content is attained. For example, an operation 225 is a process flow path indicating that after the operation 219, the operation 217 can commence again, repeating n3 times. In some embodiments, in the operation 225, n3 is the number of cycles which may be from 0 to 50 or from 20 to 40. In some embodiments, the cycle of operations from the operation 219 back to the operation 217 can be repeated as many times as necessary. As used herein, the term “cycle” refers to a particular set of sequential operations. [0087] Similarly, an operation 227 is a process flow path indicating that after the operation 221, the operation 217 can commence again, repeating n4 times. In some embodiments, in the operation 227, n4 is the number of cycles which may be from 0 to 50 or from 20 to 40. In some embodiments, the cycle of operations from the operation 221 back to the operation 217 can be repeated as many times as necessary. [0088] It should be appreciated that in some embodiments, the method of FIG.2B concludes after execution of the operation 221. It should be appreciated that in some embodiments, the method of FIG.2B concludes after execution of the operation 223. [0089] FIG.2C depicts a flowchart for a method 200C in accordance with certain disclosed embodiments. As shown in FIG.2C, the method begins at an operation 229 that includes providing the substrate in the process chamber. In some embodiments, the substrate includes the interconnect. [0090] As shown in FIG.2C, an operation 231 follows the operation 229 and includes exposing the substrate to the chlorine-free metal precursor to deposit the first metal. In some embodiments, the chlorine-free metal precursor includes a structure of a formula: M1CxNyHalz, wherein Hal includes Br, I or F, M1 is the first metal, and z, y and z are each independently an integer of from 0 to 6. In some embodiments, the chlorine-free metal precursor includes at least one carbon-metal bond. In some embodiments, the chlorine-free metal precursor includes at least one nitrogen-metal bond. In some embodiments, the chlorine-free metal precursor includes at least one oxygen-metal bond. In some embodiments, the chlorine-free metal precursor includes at least one carbon-metal bond, at least one nitrogen-metal bond, and/or at least one oxygen- metal bond. In some embodiments, the operation 231 occurs via ALD or CVD. In some embodiments, the first metal includes the transition metal. [0091] As shown in FIG.2C, an operation 233 follows the operation 231 and includes oxidizing the first metal with the halogen-free oxidant comprising the second metal to form the metal oxide. In some embodiments, the halogen-free oxidant includes a structure of a formula: M2On, wherein M2 is the second metal, and n is an integer of 2 to 4. In some embodiments, the metal oxide includes the first metal and the second metal. In some embodiments, the second metal includes the noble metal.
Attorney Docket No. LAM1P018WO-11683-1WO [0092] As shown in FIG.2C, an operation 235 follows the operation 233 and includes reducing the metal oxide with the reducing agent to form the metal film. In some embodiments, the metal film includes the first metal and the second metal. In some embodiments, the method of FIG.2C concludes at an operation 237 after the operation 235. [0093] In some embodiments where the substrate includes the interconnect, the metal film forms the diffusion barrier over the interconnect at the operation 235. [0094] In some embodiments, an optional operation follows the operation 235 and includes depositing the metal-containing film over the diffusion barrier by electrodeposition. In some embodiments, the metal-containing film includes a third metal. In some embodiments, the first metal and the third metal are the same metal. In some embodiments, the first metal and the third metal are two different metals. In some embodiments, the method of FIG.2C concludes after execution of the optional operation. [0095] FIG.2D depicts a flowchart for a method 200D in accordance with certain disclosed embodiments. As shown in FIG.2D, the method begins at an operation 239 that includes providing the substrate comprising the interconnect in the process chamber. [0096] As shown in FIG.2D, an operation 241 follows the operation 239 and includes exposing the substrate to the chlorine-free transition metal-containing precursor to deposit the transition metal-containing film. In some embodiments, the chlorine-free transition metal- containing precursor includes the first transition metal and at least one carbon-metal bond. In some embodiments, the chlorine-free transition metal-containing precursor includes the first transition metal and at least one nitrogen-metal bond. In some embodiments, the chlorine-free transition metal-containing precursor includes the first transition metal and at least one carbon- metal bond and/or at least one nitrogen-metal bond. In some embodiments, the first transition metal includes molybdenum. In some embodiments, the first transition metal includes tantalum. In some embodiments, the first transition metal includes tungsten. [0097] As shown in FIG.2D, an operation 243 follows the operation 241 and includes oxidizing the transition metal-containing film with the noble metal-containing oxidant to form the metal oxide. In some embodiments, the noble metal-containing oxidant includes RuO4. In some embodiments, the noble metal-containing oxidant includes MeReO3. In some embodiments, the noble metal-containing oxidant includes OsO4. In some embodiments, the metal oxide includes the transition metal and the noble metal. [0098] As shown in FIG.2D, an operation 245 follows the operation 243 and includes reducing the metal oxide with the reducing agent to form the transition metal and noble metal- containing film. In some embodiments, the reducing agent is the reducing agent plasma. In some embodiments, the reducing agent plasma includes hydrogen. In some embodiments, the reducing
Attorney Docket No. LAM1P018WO-11683-1WO agent plasma includes ammonia. In some embodiments, the reducing agent plasma includes hydrazine. In some embodiments, the reducing agent plasma includes an amine. In some embodiments, the reducing agent plasma includes diborane. In some embodiments, the reducing agent plasma includes silane. In some embodiments, the reducing agent plasma includes disilane. In some embodiments, the reducing agent plasma includes an alcohol. In some embodiments, the reducing agent plasma includes hydrogen sulfide. In some embodiments, the reducing agent plasma includes a thiol. In some embodiments, the method of FIG.2D concludes at an operation 247 after the operation 245. [0099] In some embodiments, an optional operation follows the operation 245 and includes exposing the transition metal and noble metal-containing film to the transition metal-containing precursor to deposit the transition metal-containing film on the transition metal and noble metal- containing film. In some embodiments, the transition metal-containing precursor includes the second transition metal. In some embodiments, the second transition metal includes molybdenum. In some embodiments, the second transition metal includes rhenium. In some embodiments, the second transition metal includes rhodium. In some embodiments, the second transition metal includes iridium. In some embodiments, the second transition metal includes tungsten. In some embodiments, the second transition metal includes copper. In some embodiments, the second transition metal includes cobalt. In some embodiments, the second transition metal includes tantalum. In some embodiments, the second transition metal includes molybdenum, rhenium, rhodium, iridium, tungsten, copper, cobalt, and/or tantalum. In some embodiments, the method of FIG.2D concludes after execution of the optional operation. [0100] FIG.2E depicts a flowchart for a method 200E in accordance with certain disclosed embodiments. As shown in FIG.2E, the method begins at an operation 249 that includes providing the substrate comprising the copper interconnect in the process chamber. In some embodiments, the substrate further includes a cobalt layer on the copper interconnect. In some embodiments, the substrate further includes a tantalum nitride layer on the copper interconnect. [0101] As shown in FIG.2E, an operation 251 follows the operation 249 and includes exposing the substrate to the chlorine-free molybdenum-containing precursor to deposit the molybdenum-containing film. In some embodiments, the chlorine-free molybdenum precursor includes at least one carbon-molybdenum bond. In some embodiments, the chlorine-free molybdenum precursor includes at least one nitrogen-molybdenum bond. In some embodiments, the chlorine-free molybdenum precursor includes at least one carbon-molybdenum bond and/or at least one nitrogen-molybdenum bond. [0102] In some embodiments, the chlorine-free molybdenum precursor includes a low valent chlorine-free molybdenum precursor. In some embodiments, the low valent chlorine-free
Attorney Docket No. LAM1P018WO-11683-1WO molybdenum precursor has an oxidation state of zero. In some embodiments, the low valent chlorine-free molybdenum precursor has the oxidation state of one. In some embodiments, the low valent chlorine-free molybdenum precursor has the oxidation state of two. In some embodiments, the low valent chlorine-free molybdenum precursor has the oxidation state of three. [0103] In some embodiments, the low valent chlorine-free molybdenum precursor includes the structure of Formula (I): MoLn (I), where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3. In some embodiments, the low valent chlorine-free molybdenum precursor includes the structure of Formula (II): Mo2Ln (II), where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3. In some embodiments, the low valent chlorine-free molybdenum precursor includes the structure of Formula (III): LnMo(L’)mMoLn (III), where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, L’ is a linking moiety, n is 2, 3, 4, 5 or 6; and m is 1, 2 or 3. [0104] In some embodiments, the low valent chlorine-free molybdenum precursor includes the structure of Formula (I), Formula (II), or Formula (III), where each L is independently a monodentate ligand. In some embodiments, the low valent chlorine-free molybdenum precursor includes the structure of Formula (I), Formula (II), or Formula (III), where each L is independently a monodentate ligand, and where the monodentate ligand includes hydrogen, halo, hydroxy, alkyl silyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, imido, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, acetylacetonato, fluorinated acetylacetonato, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, - PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, haloalkyl, alkylcarbonyl, CO, =O, =S, N, NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, fluorinated carboxyl, acetylacetonato, fluorinated acetylacetonato, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyanoalkyl, isocyanoaryl, isocyanohaloalkyl, isocyanohaloaryl, or cyclyl, with a proviso that halo, haloalkyl, isocyanohaloalkyl, and isocyanohaloaryl monodentate ligands do not include chlorine. [0105] In some embodiments, the chlorine-free molybdenum-containing precursor includes a structure of Formula (IV): Mon(OnC-Y-PPhn)m(ML)m (IV), where each L is independently a
Attorney Docket No. LAM1P018WO-11683-1WO monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, n is 2, m is 4, M is selected from the group consisting of Rh, Ir, Ru, and Au, and Y and Z are each independently an aryl group. In some embodiments, Y is phenyl. In some embodiments, Z is p-(MeO)C6H4. [0106] In some embodiments, the chlorine-free molybdenum-containing precursor includes a structure of Formula (V): Mon(ZN-C(H)-NZ)m (V), where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand, n is 2, m is 4, M is selected from the group consisting of Rh, Ir, Ru, and Au, and Y and Z are each independently an aryl group. In some embodiments, Y is phenyl. In some embodiments, Z is p-(MeO)C6H4. [0107] In some embodiments, the chlorine-free molybdenum-containing precursor includes bis(ethylbenzene)Mo. In some embodiments, the chlorine-free molybdenum-containing precursor includes Mo(CO)6. In some embodiments, the chlorine-free molybdenum-containing precursor includes MoO2(acac)2. In some embodiments, the chlorine-free molybdenum- containing precursor includes bis(tert-butylimido)bis(dimethylamido)molybdenum. In some embodiments, the chlorine-free molybdenum-containing precursor includes bis(tert- butylimido)bis(tert-butoxy)molybdenum. In some embodiments, the chlorine-free molybdenum- containing precursor includes MoO(OiPr)4. [0108] In some embodiments, the chlorine-free molybdenum-containing precursor includes a complex. In some embodiments, the complex is benzene molybdenum tricarbonyl ((C6H6)Mo(CO)3). In some embodiments, the complex is molybdenum tricarbonyl mesitylene ((C6H3Me3)Mo(CO)3). In some embodiments, the complex includes molybdenum bonded to a tri-tert-butylphenylazide ligand (e.g., (Ph[tBu]N)3Mo). In some embodiments, the complex includes molybdenum coordinated to four allyl ligands (e.g., Mo(allyl)4). In some embodiments, the complex is a diphenylphosphino benzoic acid complex. In some embodiments, the complex is a dimolybdenum complex. In some embodiments, the dimolybdenum complex is a Mo-Mo dinuclear paddlewheel compound. It should be appreciated that a Mo-Mo dinuclear paddlewheel compound is a type of metal-organic complex characterized by a central molybdenum- molybdenum (Mo-Mo) core with a quadruply bonded interaction, resembling a paddlewheel. [0109] As shown in FIG.2E, an operation 253 follows the operation 251 and includes oxidizing the molybdenum-containing film with the ruthenium-containing oxidant to form the metal oxide. In some embodiments, the metal oxide includes molybdenum and ruthenium. [0110] As shown in FIG.2E, an operation 255 follows the operation 253 and includes reducing the metal oxide with the reducing agent to form the molybdenum- and ruthenium- containing film. In some embodiments, the reducing agent is the reducing agent plasma. In some embodiments, the method of FIG.2E concludes at an operation 257 after execution of the operation 255.
Attorney Docket No. LAM1P018WO-11683-1WO [0111] In some embodiments in the method of FIG.2E, an optional operation follows the operation 255 and includes exposing the molybdenum- and ruthenium-containing film to the transition metal-containing precursor to deposit the transition metal-containing film on the molybdenum- and ruthenium-containing film. In some embodiments, the transition metal- containing precursor includes molybdenum. In some embodiments, the transition metal- containing precursor includes rhenium. In some embodiments, the transition metal-containing precursor includes rhodium. In some embodiments, the transition metal-containing precursor includes iridium. In some embodiments, the transition metal-containing precursor includes tungsten. In some embodiments, the transition metal-containing precursor includes copper. In some embodiments, the transition metal-containing precursor includes cobalt. In some embodiments, the transition metal-containing precursor includes tantalum. In some embodiments, the transition metal-containing precursor includes molybdenum, rhenium, rhodium, iridium, tungsten, copper, cobalt, and/or tantalum. In some embodiments, the method of FIG.2E concludes after execution of the optional operation. Molybdenum Precursors [0112] Generally, molybdenum precursors may have from two (MoL2) to six (MoL6) ligands and can include molybdenum in a wide range of oxidation states ranging from 0 to +6. Molybdenum precursors may also be dimolybdenum compounds having 1) two molybdenum atoms singly or multiply bonded to one another; or 2) two molybdenum atoms connected by a linking group such as a bidentate ligand. [0113] Suitable molybdenum containing precursors include molybdenum halides and oxyhalides, such as fluorides, chlorides, bromides, oxyfluorides, oxychlorides, and oxybromides where molybdenum may be in any of the oxidation states from +2 to +6. [0114] Molybdenum chloride precursors are given by the formula MoClx, where x is 2, 3, 4, 5, or 6, and include molybdenum dichloride (MoCl2), molybdenum trichloride (MoCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), and molybdenum hexachloride (MoCl6). In some embodiments, MoCl5 or MoCl6 are used. While the description chiefly refers to MoClx precursors, in other embodiments, other molybdenum halide precursors may be used. Molybdenum halide precursors are given by the formula MoXz, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and z is 2, 3, 4, 5, or 6. Examples of MoXz precursors include molybdenum fluoride (MoF6). In some embodiments, a non-fluorine-containing MoXz precursor is used to prevent fluorine etch or incorporation. In some embodiments, a non-bromine-containing and/or a non-iodine-containing MoXz precursor is used to prevent etch, or bromine or iodine incorporation.
Attorney Docket No. LAM1P018WO-11683-1WO [0115] Molybdenum oxyhalide precursors are given by the formula MoOyXz, where X is a halogen (fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) and y and z are numbers greater than 0 such that MoOyXz forms a stable compound. Examples of molybdenum oxyhalides include molybdenum dichloride dioxide (MoO2Cl2), molybdenum tetrachloride oxide (MoOCl4), molybdenum tetrafluoride oxide (MoOF4), molybdenum dibromide dioxide (MoO2Br2), and the molybdenum iodides MoO2I, and Mo4O11I. [0116] In some embodiments discussed herein, the precursors having molecular weights of less than about 450 g/mol, such as less than about 400 g/mol. [0117] In some embodiments the molybdenum-containing precursor has a formula MoXnYm, wherein X is a chalcogen (e.g., oxygen or sulfur), Y is a halogen (e.g., fluorine, chlorine, bromine, or iodine), n is 0, 1, or 2 and m is 2, 3, 4, 5, or 6. Examples of halogen-containing molybdenum-containing precursors include without limitation MoCl5, Mo2Cl10, MoO2Cl2, and MoOCl4. Another example of a halogen-containing molybdenum-containing precursor is MoF6. Low-Valent Molybdenum Complexes [0118] Low valent molybdenum complexes or compounds are those having molybdenum in low oxidation states 0, +1, +2 or +3. In certain embodiments, the low valent molybdenum complexes may be efficacious precursors as it is easier to reduce Mo(I) to Mo (0) or Mo(II)/(III) to Mo(0) than it is to reduce the more commonly utilized Mo(IV)/(V) halide precursors. [0119] Low valent molybdenum precursors may offer a less circuitous surface redox process to obtain fully reduced molybdenum metal films with minimal impurities. Without wishing to be bound by a particular theory, this is likely the result of the ease of reduction of low valent molybdenum precursors. Molybdenum Zero Complexes [0120] Mo (0) precursors are advantageous because do not require any reduction steps, and are energetically facile, as their use provides a lower energy barrier to Mo film formation upon exposure to a reducing agent. They are especially amenable in multi-step ALD processes where surface-ligand exchange and conversion (reduction) occurs. Molybdenum hexacarbonyl (Mo(CO)6) is an example of a molybdenum complex existing in the oxidation state of zero. [0121] A general structure for low valent molybdenum precursors having one molybdenum is MoLn (Formula I), and general structures for low valent molybdenum precursors with two molybdenum atoms are Mo2Ln (Formula II) or LnMo(L’)mMoLn (Formula III). For any of Formulas I-III, each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand and n is an integer of 2 to 6. For Formula III, L’ is a linking moiety
Attorney Docket No. LAM1P018WO-11683-1WO such as a bidentate ligand; and m is an integer of 1 to 3. Monodentate Ligands [0122] Suitable ligands for the low valent molybdenum complexes include monodentate ligands, also referred to as unidentate ligands. A monodentate ligand is one which binds or coordinates to a metal center via one coordination site of the metal only, or via one site of the ligand only. They may include a wide variety of substituents such as hydrogen, halo, hydroxy, alkyl silyl, silylalkyl, alkenyl, alkynyl, allyl, alkoxy, alkenoxy, alkynoxy, thioalkoxy, aliphatic acyl, -CF3, nitro, amino, imino, -N(C1-C3 alkyl)C(O)(C1-C3 alkyl), -C1-C3 alkylamino, alkenylamino, alkynylamino, di(C1-C3 alkyl)amino, -C(O)O-(C1-C3 alkyl), -C(O)NH-(C1-C3 alkyl), -CH=NOH, -P(C1-C3 alkyl)3, -PO3H2, -OPO3H2, -C(O)N(C1-C3 alkyl)2, haloalkyl, alkoxycarbonyl, alkoxyalkoxy, carboxaldehyde, carboxamide, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, aroyl, aryloxy, arylamino, biaryl, thioaryl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, heterocycloyl, alkylaryl, alkylcarbonyl, CO, =O, =S, ≡N, ≡CR, =CR2, -NO, aralkenyl, aralkyl, sulfonyl, sulfonamido, sulfonimido, carbamate, aryloxyalkyl, carboxyl, carboxy, -C(O)NH(benzyl), amido, azido, isocyanato, thiocyanato, isothiocyanato, cyano, isocyano or cyclyl groups where each R is independently an aliphatic such as haloalkyl or aryl such as a haloaryl group. [0123] In some embodiments, the low valent molybdenum precursors include at least one OR, P(R)3, CNR, allyl or aryl group, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. [0124] In some embodiments, the monodentate ligand can include an oxygen atom. In particular embodiments, one or more ligands can be optionally substituted alkoxy. Non-limiting ligands include, e.g., methoxy, ethoxy, isopropoxy (i-PrO) and t-butoxy (t-BuO). Non-limiting molybdenum-containing precursors include, e.g., Mo(CH2F)(t-BuO)3, Mo(CF3)(t-BuO)3, Mo(CH2I)(t-BuO)3, Mo(CI3)(t-BuO)3, Mo(CH2CH2F)(t-BuO)3, Mo(CH2CH2I)(t-BuO)3, Mo(CH2F)2(t-BuO)2, Mo(CF3)2(t-BuO)2, Mo(CH2I)2(t-BuO)2, Mo(CI3)2(t-BuO)2, Mo(CH2CH2F)2(t-BuO)2, Mo(CH2CH2I)2(t-BuO)2, Mo(t-BuO)2, Mo(CH3)(t-BuO)3, Mo(CH2CH3)(t-BuO)3, Mo(CH=CH2)(t-BuO)3, Mo(CH=CHCH3)(t-BuO)3, Mo(CH2- CH=CH2)(t-BuO)3, Mo(C≡CH)(t-BuO)3, Mo(C≡CCH3)(t-BuO)3, Mo(CH2C≡CH)(t-BuO)3, or Mo(acac)2. [0125] In certain embodiments, the oxygen-containing monodentate ligand may be -OC(CH3)(CF3)2, -OC(CH3)2(CF3), -OC(CH3)3, -OSiR3 (such as -OSiPh3), C O (carbonyl ligand) or -OAr (where Ar groups include but are not limited to phenyl, mesitylenyl, 2,6- iPr2C6H3, hexa-iso-propyl-ter-phenyl, and 2,3,5,6-Ph4C6H). In certain embodiments, the oxygen-
Attorney Docket No. LAM1P018WO-11683-1WO containing ligand is an ether, epoxide, or ketone. In some cases, the oxygen-containing ligand may be a silyloxy group. [0126] In certain embodiments, the ligand is a phosphorous-containing ligand. Suitable complexes may be of the formula R3P where R is a halo, aliphatic or aryl group. Examples include secondary or tertiary organophosphines such as P(t-Bu)3, PMe3, PPh3, p(OMe)3, p(OEt)3, PMe2Cl, PMeCl2, PEtMeCl, PEt2Cl, PEtCl2, PCl3 or PF3. In some embodiments, the phosphorus containing ligand is phosphanetriyltris(benzene sulfonic acid). Other phosphorus containing ligands include -CH2P(CH3)3, -P(O)OH, -P(O)(OCH3)2, -P(O)(OCH2CH3)2, and - CH(Si(CH3)3)(P(CH3)3). [0127] In some embodiments, the ligand is an isocyano functional group, including isonitriles of the formula -C≡NR, such as isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, isocyanohaloaryl. In some embodiments, R is an aliphatic group such as a haloalkyl, or an aryl group such as haloaryl. In certain embodiments, R may be -CH2CF3, -C(F)=CF2, -C(F)=C(F)CF3, -CF2C(F)=CF2, -CH(CF3)2, -CH(CH3)(CF3), or -C(CH3)2(CF3). In certain embodiments, R is a perfluoroalkyl substituent of one to ten carbon atoms such as perfluorinated methyl, ethyl, i- propyl, n-propyl, t-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl or n-hexyl group. [0128] In some embodiments, the monodentate ligand is one with sp2 hybridized character such as an allyl, allenyl, ethenyl, indenyl or cyclopentadienyl group. Two of the same such substituents or two different such substituents may be utilized to form precursors with a sandwich structure. In some embodiments, one such substituent is utilized to form a half- sandwich complex. In certain embodiments, the ligand may be mesitylenyl, tolyl, xylyl, benzyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, or pyrimidinyl. [0129] In some embodiments, the ligand is an atom which is connected directly to molybdenum via a multiple bond such as a double or triple bond. Examples include =O, =NR, =S, ≡N, =CR2 or ≡CR, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. [0130] In some embodiments, the molybdenum-containing precursor has at least one optionally substituted haloalkyl group. Non-limiting haloaliphatic group ligands include -CXyH3- y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); - CXzH2-zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; or -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I). Yet other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-
Attorney Docket No. LAM1P018WO-11683-1WO CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (- CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2- chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2- difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI), and the like. In particular embodiments, the C1-2 haloalkyl includes β-halo-substituted ethyl. Yet other haloaliphatic groups include C1-4 haloalkyl, C2-4 haloalkenyl, and C2-4 haloalkynyl. [0131] In other embodiments, the ligand is an optionally substituted alkyl group, optionally substituted alkenyl, or optionally substituted alkynyl. Non-limiting groups include -CnH2n+1, in which n is 1 or 2; -CnH2n-1, in which n is 2, 3, or 4; or -CnH2n-3, in which n is 2, 3, or 4. Yet other non-limiting groups include methyl (-CH3), ethyl (CH2CH3), vinyl or ethenyl (-CH=CH2), 1- propenyl (-CH=CHCH3), allyl or 2propenyl (-CH2-CH=CH2), 1-butenyl (CH=CHCH2CH3), 2- butenyl (CH2CH=CHCH3), 3-butenyl (e.g. CH2CH2CH=CH2), ethynyl (C≡CH), 1-propynyl (- C≡CCH3), 2-propynyl or propargyl (-CH2C≡CH), 1-butynyl (C≡CCH2CH3), 2butynyl (CH2C≡CCH3), 3-butynyl (CH2CH2C≡CH), 2-methyl-1-propenyl (CH=C(CH3)2, isopropenyl (C(CH3)=CH2, 1-methylallyl (CH(CH3)CH=CH2 and the like. [0132] In some embodiments, the monodentate ligand may be CH2P(CH3)3, CH(Si(CH3)3)(P(CH3)3), -C(O)C3F7, or -CHCHSO2C6H5. [0133] In some embodiments, the monodentate ligand includes a sulfur atom. In particular embodiments, one or more monodentate ligands can be SO2CF3, SO2C3N2H3, -CHCHSO2C6H5, - SO2OCH3, or -SO2C6H4CH3. [0134] In some embodiments, the monodentate ligand includes a nitrogen atom. In particular embodiments, one or more monodentate ligands can be optionally substituted amino or optionally substituted bis(trialkylsilyl)amino. Non-limiting ligands can include, e.g., -NMe2, - NEt2, -NMeEt, -N(t-Bu)-[CHCH3]2-N(t-Bu)- (tbba), N(SiMe3)2, and N(SiEt3)2. [0135] In some embodiments, the optionally substituted amino is NR1R2, in which each R1 and R2 is, independently, H or alkyl; or in which R1 and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the optionally substituted bis(trialkylsilyl)amino is N(SiR1R2R3)2, in which each R1, R2, and R3 is, independently, alkyl. In yet other embodiments, the optionally substituted trialkylsilyl is SiR1R2R3, in which each R1, R2, and R3 is, independently, alkyl. [0136] In other embodiments, the low valent molybdenum precursor includes a first ligand that is NR1R2 and a second ligand that is NR1R2, in which each R1 and R2 is, independently, H or alkyl. In yet other embodiments, the formula includes a first ligand that is OR1 and a second
Attorney Docket No. LAM1P018WO-11683-1WO ligand that is OR1, in which each R1 is, independently, H or alkyl. [0137] In some embodiments, the monodentate ligand is optionally substituted alkyl. Non- limiting alkyl groups include, e.g., CnH2n+1, where n is 1, 2, 3, or greater, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl. In various embodiments, the ligand has at least one beta-hydrogen or beta-halogen. [0138] In some embodiments, at least one monodentate ligand is optionally substituted haloalkyl. Non-limiting haloalkyl groups include, e.g., CnH2n+1-zXz, wherein n is 1, 2, 3, or greater; wherein z is 1 to 2n+1 (e.g., 1 to 3, 1 to 5, or 1 to 7); and wherein each X is, independently, halo (F, Cl, Br, or I). [0139] In some embodiments, at least one monodentate ligand is optionally substituted alkenyl or optionally substituted alkynyl. Non-limiting alkenyl groups include, e.g., CnH2n-1, where n is 2, 3, 4, or greater, such as ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, or 3-butenyl. Non-limiting alkynyl groups include, e.g., CnH2n-3, where n is 2, 3, 4, or greater, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, or 3-butynyl. [0140] Alkynyl groups are also suitable monodentate ligands in certain embodiments. In some embodiments, the carbon-carbon triple bond is not bound directly to the molybdenum, for example in a formula R1CCCH2MoL3 where R1 is a C1-C2 linear or branched alkane such as methyl or ethyl; and L is an amino (dimethylamino, diethylamino, ethylmethylamino, methylpropylamino, aminiocyclopentane, aminocyclohexane) or alkoxy group (methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, sec-butoxy, or n-butoxy). [0141] Alkyne compounds which have a carbon-carbon triple bond directly bonded to the molybdenum atom will hydrolyze in the presence of water similar to, although much slower than, amino and alkoxy groups. Therefore, compounds such as (R1C≡C)3MoR2 and (R1C≡C)4Mo where R1 is a simple alkane such as methyl or ethyl, and R2 is a C1-C2 hydrocarbon are precursors having monodentate ligands in accordance with certain embodiments. In compound (R1C≡C)3MoR2 the molybdenum center has three alkynes with the carbon-carbon triple bond bonded to the molybdenum center. Tetra-alkynes such as those shown for (R1C≡C)4Mo. [0142] In some embodiments, the monodentate ligand is halo. In particular, the metal- containing precursor can be a metal halide or organometal halide. Non-limiting metal halides and organometal halides include FCH2MoX3, CF3MoX3, ICH2MoX3, CI3MoX3, CH2FCH2MoX3, CH2ICH2MoX3, MoX2, or MoX4, in which each X is, independently, halo. In other embodiments, the metal-containing precursor is RMoX3, in which R is C1-4 haloalkyl, C2-4 haloalkenyl, or C2-4 haloalkynyl; and in which each X is, independently, halo. In yet other embodiments, the metal-containing precursor is RMoX3, in which R is C1-2 alkyl, C2-4 alkenyl, or C2-4 alkynyl; and in which each X is, independently, halo.
Attorney Docket No. LAM1P018WO-11683-1WO [0143] In other embodiments, the monodentate ligand is C1- C3 aliphatic (wherein the C1-C3 aliphatic may be optionally substituted with a ketone, an alkoxy group, an epoxy group) or a - C(O)C1-C3 alkyl group. Ethers, ketones or epoxide-containing ligands on the low valent molybdenum-containing precursors may be advantageous to assist in crosslinking. [0144] In some embodiments, the monodentate ligand can include a silicon atom. In some embodiments, the monodentate ligand may be -Si(CH3)3, -Si(C2H5)3, -CH2Si(CH3)3, - CH(Si(CH3)3)2 or -C(Si(CH3)3)3. In particular embodiments, one or more ligands can be optionally substituted trialkylsilyl or optionally substituted bis(trialkylsilyl)amino. Non-limiting ligands can include, e.g., -SiMe3, -SiEt3, -N(SiMe3)2, and -N(SiEt3)2. [0145] For any formula herein, each monodentate ligand may independently be hydrogen, halo, azido, cyano, alkylcarbonyl, isothiocyanato, thiocyanato, optionally substituted alkyl, optionally substituted aryl, optionally substituted amino, optionally substituted bis(trialkylsilyl)amino, optionally substituted trialkylsilyl, or optionally substituted alkoxy (e.g., -OR1, in which R1 can be alkyl). [0146] The present disclosure also encompasses hydrogen as a monodentate ligand. An example of a complex having a hydrogen monodentate ligand is a molybdenum hydride precursor such as Mo(Cp)2H2, where Cp is cyclopentadienyl. [0147] The monodentate ligand may be an ambidentate ligand, which has two potential donor atoms, but only attaches to a metal via one of the two. In certain embodiments, the ambidentate ligand is NO2-, which may bond to a metal through either the nitrogen atom or the oxygen atom. Bidentate Ligands [0148] Suitable ligands for the low valent molybdenum complexes include bidentate ligands. A bidentate ligand (also referred to as a chelating ligand) is one which binds or coordinates to a metal center via two coordination sites of the metal, or via two sites of the ligand. Bidentate ligands are Lewis bases that donate two pairs of electrons to a metal atom. The bidentate ligands may be neutral or anionic. Furthermore, the bidentate ligands may have the same two coordination atoms, or may be unsymmetrical bidentate ligands, where the two coordination atoms are not the same. In some embodiments, the bidentate ligands may be ethylenediamine (en), bipyridyl (bpy), 1,2-bis(dimethylphosphino)ethane (dmpe), phenanthroline (phen), 1,2- bis(diphenylphosphino)ethane (dppe), acetate (OAc), oxalate (ox), or acetylacetonate (acac). Precursors with bidentate ligands include, but are not limited to, molybdenum diacetylacetonate dioxide (MoO2(acac)2). [0149] Example structures containing the bidentate ligand include, but are not limited to the structures of Formula (VI) and Formula (VII):
Attorney Docket No. LAM1P018WO-11683-1WO . The bidentate ligand may be a linking moiety L’ includes NR, C(R)n, Si(R)n, S, O or P(R)n;
amino or aliphatic; n is 0, 1 or 2 and e is 1, 2, 3, 4 or 5. Suitable low valent molybdenum precursors may contain one, two or three bidentate each of which may be the same or different. [0151] The bidentate ligand may be an amidinate, an amidate, an iminopyrrolidinate, a diazabutadiene, a beta-imino amide, an alpha-imino alkoxide, a beta-diketiminate, a beta- ketoiminate, a beta-diketonate, a pyrazolate, a beta-amino alkoxide, a guanidinidate, a dithiolene, an alpha-iminothiolene, an alpha-dithiolate, or a beta-dithiolate. Other examples of suitable materials include the bidentate ligands described in US 2022/0170155 and WO 2021/035236, which are incorporated herein by reference in their entireties. Tridentate Ligands [0152] A tridentate ligand is one with three atoms that can function as acceptors in a coordination complex. In certain embodiments, the tridentate ligand three nitrogen, three sulfur, three phosphorus or three oxygen atoms available for chelation. Tridentate ligands include cis,cis-1,3,5-triaminocyclohexane, 1,4,7-triazacyclononane, 1,4,7,-trimethyl-1,4,7- triazacyclononane, 1,4,7-trithiacyclononane, bis(diphenylphosphinoethyl)phenylphosphine, N,N,N’,N”N”-pentamethyldiethylenetriamine, tris(4S-isopropyl-2-oxazolinyl)phenylborate, tris(4,4-dimethyl-2-oxazolinyl)phenyl borate, trispyrazolylborate, 1,4,7-trioxonane, diethylenetriamine, or an iminodiacetate anion. Suitable low valent molybdenum precursors may contain one, two or more tridentate ligands which may be the same or different. [0153] The low valent molybdenum precursors may have two to six ligands. Each occurrence of L may independently be a monodentate, ambidentate, bidentate or tridentate ligand as described above. Low valent molybdenum precursors having two ligands may be of the formula MoL2. Precursors with two ligands include, but are not limited to, bis(ethylbenzene)molybdenum (C16H20Mo). [0154] FIG.4 illustrates example structures for molybdenum precursors having three ligands (Formula (VIII)), four ligands (Formula (X) and Formula (IX)) or five ligands (Formula (XI) and
Attorney Docket No. LAM1P018WO-11683-1WO Formula (XII)) in certain embodiments. In Formula (VIII), Formula (IX), Formula (XI), and Formula (XII), each R15, R4, R6, and R7, respectively, is independently -CH3, -C2H5, -C3H7, - C4H9, -C5H11, -CF3, -C4F9, -C5F11, -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), -C(CH3)2(CF3), - C(CF3)3, -Si(CH3)3, -Si(C2H5)3 or -CH2Si(CH3)3, -CH(Si(CH3)3)2, -C(Si(CH3)3)3, -P(CH3)3, - CH2P(CH3)3, -P(O)OH, -P(O)(OCH3)2, -P(O)(OCH2CH3)2, -CH(Si(CH3)3)(P(CH3)3), -SO2CF3, - SO2C3N2H3, -C(O)C3F7, -CHCHSO2C6H5, -SO2OCH3, or -SO2C6H4CH3. In Formula (XII), each R8 is independently any of the monodentate, ambidentate or bidentate ligands described above. For Formula (XI), G may be =O, =NR, =S or =CR2, where each R is independently an aliphatic, aryl, haloalkyl or haloaryl group. Suitable precursors having four ligands include, but are not limited to, Mo(ntBu)2(OBu)2 and (iPrCp)2MoH2. Suitable precursors having five ligands include, but are not limited to, MoO(OiPr)4. For Formula (X), R1 may be aliphatic, R2 may be any of the monodentate, ambidentate, bidentate or tridentate ligands described above, and n may be 1, 2, 3, 4 or 5. [0155] Low valent molybdenum precursors may also have six ligands. Precursors with six ligands include, but are not limited to, molybdenum hexafluoride (MoF6) and molybdenum hexacarbonyl (Mo(CO)6). In some embodiments, such precursors may have the general formula Mo(X)p(R10)q (XIII) where each X independently includes chloro, fluoro, bromo or iodo; each R10 independently includes allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N-dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, - P(CH2CH3)3 or -CNR11, where R11 includes aliphatic, aryl or heterocyclyl; p is 1 to 4; q is 2 to 5; and p + q = 6. [0156] Low valent molybdenum precursors having six ligands may also be of the formula the Formula (XIV): Mo(R12)r(R13)s (XIV) where each R12 independently includes allyl, allenyl, ethenyl, mesitylenyl, tolyl, xylyl, benzyl, cyclopentadienyl, indenyl, anilinyl, N,N- dimethylanilinyl, tetrahydrofuranyl, piperidinyl, pyrrolyl, pyrrolidinyl, pyridinyl, piperidinyl, imidazolyl, pyrimidinyl, -NO, -CO, -P(CH3)3, -P(CH2CH3)3 or -CNR14, where R14 includes aliphatic, aryl or heterocyclyl; each R13 independently includes trimethylphosphine, triethylphosphine, tri-i-propyl phosphine, triphenylphosphine, tris(trimethylsilyl)phosphine, tris(2-carboxyethyl)phosphine, tris(dimethylamino)phosphine, tris(o-tolyl)phosphine, tris(4- methoxyphenyl)phosphine or tris(2-furyl)phosphine; r is 1 to 6; s is 0 to 5; and r + s = 6. [0157] FIG.5 illustrates example structures for low valent molybdenum precursors having six ligands. Structures 1-9 have one or more CNR ligands which may be isocyanoalkyl, isocyanohaloalkyl, isocyanoaryl, or isocyanohaloaryl groups. In some embodiments, R is an aliphatic group such as a haloalkyl, or an aryl group such as haloaryl. In certain embodiments, R
Attorney Docket No. LAM1P018WO-11683-1WO may be -CH2CF3, -CH(CF3)2, -CH(CH3)(CF3), or -C(CH3)2(CF3). In certain embodiments, R is a perfluoroalkyl substituent of one to ten carbon atoms such as perfluorinated methyl, ethyl, i- propyl, n-propyl, t-butyl, sec-butyl, n-butyl, cyclopentyl, n-pentyl, cyclohexyl or n-hexyl group. Structures 10-18 have one or more PMe3 ligands. [0158] Molybdenum complexes can be prepared using a zero valent starting material such as molybdenum hexacarbonyl. Other synthetic routes include reaction of MoCl3(THF)3 with the appropriate ligand followed by reduction and reaction of MoX5 (X = Cl, Br, I) with the appropriate ligand followed by reduction. [0159] The starting material can be treated with a neutral ligand, such as a thioether (dialkylsulfide), to induce redox neutral ligand exchange. The zero valent starting material can also be treated with a ligand precursor, such as bis(diethylthiocarbamoyl)disulfide or bis(trifluoromethyl)-1,2-dithiete, to induce oxidative addition and form the sulfur-containing complexes described herein. [0160] The reactions may be conducted in a variety of non-protic solvents. For example the reaction may be conducted in an ether solvent, such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, methyl-tert-butyl ether, 1,2-dimethoxyethane, in a hydrocarbon solvent such as toluene, benzene, heptane, hexane, pentane, or in a halocarbon solvent such as chlorobenzene, dichlorobenzene, fluorobenzene, difluorobenzene, dichloromethane, chloroform, etc. The reactions can be conducted in a wide temperature range depending on the boiling point of the solvent and on solubility of the products. In some embodiments, the starting materials, reaction intermediates, and the desired products are unstable toward moisture and oxygen. Accordingly, the reaction process should be conducted using anhydrous and air-free conditions using a protective inert gas, such as nitrogen or argon. Dimolybdenum Complexes [0161] In another aspect, precursors for deposition of molybdenum-containing films are di- molybdenum compounds containing a direct molybdenum-molybdenum bond (e.g., a multiple molybdenum-molybdenum bond, such as a double bond, or any multiple bond with a bond order of 2-5). The directly bonded dimolybdenum precursors may be of the structure Mo2Ln (II), where each occurrence of L is independently a monodentate, ambidentate, bidentate or tridentate ligand as described above, and n is 2 to 6. One example precursor is Mo2(O-isopropyl)6. Other example precursors are shown in FIG.6. In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a double bond (such as structure 19). In some embodiments, the dimolybdenum precursor has molybdenum atoms directly connected by a triple bond (such as structures 20-23). For structures 20 and 21, R may be an aliphatic group
Attorney Docket No. LAM1P018WO-11683-1WO such as an alkyl group, a haloalkyl group or a silyl group. For structure 23, L may be any ligand described above, or may be any one of CO, cNR or PMe3 (where R is aliphatic, aryl or heterocyclyl) and X is halo. Such precursors are particularly useful for deposition of molybdenum metal and high purity molybdenum metal because it may be easier to reduce such compounds to metallic molybdenum than some monoatomic molybdenum compounds. [0162] Di-molybdenum precursors described herein can be synthesized using dimolybdenum tetraacetate as a starting material by treatment with a ligand salt such as lithium amidate. In one aspect, a container housing any of the precursors described herein in a solid or liquid form is provided. In another aspect a solution of any of these precursors is provided, where the solvent may include, for example, a high boiling point hydrocarbon solvent, such as a higher alkane. In some embodiments a container holding the molybdenum precursor (in solid or liquid form or in solution) is filled with an inert gas, such as nitrogen (N2), or argon (Ar), to prevent contact of the precursor with air, and possible decomposition due to contact with moisture and/or air. In some embodiments the container is adapted for vaporization of the precursor inside the container. For example, the container may include an inlet and an outlet, where the inlet is adapted to be connected with a source of a carrier gas that can be flowed over or through the precursor thereby assisting in precursor vaporization. The outlet is adapted for removing the carrier gas and the precursor vapor from the container and is configured to be connected to a conduit that can be used to deliver the precursor vapor to the processing chamber. The inlet and the outlet each has a closed position and an open position, and, for example, can include manual valves that can be used to switch from closed to open positions and back. When the container is stored or transported the inlet and the outlet are closed. When the container is fitted to the deposition apparatus for use, the inlet and the outlet valves may be open, and a carrier gas may be flown into the inlet, and out from the outlet carrying the precursor vapor. [0163] In some embodiments the container has a flow-over design, in which the inlet and the outlet are positioned above the surface of the precursor. For example, in a cylindrical container the inlet and the outlet may be positioned at a similar vertical elevation (e.g., the vertical distance between the inlet and the outlet may be less than about 20% of the cylinder height). In other embodiments the container has a bubbler design, in which the inlet is positioned below the surface of the precursor and the outlet is positioned above the inlet (e.g., above the surface of the precursor). For example, in a cylindrical container the inlet and the outlet may be positioned far from each other in a vertical direction (e.g., the vertical distance between the inlet and the outlet may be more than about 30%, such as more than about 50%, or more than about 80% of the cylinder height. [0164] A low valent dimolybdenum complex may also contain two molybdenum atoms
Attorney Docket No. LAM1P018WO-11683-1WO connected indirectly to each other by a linking moiety. Such precursors may be of the formula LnMo(L’)mMoLn (III) where each L is independently a monodentate ligand, ambidentate ligand, bidentate ligand or tridentate ligand as described above; L’ is a linking moiety; n is 2 to 6; and m is 1 to 3. The linking moiety L’ may be of the structure –(E)e- where each E independently includes C(R)n, NR, Si(R)n, S, O or P(R)n; each R independently includes hydrogen, aryl, amino or aliphatic; n is 0, 1 or 2 and e is 1, 2, 3, 4 or 5. [0165] In some embodiments, the low valent dimolybdenum complex may contain two molybdenum atoms both directly bonded to each other and also connected indirectly to each by a linking moiety as described above. Returning to FIG.6, example structures 24 and 25 having both types of connections are shown. For structures 24 and 25, L may be any ligand described above, or preferably CO, CNR or PMe3 (where R is aliphatic, aryl or heterocyclyl) and X is halo. [0166] The molybdenum-containing films, and, particularly, high purity molybdenum metal, provided herein can be used in interconnect metallization (e.g., for filling recessed features to form contacts), in logic gate applications in FinFETs, as adhesion layers or diffusion barriers, and in 3D NAND fabrication. Examples of applications include logic and memory contact fill, DRAM buried wordline fill, vertically integrated memory gate, and wordline fill, and 3-D integration using through-silicon vias (TSV). The resistivity of molybdenum scales better than that of tungsten, and in some embodiments, molybdenum is particularly advantageous metal for filling narrow recessed features, e.g., features with widths of less than about 20 nm. [0167] In one application, molybdenum metal is used for manufacturing barrierless contacts. In this application, molybdenum metal is deposited directly into the recessed features (contact holes) having widths of about 5 – 100 nm, e.g., about 5 – 20 nm, where the recessed features are formed in the dielectric layer, and include exposed dielectric, such as silicon oxide, silicon nitride, or a low-k material such as silicon oxycarbide at the sidewalls and exposed silicon or silicon germanium at the bottom. In alternative embodiments, the contact hole prior to deposition may be lined with a barrier layer, such as WN, MoN, MoC, or TiN onto which the molybdenum metal is deposited. [0168] FIG.3A and FIG.3B are graphical illustrations of the metal films formed by the methods described herein. Films were deposited on substrates such as Si or TiN using an ALD process at a temperature of about 100°C and at a pressure of about 6 Torr using sequential and alternating pulses of RuO4 in a solvent and Mo(CO)6 separated by Ar purges. A periodic thermal H2 reduction step was employed every 10-25 cycles for oxygen removal and film densification. The Ru:Mo ratio was approximately 3:1 or 4:1 according to different analytical methods, with C content below X-ray photoelectron spectroscopy (XPS) detection limit and <5% by electron energy loss spectroscopy (EELS). The as-deposited resistivity of a 100 Å film was 125 µΩ·cm,
Attorney Docket No. LAM1P018WO-11683-1WO which decreased to 70 µΩ·cm after annealing at 450 °C. [0169] The graphs in each of FIG.3A and FIG.3B have an x-axis associated with binding energy (eV) and a y-axis associated with intensity (CPS). The graphs illustrate the results of the high-resolution XPS of the Mo 3d peak (FIG.3A) and the Ru 3d peak (FIG.3B) envelopes, revealing the presence of pure metallic RuMo. The Mo3d region is dominated by metallic peaks attributed to Ru-rich RuMo with Mo3d5/2 appearing at the binding energy of approximately 227.5eV and Mo-rich RuMo/pure Mo appearing at the binding energy of approximately 228 eV, as well as loss peaks for the Mo metal component. The asymmetry of the peak envelope also supports the presence of only metallic species. No evidence of C impurities were found based on the Ru3d core-level data as evidenced by the absence of carbidic C signals at the binding energy in the range of 282-283.5eV. The presence of pure RuMo is also supported by the lack of broadening — beyond the partial broadening of Ru 3d3/2 peak which is typical for metallic Ru — in either of the spin-orbit split Ru3d peaks (i.e. Ru3d5/2 and 3d3/2 doublet) and the 3:2 fitting ratio. Due to the overlap of C1s and Ru3d region in XPS, the presence of carbon would broaden these peaks and cause closer to a 1:1 or similar Ru3d3/2:Ru3d5/2 fitting ratio. Apparatus [0170] The deposition methods described herein can be carried out in a variety of apparatuses. A suitable apparatus includes a processing chamber having one or more inlets for introduction of reactants, a substrate holder in the process chamber configured to hold the substrate in place during deposition, and, optionally, a plasma generating mechanism configured for generating a plasma in a process gas. The apparatus may include a controller having program instructions configured to cause performance of any of the method steps described herein. [0171] For example, in some embodiments the apparatus includes a controller having program instructions that include instructions for: causing exposure of a semiconductor substrate to a silicon-containing reactant, a molybdenum-containing precursor, and a reducing agent at the temperature of between about 25 ºC and about 500 ºC in any of the process sequences described herein to deposit molybdenum metal and/or molybdenum silicide. The controller may include program instructions for causing any of the methods described herein. [0172] An example of a deposition apparatus suitable for depositing molybdenum-containing films using provided methods is shown in FIG.7. Specifically, FIG.7 schematically shows an embodiment of a process station 700 that may be used to deposit material using ALD and/or CVD, either of which may be plasma-enhanced. For simplicity, the process station 700 is depicted as a standalone process station having a process chamber body 702 for maintaining a
Attorney Docket No. LAM1P018WO-11683-1WO low-pressure environment. However, it will be appreciated that a plurality of process stations 700 may be included in a common process tool environment. Further, it will be appreciated that, in some embodiments, one or more hardware parameters of the process station 700, including those discussed in detail below, may be adjusted programmatically by one or more computer controllers. [0173] In some embodiments, the process station 700 fluidly communicates with a reactant delivery system 701 for delivering process gases to a distribution showerhead 706. The reactant delivery system 701 includes a mixing vessel 704 for blending and/or conditioning process gases for delivery to the showerhead 706. One or more mixing vessel inlet valves 720 may control introduction of process gases to the mixing vessel 704. Similarly, a showerhead inlet valve 705 may control introduction of process gasses to the showerhead 706. [0174] Some molybdenum-containing precursors may be stored in solid or liquid form prior to vaporization and subsequent delivery to the process station. For example, the embodiment of FIG.7 includes a vaporization point 703 for vaporizing solid reactant to be supplied to the mixing vessel 704. In some embodiments, the vaporization point 703 may be a heated vaporizer. In some embodiments a flow of an inert gas is passed over the heated solid molybdenum precursor, or bubbled through the heated liquid molybdenum precursor, under sub-atmospheric pressure, and carries the precursor vapor to the process chamber. The precursor vapor produced from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may create small particles. These small particles may clog piping, impede valve operation, contaminate substrates, etc. Some approaches to addressing these issues involve sweeping and/or evacuating the delivery piping to remove residual reactant. However, sweeping the delivery piping may increase process station cycle time, degrading process station throughput. Thus, in some embodiments, delivery piping downstream of the vaporization point 703 may be heat-traced. In some examples, the mixing vessel 704 may also be heat-traced. In one non-limiting example, piping downstream of the vaporization point 703 has an increasing temperature profile extending from approximately 100°C to approximately 200°C at the mixing vessel 704. [0175] In some embodiments, the showerhead 706 distributes process gases toward a substrate 712. In the embodiment shown in FIG.7, the substrate 712 is located beneath the showerhead 706, and is shown resting on a pedestal 708. It will be appreciated that the showerhead 706 may have any suitable shape and may have any suitable number and arrangement of ports for distributing processes gases to the substrate 712. While not explicitly shown, in some embodiments the showerhead 706 is a dual plenum showerhead that includes at least two types of conduits, where the first type of conduit is dedicated to delivery of molybdenum-containing
Attorney Docket No. LAM1P018WO-11683-1WO precursor vapor, and the second type of conduit is dedicated to delivery of the second (or other) reactant. In these embodiments the molybdenum-containing precursor and the reactant are not allowed to mix in the conduits prior to entry to the process chamber, and do not share the conduits if delivered to the chamber consecutively. [0176] In some embodiments, a microvolume 707 is located beneath the showerhead 706. Performing an ALD and/or CVD process in a microvolume rather than in the entire volume of a process station may reduce reactant exposure and sweep times, may reduce times for altering process conditions (e.g., pressure, temperature, etc.), may limit an exposure of process station robotics to process gases, etc. Example microvolume sizes include, but are not limited to, volumes between 0.1 liter and 2 liters. This microvolume also impacts productivity throughput. While deposition rate per cycle drops, the cycle time also simultaneously reduces. In certain cases, the effect of the latter is dramatic enough to improve overall throughput of the module for a given target thickness of film. [0177] In some embodiments, the pedestal 708 may be raised or lowered to expose the substrate 712 to the microvolume 707 and/or to vary a volume of the microvolume 707. For example, in a substrate transfer phase, the pedestal 708 may be lowered to allow the substrate 712 to be loaded onto the pedestal 708. During a deposition process phase, the pedestal 708 may be raised to position the substrate 712 within the microvolume 707. In some embodiments, the microvolume 707 may completely enclose the substrate 712 as well as a portion of the pedestal 708 to create a region of high flow impedance during a deposition process. [0178] Optionally, the pedestal 708 may be lowered and/or raised during portions the deposition process to modulate process pressure, reactant concentration, etc., within the microvolume 707. In one scenario where the process chamber body 702 remains at a base pressure during the deposition process, lowering the pedestal 708 may allow the microvolume 707 to be evacuated. Example ratios of microvolume to process chamber volume include, but are not limited to, volume ratios between 1:700 and 1:10. It will be appreciated that, in some embodiments, pedestal height may be adjusted programmatically by a suitable computer controller. [0179] While the example microvolume variations described herein refer to a height-adjustable pedestal, it will be appreciated that, in some embodiments, a position of the showerhead 706 may be adjusted relative to the pedestal 708 to vary a volume of the microvolume 707. Further, it will be appreciated that a vertical position of the pedestal 708 and/or the showerhead 706 may be varied by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 708 may include a rotational axis for rotating an orientation of the substrate 712. It will be appreciated that, in some embodiments, one or more of these example
Attorney Docket No. LAM1P018WO-11683-1WO adjustments may be performed programmatically by one or more suitable computer controllers. [0180] Returning to the embodiment shown in FIG.7, the showerhead 706 and the pedestal 708 electrically communicate with an radio frequency (RF) power supply 714 and a matching network 716 for powering a plasma. In other embodiments apparatuses without a plasma generator are used for depositing molybdenum-containing films using provided methods. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, a RF source power, an RF source frequency, and a plasma power pulse timing. For example, the RF power supply 714 and the matching network 716 may be operated at any suitable power to form a plasma having a desired composition of radical species. Likewise, the RF power supply 714 may provide RF power of any suitable frequency. In some embodiments, the RF power supply 714 may be configured to control high- and low- frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 700 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasmas. [0181] In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and/or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers. [0182] In some embodiments, the plasma may be controlled via input/output control (IOC) sequencing instructions. In one example, the instructions for setting plasma conditions for a plasma process phase may be included in a corresponding plasma activation recipe phase of a deposition process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a deposition process phase are executed concurrently with that process phase. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe phase preceding a plasma process phase. For example, a first recipe phase
Attorney Docket No. LAM1P018WO-11683-1WO may include instructions for setting a flow rate of an inert and/or a reactant gas, instructions for setting a plasma generator to a power set point, and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for enabling the plasma generator and time delay instructions for the second recipe phase. A third recipe phase may include instructions for disabling the plasma generator and time delay instructions for the third recipe phase. It will be appreciated that these recipe phases may be further subdivided and/or iterated in any suitable way within the scope of the present disclosure. [0183] In some embodiments, the pedestal 708 may be temperature controlled via a heater 710. Further, in some embodiments, pressure control for process station 700 may be provided by a butterfly valve 718. As shown in the embodiment of FIG.7, the butterfly valve 718 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the process station 700 may also be adjusted by varying a flow rate of one or more gases introduced to the process station 700. [0184] FIG.8 shows a schematic view of an embodiment of a multi-station processing tool 800 with an inbound load lock 802 and an outbound load lock 804, either or both of which may include a remote plasma source. Such tool may be used for processing the substrates using the methods provided herein. A robot 806, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 808 into the inbound load lock 802 via an atmospheric port 810. A wafer is placed by the robot 806 on a pedestal 812 in the inbound load lock 802, the atmospheric port 810 is closed, and the load lock is pumped down. Where the inbound load lock 802 includes a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 814. Further, the wafer also may be heated in the inbound load lock 802 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 816 to the processing chamber 814 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in FIG.8 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided. [0185] The depicted processing chamber 814 includes four process stations, numbered from 1 to 4 in the embodiment shown in FIG.8. Each station has a heated pedestal (shown at 818 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. While the depicted processing chamber 814 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
Attorney Docket No. LAM1P018WO-11683-1WO chamber may have three or fewer stations. [0186] FIG.8 also depicts an embodiment of a wafer handling system 890 for transferring wafers within the processing chamber 814. In some embodiments, the wafer handling system 890 may transfer wafers between various process stations and/or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non- limiting examples include wafer carousels and wafer handling robots. FIG.8 also depicts an embodiment of a system controller 850 employed to control process conditions and hardware states of the process tool 800. In some embodiments, the system controller 850 may include one or more memory devices 856, one or more mass storage devices 854, and one or more processors 852. In some embodiments, the one or more processors 852 may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc. [0187] In some embodiments, the system controller 850 controls all of the activities of the process tool 800. In some embodiments, the system controller 850 controls one or more operations of at least one method disclosed herein. In some embodiments, the system controller 850 executes system control software 858 stored in the mass storage device 854, loaded into the memory device 856, and executed on the processor 852. In some embodiments, the system control software 858 may include instructions for controlling the timing, mixture of gases, chamber and/or station pressure, chamber and/or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck and/or susceptor position, and other parameters of a particular process performed by the process tool 800. In some embodiments, the system control software 858 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes in accordance with the disclosed methods. In some embodiments, the system control software 858 may be coded in any suitable computer readable programming language. [0188] In some embodiments, the system control software 858 may include input/output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of an ALD process may include one or more instructions for execution by the system controller 850. The instructions for setting process conditions for an ALD process phase may be included in a corresponding ALD recipe phase. In some embodiments, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase. [0189] Other computer software and/or programs stored on the mass storage device 854 and/or the memory device 856 associated with system controller 850 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate
Attorney Docket No. LAM1P018WO-11683-1WO positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program. [0190] A substrate positioning program may include program code for process tool components that are used to load the substrate onto the pedestal 818 and to control the spacing between the substrate and other parts of the process tool 800. [0191] A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. The process gas control program may include code for controlling gas composition and flow rates within any of the disclosed ranges. A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. The pressure control program may include code for maintaining the pressure in the process station within any of the disclosed pressure ranges. [0192] A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. The heater control program may include instructions to maintain the temperature of the substrate within any of the disclosed ranges. [0193] A plasma control program may include code for setting RF power levels and frequencies applied to the process electrodes in one or more process stations, for example using any of the RF power levels disclosed herein. The plasma control program may also include code for controlling the duration of each plasma exposure. [0194] In some embodiments, there may be a user interface associated with the system controller 850. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc. [0195] In some embodiments, parameters adjusted by the system controller 850 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power levels, frequency, and exposure time), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface. [0196] Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller 850 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of the process tool 800. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately
Attorney Docket No. LAM1P018WO-11683-1WO programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions. [0197] Any suitable chamber may be used to implement the disclosed embodiments. Two or more of the stations may perform the same functions. Similarly, two or more stations may perform different functions. Each station can be designed/configured to perform a particular function/method as desired. [0198] FIG.9 is a block diagram of a processing system 900 suitable for conducting thin film deposition processes in accordance with certain embodiments. In some embodiments, the system 900 includes a transfer module 903. The transfer module 903 provides a clean, pressurized environment to minimize risk of contamination of substrates being processed as they are moved between various reactor modules. In some embodiments, mounted on the transfer module 903 are two multi-station reactors 909 and 910, each capable of performing ALD and/or CVD, according to certain embodiments. In some embodiments, the two multi-station reactors 909 and 910 may include multiple stations 911, 913, 915, and 917 that may sequentially or non- sequentially perform operations in accordance with disclosed embodiments. The stations may include a heated pedestal or substrate support, one or more gas inlets or showerhead or dispersion plate. [0199] Also mounted on the transfer module 903 may be one or more single or multi-station modules 907 capable of performing plasma or chemical (non-plasma) pre-cleans, or any other processes described in relation to the disclosed methods. The one or more single or multi-station modules 907 may in some cases be used for various treatments to, for example, prepare a substrate for a deposition process. In some embodiments, the one or more single or multi-station modules 907 may also be designed/configured to perform various other processes such as etching or polishing. In some embodiments, the system 900 also includes one or more wafer source modules 901, where wafers are stored before and after processing. An atmospheric robot (not shown) in an atmospheric transfer chamber 919 may first remove wafers from the one or more wafer source modules 901 to loadlocks 921. A wafer transfer device (generally a robot arm unit) in the transfer module 903 moves the wafers from loadlocks 921 to and among the modules mounted on the transfer module 903. [0200] In various embodiments, a system controller 929 is employed to control process conditions during deposition. In some embodiments, the system controller 929 will typically include one or more memory devices and one or more processors. A processor may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc. [0201] In some embodiments, the system controller 929 may control all of the activities of the
Attorney Docket No. LAM1P018WO-11683-1WO deposition apparatus. In some embodiments, the system controller 929 executes system control software, including sets of instructions for controlling the timing, mixture of gases, chamber pressure, chamber temperature, wafer temperature, radio frequency (RF) power levels, wafer chuck or pedestal position, and other parameters of a particular process. Other computer programs stored on memory devices associated with the system controller 929 may be employed in some embodiments. [0202] Typically, there will be a user interface associated with the system controller 929. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc. [0203] System control logic may be configured in any suitable way. In general, the logic can be designed or configured in hardware and/or software. The instructions for controlling the drive circuitry may be hard coded or provided as software. The instructions may be provided by “programming.” Such programming is understood to include logic of any form, including hard coded logic in digital signal processors, application-specific integrated circuits, and other devices which have specific algorithms implemented as hardware. Programming is also understood to include software or firmware instructions that may be executed on a general purpose processor. System control software may be coded in any suitable computer readable programming language. [0204] The computer program code for controlling the silicon-containing reagent flow, reducing agent flow, and metal-containing precursor flow, and other processes in a process sequence can be written in any conventional computer readable programming language: for example, assembly language, C, C++, Pascal, Fortran, or others. Compiled object code or script is executed by the processor to perform the tasks identified in the program. Also as indicated, the program code may be hard coded. [0205] The controller parameters relate to process conditions, such as, for example, process gas composition and flow rates, temperature, pressure, cooling gas pressure, substrate temperature, and chamber wall temperature. These parameters are provided to the user in the form of a recipe and may be entered utilizing the user interface. Signals for monitoring the process may be provided by analog and/or digital input connections of the system controller 929. The signals for controlling the process are output on the analog and digital output connections of the processing system 900. [0206] 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 operation of the chamber components necessary to carry out the deposition processes (and other
Attorney Docket No. LAM1P018WO-11683-1WO processes, in some cases) 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. [0207] In some implementations, the system controller 929 is part of a system, which may be part of the above-described examples. Such systems can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The system controller 929, depending on the processing requirements and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system. [0208] Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing steps during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer. [0209] The controller, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a
Attorney Docket No. LAM1P018WO-11683-1WO history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing steps to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus, as described above, the controller may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber. [0210] Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a CVD chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers. [0211] As noted above, depending on the process step or steps to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory. Further Implementations [0212] The apparatus and processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels, and the like. Typically, though not necessarily, such apparatus and processes will be used or conducted together in a common
Attorney Docket No. LAM1P018WO-11683-1WO fabrication facility. Lithographic patterning of a film typically includes some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a work piece, i.e., a substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench; (5) transferring the resist pattern into an underlying film or work piece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper. Definitions [0213] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1- 10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. Such an aliphatic can be unsubstituted or substituted with one or more groups, such as groups described herein for an alkyl group. [0214] By “alkenyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). An exemplary alkenyl includes an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl. [0215] By “alkenylene” is meant a multivalent (e.g., bivalent) form of an alkenyl group, as defined herein. The alkenylene group can be substituted or unsubstituted. For example, the alkenylene group can be substituted with one or more substitution groups, as described herein for alkyl. [0216] By “alkoxy” is meant -OR, where R is an optionally substituted alkyl group, as described herein. Exemplary alkoxy groups include methoxy, ethoxy, butoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For
Attorney Docket No. LAM1P018WO-11683-1WO example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, C1-18, C120, or C1-24 alkoxy groups. [0217] By “alkyl” is meant a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (C1-10), wherein the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., alkane). An alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). An exemplary alkyl includes a branched or unbranched saturated hydrocarbon group of 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. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. For example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (3) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (e.g., -C(O)NR1R2 or -NHCOR1, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1 and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N- protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C1-6 thioalkoxy (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1 is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(O)NR1R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1 is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl-
Attorney Docket No. LAM1P018WO-11683-1WO C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) -SO2NR1R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (26) -SiR1R2R3, where each of R1 and R2 and R3 is, independently, selected from the group consisting of (a) hydrogen, (b) halo, such as F, Cl, Br, or I, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2- 6 alkynyl, or (f) C1-6 alkoxy (e.g., -OR, in which R is C1-6 alkyl); and (27) -NR1R2, where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N- protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4- 18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, or C1-24 alkyl group. [0218] By “alkylene” is meant a multivalent (e.g., bivalent) form of an alkyl group, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, etc. In some embodiments, the alkylene group is a C1-3, C1-6, C1-12, C1-16, C1-18, C1-20, C1-24, C2-3, C2-6, C2-12, C2-16, C2-18, C2-20, or C2-24 alkylene group. The alkylene group can be branched or unbranched. The alkylene group can also be substituted or unsubstituted. For example, the alkylene group can be substituted with one or more substitution groups, as described herein for alkyl. [0219] By “alkylcarbonyl” is meant an alkyl group as previously defined appended to the parent molecular moiety through a carbonyl group. Exemplary, non-limiting alkylcarbonyl groups include methylcarbonyl, ethylcarbonyl, and isopropylcarbonyl among others. [0220] The term “alkylsilyl”, as used herein, refers to SiR3 group, wherein at least one R is an alkyl, and each R is independently selected from H and an alkyl. Alkylsilyls include mono, bis, and tris alkylsilyls. Examples of alkylsilyls include trimethylsilyl, dimethylsilyl, methylsilyl, triethylsilyl, diethylsilyl, and ethylsilyl. [0221] By “alkyleneoxy” is meant an alkylene group, as defined herein, attached to the parent molecular group through an oxygen atom. [0222] By “alkynyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight-chain, or cyclic (e.g.,
Attorney Docket No. LAM1P018WO-11683-1WO cycloalkynyl). An exemplary alkynyl includes an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl. [0223] By “alkynylene” is meant a multivalent (e.g., bivalent) form of an alkynyl group, as defined herein. The alkynylene group can be substituted or unsubstituted. For example, the alkynylene group can be substituted with one or more substitution groups, as described herein for alkyl. [0224] By “amido” is meant -N(RN1)C(O)-, where RN1 is H, optionally substituted alkyl, or optionally substituted aryl. [0225] By “amino” is meant -NRN1RN2, where each of RN1 and RN2 is, independently, H, optionally substituted alkyl, or optionally substituted aryl, or RN1 and RN2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. [0226] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amino group, as defined herein. [0227] By “aminoaryl” is meant an aryl group, as defined herein, substituted by an amino group, as defined herein. [0228] By “aromatic” is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized π- electron system. Typically, the number of out of plane π-electrons corresponds to the Huckel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system. Such an aromatic can be unsubstituted or substituted with one or more groups, such as groups described herein for an alkyl or aryl group. Yet other substitution groups can include aliphatic, haloaliphatic, halo, nitrate, cyano, sulfonate, sulfonyl, or others. [0229] By “aryl” is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C5-15), such as five to ten carbon atoms (C5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. Aryl groups may be substituted with one or more groups
Attorney Docket No. LAM1P018WO-11683-1WO 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 includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C1-6 alkanoyl (e.g., -C(O)-R, in which R is C1-6 alkyl); (2) C1-6 alkyl; (3) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (4) C1-6 alkoxy-C1-6 alkyl (e.g., -L-O-R, in which each of L and R is, independently, C1-6 alkyl); (5) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (6) C1-6 alkylsulfinyl-C1-6 alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, C1-6 alkyl); (7) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (8) C1-6 alkylsulfonyl-C1-6 alkyl (e.g., -L-SO2-R, in which each of L and R is, independently, C1-6 alkyl); (9) aryl; (10) amine (e.g., -NR1R2, where each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1 and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (11) C1-6 aminoalkyl (e.g., -L1-NR1R2 or -L2-C(NR1R2)(R3)-R4, in which L1 is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; each of R1 and R2 is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1 and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; and each of R3 and R4 is, independently, H or C1-6 alkyl); (12) heteroaryl; (13) C1-6 alkyl- C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (14) aryloyl (e.g., -C(O)-R, in which R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C1-6 azidoalkyl (e.g., -L-N3, in which L is C1-6 alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-C1-6 alkyl (e.g., -L-C(O)H, in which L is C1-6 alkyl); (20) C3-8 cycloalkyl; (21) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl); (22) halo; (23) C1-6 haloalkyl (e.g., -L1-X or -L2- C(X)(R1)-R2, in which L1 is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1 and R2 is, independently, H or C1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6- or 7-membered ring containing one, two, three, or four non- carbon heteroatoms); (25) heterocyclyloxy (e.g., -O-R, in which R is heterocyclyl, as defined herein); (26) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C1-6 hydroxyalkyl (e.g., -L1-OH or -L2-C(OH)(R1)-R2, in which L1 is C1-6
Attorney Docket No. LAM1P018WO-11683-1WO alkyl; L2 is a covalent bond or alkyl; and each of R1 and R2 is, independently, H or C1-6 alkyl, as defined herein); (29) nitro; (30) C1-6 nitroalkyl (e.g., -L1-NO or -L2-C(NO)(R1)-R2, in which L1 is C1-6 alkyl; L2 is a covalent bond or alkyl; and each of R1 and R2 is, independently, H or C1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C1-6 alkyl; (33) oxo (e.g., =O); (34) C1-6 thioalkoxy (e.g., -S-R, in which R is C1-6 alkyl); (35) thio-C1-6 alkoxy-C1-6 alkyl (e.g., -L-S-R, in which each of L and R is, independently, C1-6 alkyl); (36) -(CH2)rCO2R1, where r is an integer of from zero to four, and R1 is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1 and R2 is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (38) -(CH2)rSO2R1, where r is an integer of from zero to four and where R1 is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (39) -(CH2)rSO2NR1R2, where r is an integer of from zero to four and where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (40) -(CH2)rNR1R2, where r is an integer of from zero to four and where each of R1 and R2 is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-C3-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, in which R is aryl); (45) cycloalkoxy (e.g., -O-R, in which R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L-R, in which L is alkyl and R is cycloalkyl); (47) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); and (48) -SiR1R2R3, where each of R1 and R2 and R3 is, independently, selected from the group consisting of (a) hydrogen, (b) halo, such as F, Cl, Br, or I, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, or (f) C1-6 alkoxy (e.g., -OR, in which R is C1-6 alkyl). In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 aryl group. [0230] By “arylene” is meant a multivalent (e.g., bivalent) form of an aryl group, as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is a C4-18, C4-14, C4-12, C4-10, C6-18, C6-14, C6-12, or C6-10 arylene group. The arylene
Attorney Docket No. LAM1P018WO-11683-1WO group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substitution groups, as described herein for aryl. [0231] By “aryleneoxy” is meant an arylene group, as defined herein, attached to the parent molecular group through an oxygen atom. [0232] By “azido” is meant -N3. [0233] By “branched alkenyl” is meant an isomer of a straight chain alkenyl compound; one having alkyl groups bonded to the main carbon chain. [0234] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O. [0235] By “cyano” is meant -CN. [0236] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic. Such cycloaliphatic groups can be saturated or unsaturated. [0237] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl. [0238] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic. Such cycloheteroaliphatic groups can be saturated or unsaturated. [0239] By “cycloheteroalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons and having at least one heteroatom, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. The cycloheteroalkyl group can also be substituted or unsubstituted. For example, the cycloheteroalkyl group can be substituted with one or more groups including those described herein for alkyl. [0240] By “dicarbonyl” is meant any moiety or compound including two carbonyl groups, as defined herein. Non-limiting dicarbonyl moieties include 1,2-dicarbonyl (e.g., RC1-C(O)- C(O)RC2, in which each of RC1 and RC2 is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group); 1,3-dicarbonyl (e.g., RC1-C(O)- C(R1aR2a)-C(O)RC2, in which each of RC1 and RC2 is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1a and R2a is, independently, H or an optional substituent provided for alkyl, as defined herein); and 1,4- dicarbonyl (e.g., RC1-C(O)-C(R1aR2a)-C(R3aR4a)-C(O)RC2, in which each of RC1 and RC2 is, independently, optionally substituted alkyl, halo, optionally substituted alkoxy, hydroxyl, or a leaving group and in which each of R1a, R2a, R3a, and R4a is, independently, H or an optional
Attorney Docket No. LAM1P018WO-11683-1WO substituent provided for alkyl, as defined herein). [0241] The term “fluoroalkyl”, as used herein, refers alkyl groups containing one or more fluorine substituents. In some implementations fluoroalkyls contain exclusively fluorine substituents, such as in CF3, C2F5, C3F7. Fluoroalkyls may be linear, branched and cyclic. [0242] By “halo” is meant F, Cl, Br, or I. [0243] By “halo containing substituent” is meant a group that contains a halo, such as a haloaliphatic or haloalkyl group. [0244] By “haloaliphatic” is meant an aliphatic group, as defined herein, substituted with one or more halo. [0245] By “haloalkenyl” is meant an alkenyl group, as defined herein, substituted with one or more halo. [0246] By “haloalkynyl” is meant an alkynyl group, as defined herein, substituted with one or more halo. [0247] By “haloalkyl” is meant an alkyl group, as defined herein, substituted with one or more halogen. Non-limiting unsubstituted haloalkyl groups include C1-2 haloalkyl, C1-3 haloalkyl, C1-4 haloalkyl, C1-5 haloalkyl, C1-6 haloalkyl, C2-3 haloalkyl, C2-4 haloalkyl, C2-5 haloalkyl, C2-6 haloalkyl, or C3-6 haloalkyl. Other non-limiting haloalkyl groups include -CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXzH2zCXyH3-y, wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z or y is not 0; -CH2CXyH3-y, wherein y is 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I); -CXz1H2z1CXz2H2z2CXyH3-y, wherein each of z1 and z2 is, independently, 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z1, z2, or y is not 0; and -CXzH1z[CXy1H3-y1][CXy2H3-y2], wherein z is 0 or 1, wherein each of y1 and y2 is, independently, 0, 1, 2, or 3, and wherein each X is, independently, halo (F, Cl, Br, or I), in which at least one of z, y1, or y2 is not 0. [0248] By “haloalkylene” is meant an alkylene group, as defined herein, substituted with one or more halo. [0249] By “heteroaliphatic” is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. [0250] By “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” is meant an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon,
Attorney Docket No. LAM1P018WO-11683-1WO boron, selenium, phosphorous, and oxidized forms thereof within the group. The heteroalkyl, heteroalkenyl, and/or heteroalkynyl groups can also be substituted or unsubstituted. For example, the heteroalkyl, heteroalkenyl, and/or heteroalkynyl groups can be substituted with one or more groups including those described herein for alkyl. [0251] By “heteroalkylene,” “heteroalkenylene,” and “heteroalkynylene” is meant an alkylene, alkenylene, or alkynylene group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group. The heteroalkylene, heteroalkenylene, and/or heteroalkynylene groups can also be substituted or unsubstituted. For example, the heteroalkylene, heteroalkenylene, and/or heteroalkynylene groups can be substituted with one or more groups including those described herein for alkyl. [0252] By “heterocyclyl” is meant a 3-, 4-, 5-, 6- or 7-membered ring (e.g., a 5-, 6- or 7- membered ring), unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, selenium, or halo). The 3-membered ring has zero to one double bonds, the 4- and 5-membered ring has zero to two double bonds, and the 6- and 7-membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include acridinyl, adenyl, alloxazinyl, azaadamantanyl, azabenzimidazolyl, azabicyclononyl, azacycloheptyl, azacyclooctyl, azacyclononyl, azahypoxanthinyl, azaindazolyl, azaindolyl, azecinyl, azepanyl, azepinyl, azetidinyl, azetyl, aziridinyl, azirinyl, azocanyl, azocinyl, azonanyl, benzimidazolyl, benzisothiazolyl, benzisoxazolyl, benzodiazepinyl, benzodiazocinyl, benzodihydrofuryl, benzodioxepinyl, benzodioxinyl, benzodioxanyl, benzodioxocinyl, benzodioxolyl, benzodithiepinyl, benzodithiinyl, benzodioxocinyl, benzofuranyl, benzophenazinyl, benzopyranonyl, benzopyranyl, benzopyrenyl, benzopyronyl, benzoquinolinyl, benzoquinolizinyl, benzothiadiazepinyl, benzothiadiazolyl, benzothiazepinyl, benzothiazocinyl, benzothiazolyl, benzothienyl, benzothiophenyl, benzothiazinonyl, benzothiazinyl, benzothiopyranyl, benzothiopyronyl, benzotriazepinyl, benzotriazinonyl, benzotriazinyl, benzotriazolyl, benzoxathiinyl, benzotrioxepinyl, benzoxadiazepinyl, benzoxathiazepinyl, benzoxathiepinyl, benzoxathiocinyl, benzoxazepinyl, benzoxazinyl,
Attorney Docket No. LAM1P018WO-11683-1WO benzoxazocinyl, benzoxazolinonyl, benzoxazolinyl, benzoxazolyl, benzylsultamyl benzylsultimyl, bipyrazinyl, bipyridinyl, carbazolyl (e.g., 4H-carbazolyl), carbolinyl (e.g., β- carbolinyl), chromanonyl, chromanyl, chromenyl, cinnolinyl, coumarinyl, cytdinyl, cytosinyl, decahydroisoquinolinyl, decahydroquinolinyl, diazabicyclooctyl, diazetyl, diaziridinethionyl, diaziridinonyl, diaziridinyl, diazirinyl, dibenzisoquinolinyl, dibenzoacridinyl, dibenzocarbazolyl, dibenzofuranyl, dibenzophenazinyl, dibenzopyranonyl, dibenzopyronyl (xanthonyl), dibenzoquinoxalinyl, dibenzothiazepinyl, dibenzothiepinyl, dibenzothiophenyl, dibenzoxepinyl, dihydroazepinyl, dihydroazetyl, dihydrofuranyl, dihydrofuryl, dihydroisoquinolinyl, dihydropyranyl, dihydropyridinyl, dihydroypyridyl, dihydroquinolinyl, dihydrothienyl, dihydroindolyl, dioxanyl, dioxazinyl, dioxindolyl, dioxiranyl, dioxenyl, dioxinyl, dioxobenzofuranyl, dioxolyl, dioxotetrahydrofuranyl, dioxothiomorpholinyl, dithianyl, dithiazolyl, dithienyl, dithiinyl, furanyl, furazanyl, furoyl, furyl, guaninyl, homopiperazinyl, homopiperidinyl, hypoxanthinyl, hydantoinyl, imidazolidinyl, imidazolinyl, imidazolyl, indazolyl (e.g., 1H-indazolyl), indolenyl, indolinyl, indolizinyl, indolyl (e.g., 1H-indolyl or 3H- indolyl), isatinyl, isatyl, isobenzofuranyl, isochromanyl, isochromenyl, isoindazoyl, isoindolinyl, isoindolyl, isopyrazolonyl, isopyrazolyl, isoxazolidiniyl, isoxazolyl, isoquinolinyl, isoquinolinyl, isothiazolidinyl, isothiazolyl, morpholinyl, naphthindazolyl, naphthindolyl, naphthiridinyl, naphthopyranyl, naphthothiazolyl, naphthothioxolyl, naphthotriazolyl, naphthoxindolyl, naphthyridinyl, octahydroisoquinolinyl, oxabicycloheptyl, oxauracil, oxadiazolyl, oxazinyl, oxaziridinyl, oxazolidinyl, oxazolidonyl, oxazolinyl, oxazolonyl, oxazolyl, oxepanyl, oxetanonyl, oxetanyl, oxetyl, oxtenayl, oxindolyl, oxiranyl, oxobenzoisothiazolyl, oxochromenyl, oxoisoquinolinyl, oxoquinolinyl, oxothiolanyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenothienyl (benzothiofuranyl), phenoxathiinyl, phenoxazinyl, phthalazinyl, phthalazonyl, phthalidyl, phthalimidinyl, piperazinyl, piperidinyl, piperidonyl (e.g., 4-piperidonyl), pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolopyrimidinyl, pyrazolyl, pyridazinyl, pyridinyl, pyridopyrazinyl, pyridopyrimidinyl, pyridyl, pyrimidinyl, pyrimidyl, pyronyl, pyrrolidinyl, pyrrolidonyl (e.g., 2-pyrrolidonyl), pyrrolinyl, pyrrolizidinyl, pyrrolyl (e.g., 2H-pyrrolyl), pyrylium, quinazolinyl, quinolinyl, quinolizinyl (e.g., 4H-quinolizinyl), quinoxalinyl, quinuclidinyl, selenazinyl, selenazolyl, selenophenyl, succinimidyl, sulfolanyl, tetrahydrofuranyl, tetrahydrofuryl, tetrahydroisoquinolinyl, tetrahydroisoquinolyl, tetrahydropyridinyl, tetrahydropyridyl (piperidyl), tetrahydropyranyl, tetrahydropyronyl, tetrahydroquinolinyl, tetrahydroquinolyl, tetrahydrothienyl, tetrahydrothiophenyl, tetrazinyl, tetrazolyl, thiadiazinyl (e.g., 6H-1,2,5- thiadiazinyl or 2H,6H-1,5,2-dithiazinyl), thiadiazolyl, thianthrenyl, thianyl, thianaphthenyl, thiazepinyl, thiazinyl, thiazolidinedionyl, thiazolidinyl, thiazolyl, thienyl, thiepanyl, thiepinyl,
Attorney Docket No. LAM1P018WO-11683-1WO thietanyl, thietyl, thiiranyl, thiocanyl, thiochromanonyl, thiochromanyl, thiochromenyl, thiodiazinyl, thiodiazolyl, thioindoxyl, thiomorpholinyl, thiophenyl, thiopyranyl, thiopyronyl, thiotriazolyl, thiourazolyl, thioxanyl, thioxolyl, thymidinyl, thyminyl, triazinyl, triazolyl, trithianyl, urazinyl, urazolyl, uretidinyl, uretinyl, uricyl, uridinyl, xanthenyl, xanthinyl, xanthionyl, and the like, as well as modified forms thereof (e.g., including one or more oxo and/or amino) and salts thereof. The heterocyclyl group can be substituted or unsubstituted. For example, the heterocyclyl group can be substituted with one or more substitution groups, as described herein for aryl. [0253] By “heterocyclyldiyl” is meant a bivalent form of a heterocyclyl group, as described herein. In one instance, the heterocyclyldiyl is formed by removing a hydrogen from a heterocyclyl group. Exemplary heterocyclyldiyl groups include piperdylidene, quinolinediyl, etc. The heterocyclyldiyl group can also be substituted or unsubstituted. For example, the heterocyclyldiyl group can be substituted with one or more substitution groups, as described herein for heterocyclyl. [0254] By “hydroxyl” is meant -OH. [0255] The term “independently selected”, when referring to R substituent selection in a molecule containing multiple R groups, means that the selection of R substituents at different atoms of a molecule is independent and that the selection of R substituents at one atom having multiple R substituents is also independent. [0256] By “imido” is meant M=NR, in which M is a metal and R can be H or optionally substituted alkyl. [0257] By “imino” is meant -NR-, in which R can be H or optionally substituted alkyl. [0258] By “isocyanato” is meant -NCO. [0259] By “isocyano” is meant -N≡C-, and includes nitriles of the formula RN≡C-, wherein R is an aliphatic, aryl or heteroaryl group. [0260] By “isothiocyanato” is meant -N=C=S. [0261] The term “lower” modifying “alkyl”, “alkenyl”, “alkynyl”, “alkoxy” or “alkoxycarbonyl” refers to a C1-C6 unit for a particular functionality. For example, “lower alkyl” means C1-C6 alkyl. [0262] By “low valent” is meant the lower oxidation states when a metal has multiple oxidation states. [0263] By “oxo” is meant an =O group. [0264] By “oxy” is meant -O-. [0265] By “silyl” is meant a -SiR1R2R3 or -SiR1R2- group. In some embodiments, each of R1, R2, and R3 is, independently, H, optionally substituted aliphatic, optionally substituted
Attorney Docket No. LAM1P018WO-11683-1WO heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. [0266] By “silyloxy” is meant -OR, where R is an optionally substituted silyl group, as described herein. In some embodiments, the silyloxy group is -O-SiR1R2R3, in which each of R1, R2, and R3 is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In particular embodiments, each of R1, R2, and R3 is, independently, H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R)a(OR)b(NR2)c, in which each R is, independently, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; each of a, b, and c ≥ 0; and a + b + c = 3. In particular embodiments, each R is, independently, H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. [0267] By “thiocyanato” is meant -SCN. [0268] By “thioether” is meant to include to include both unidentate and multidentate (e.g. bidentate or tridentate) thioethers, as well as ligands that contain both thioether and thiolate (or other) moieties. [0269] By “unsaturated” is meant a moiety that contains double or triple carbon-carbon bonds. [0270] By “unsaturated substituent” is meant a double or triple bond containing aliphatic chain, cyclic, aryl or heteroaryl group. [0271] Use of the above terms is meant to encompass substituted and unsubstituted moieties. Substitution may be by one or more groups such as alcohols, ethers, esters, amides, sulfones, sulfides, hydroxyl, nitro, cyano, carboxy, amines, heteroatoms, lower alkyl, lower alkoxy, lower alkoxycarbonyl, alkoxyalkoxy, acyloxy, halogens, trifluoromethoxy, trifluoromethyl, alkyl, aralkyl, alkenyl, alkynyl, aryl, cyano, carboxy, carboalkoxy, carboxyalkyl, cycloalkyl,
Attorney Docket No. LAM1P018WO-11683-1WO cycloalkylalkyl, heterocyclyl, alkylheterocyclyl, heterocyclylalkyl, oxo, arylsulfonyl and aralkyaminocarbonyl, or any of the substituents of the preceding paragraphs or any of those substituents either directly attached or by suitable linkers. The linkers are typically short chains of 1-3 atoms containing any combination of -C-, -C(O)-, -NH-, -S-, -S(O)-, -O-, -C(O)- or - S(O)O-. Rings may be substituted multiple times. [0272] By “substituted” is meant having one or more substituent moieties whose presence does not interfere with the desired function or reactivity. Examples of substituents alkyl, alkenyl, alkynyl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, guanidine, hydroxyl, thioether, alkylcarbonyl, alkylcaronyloxy, alkoxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonato, cyano, halo, acylamino, imino, sulfhydryl, alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfato, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether, ester, silicon-containing moieties, thioester or a combination thereof. The substituents may themselves be substituted. For instance, an amino substituent may itself be mono or independently disubstituted by further substituents defined above, such as alkyl, alkenyl, alkynyl, and cycloalkyl (non-aromatic ring). [0273] By “unsubstituted” is meant any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position on an atom is not specified, then it is hydrogen. [0274] A person of ordinary skill in the art would recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., methyl substituted with 5 different groups, and the like). Such impermissible substitution patterns are easily recognized by a person of ordinary skill in the art. Any functional group disclosed herein and/or defined above can be substituted or unsubstituted, unless otherwise indicated therein. [0275] As used herein, the term “about” is understood to account for minor increases and/or decreases beyond a recited value, which changes do not significantly impact the desired function of the parameter beyond the recited value(s). In some cases, “about” encompasses +/-10% of any recited value. As used herein, this term modifies any recited value, range of values, or endpoints of one or more ranges. [0276] As used herein, the terms “top,” “bottom,” “upper,” “lower,” “above,” and “below” are used to provide a relative relationship between structures. The use of these terms does not indicate or require that a particular structure must be located at a particular location in the apparatus. [0277] The term “ampoule” may generally represent a vessel for holding a chemical. An ampoule may be at least partially filled with a chemical in liquid phase such that a remaining portion of the ampoule includes the chemical in vapor phase.
Attorney Docket No. LAM1P018WO-11683-1WO [0278] The term “ampoule assembly” may generally represent components of a processing tool including an ampoule, ampoule heater, and gas lines for delivering a vaporized chemical from the ampoule to a processing chamber of the processing tool. [0279] The term “ampoule heater” may generally represent a heater for heating liquid contained in an ampoule. [0280] The term “bulkfill port” may generally represent an inlet of an ampoule for refilling the ampoule with a liquid chemical. [0281] The term “carrier gas” may generally represent a gas used various processes to transport a chemical vapor. Suitable carrier gases include inert gases such as nitrogen (N2), argon (Ar), helium (He), neon (Ne), and krypton (Kr). [0282] The term “chemical vapor deposition” (CVD) may generally represent a process for depositing a film on a substrate by flowing one or more chemicals over the substrate under conditions which cause the chemicals to form a film on the substrate. [0283] By “deposition” or “vapor deposition” is meant a process in which a metal layer is formed on one or more surfaces of a substrate from vaporized precursor composition(s) including one or more metal containing compounds. The metal-containing compounds are vaporized and directed to and/or contacted with one or more surfaces of a substrate (i.e., semiconductor substrate or semiconductor assembly) placed in a deposition chamber. Typically, the substrate is heated. These metal containing compounds form a non-volatile, thin, uniform metal-containing layer on the surface(s) of the substrate. One operation of the method is one cycle, and the process can be repeated for as many cycles necessary to obtain the desired metal thickness. [0284] The term “film” may generally represent a layer of material deposited on a substrate. [0285] The term “flow-over vapor” (FOV) may generally represent the flow of a carrier gas over a surface of a liquid chemical to draw and transport chemical vapor with the flow of the carrier gas. [0286] The term “flow-over vapor gas inlet” may generally represent a port on an ampoule for flowing a carrier gas into the ampoule. [0287] The term “flow-over vapor gas outlet” may generally represent a port on an ampoule for flowing a carrier gas and vapor out of the ampoule. [0288] The term “heated gas line” may generally represent a conduit of a chemical vapor deposition tool that is heated by one or more heaters and that is used to transport a gas-phase chemical substance. [0289] The term “inhibitor” may generally represent a processing chemical that physisorbs or chemisorbs to a material forming a substrate surface and prevents growth of, or reduces a rate of
Attorney Docket No. LAM1P018WO-11683-1WO growth of, a film on the substrate surface compared to areas of the substrate surface comprising the material without the inhibitor. [0290] The term “intermetal dielectric” may generally represent a dielectric material positioned between metal regions in a substrate. [0291] The term “liquid level sensor” may generally represent a sensor configured to detect a level of a liquid within an ampoule. Example liquid level sensors include discrete liquid level sensors and continuous liquid level sensors. A discrete liquid level sensor may generally represent a sensor configured to sense presence of liquid at one or more fixed levels. A continuous liquid level sensor may generally represent a sensor configured to detect a liquid level over a continuous range of levels. [0292] The term “low vapor pressure,” in reference to a chemical, may generally represent a vapor pressure that is below 10 torr at a temperature of 60 ºC. [0293] As used herein, “metal-containing film” refers to a film only including metal or a film which contains a metal and additional components. [0294] The term “processing chamber” may generally represent an enclosure in which chemical and/or physical processes are performed on substrates. [0295] The term “processing gas outlet” may generally represent a structure for injecting a gas- phase processing chemical into a processing chamber of a processing tool. A processing gas outlet may include a nozzle or showerhead in various examples. Example processing chemicals include film precursors, reactants, and inert gases. [0296] The term “processing tool” may generally represent a machine comprising a processing chamber and other hardware configured to enable processing to be carried out in the processing chamber. [0297] The term “substrate” may generally represent any object on which a film can be deposited. [0298] The term “substrate heater” may generally represent a heater in a processing chamber configured to heat a substrate. A substrate heater may be integrated with a substrate support, or may be located elsewhere in a processing chamber. [0299] The term “substrate support” may generally represent any structure for supporting a substrate in a processing chamber. Examples include pedestals, electrostatic chuck pedestals, and showerhead pedestals used for backside deposition processes. Conclusion [0300] 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
Attorney Docket No. LAM1P018WO-11683-1WO practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein.