Metal and phosphorus containing films and methods and systems for producing said films and uses

Abstract

The present disclosure relates generally to metal and phosphorus containing thin films and methods and systems for forming the films, and to semiconductor device structures including the films. An exemplary method for forming a metal and phosphorus containing thin film includes performing one or more deposition cycles of a cyclic deposition process including sequentially exposing at least a portion of a substrate surface to a metal precursor and a phosphorus precursor, thereby forming a metal and phosphorus containing film on at least a portion of the substrate surface. An exemplary semiconductor device structure including a metal and phosphorus containing film may include a field effect transistor structure, wherein the metal and phosphorus containing film may serve as a threshold voltage offset layer.

Description

Technical Field

[0001] The present disclosure generally relates to the field of semiconductor devices. More specifically, the present disclosure generally relates to thin films containing metal and phosphorus, methods and systems for forming such thin films, and semiconductor device structures including such thin films. Background Art

[0002] The scaling down of semiconductor devices (e.g., complementary metal oxide semiconductor (CMOS) devices) has led to a significant increase in the speed and density of integrated circuits. However, further scaling down of next-generation node device sizes is challenging and requires the use of alternative materials and new processing technologies. For example, one challenge is to find a suitable dielectric stack for forming an insulating barrier layer between the gate and the channel of a field effect transistor. As the scaling continues, the reduced size of the gate cavity will only allow thin layers of dielectric stack materials, including threshold voltage offset materials. Thus, methods for obtaining very thin films of novel materials for threshold voltage offset are of great interest. The present disclosure addresses and meets these needs.

[0003] Any discussion set forth in this section, including discussions of problems and solutions, has been included in the present disclosure merely to provide background for the present disclosure. Such discussion should not be construed as an admission that any information was known at the time of the invention or constitutes prior art. Summary of the Invention

[0004] This summary of the invention may introduce some concepts in a simplified form that will be further described in detail below. This summary of the invention is not necessarily intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] The present disclosure relates to a film containing metal and phosphorus, methods and systems for forming such a film, and semiconductor device structures including such a film. The film containing metal and phosphorus can advantageously be used as a threshold voltage offset layer in a gate stack of a field effect transistor (FET).

[0006] One aspect of the present disclosure relates to a film of a material containing metal and phosphorus. The film containing metal and phosphorus can be located on or above at least a portion of a substrate surface, or directly on the substrate surface, or on one or more other layers on the substrate, or can be disposed between two or more other layers on the substrate.

[0007] Another aspect of the present disclosure relates to a structure including a substrate and a threshold voltage offset layer, the threshold voltage offset layer including a metal- and phosphorus-containing material. In some embodiments, the structure may be or form part of a gate stack, where the gate stack includes the threshold voltage offset layer. In some embodiments, the structure may be or form part of a field effect transistor (FET). In some embodiments, the structure may be or form part of a CMOS device.

[0008] Another aspect of the present disclosure relates to a method of forming a film of a metal- and phosphorus-containing material. The method for forming a film of a metal- and phosphorus-containing material can be used to form a structure including a threshold voltage offset layer, the threshold voltage offset layer including a metal- and phosphorus-containing material. Accordingly, the present disclosure also relates to a method for forming a semiconductor device structure including a threshold voltage offset layer, the threshold voltage offset layer including a metal- and phosphorus-containing material. The method includes providing a substrate in a reaction space and performing one or more deposition cycles of a cyclic deposition process, including exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor and exposing at least a portion of the substrate surface to the other of the metal precursor and the phosphorus precursor, thereby forming a metal- and phosphorus-containing film on at least a portion of the substrate surface. The cyclic deposition process may further include purging the reaction space between the exposure steps.

[0009] In some embodiments, the method for forming a metal- and phosphorus-containing film further includes exposing at least a portion of the substrate surface to a halogen reactant. In some embodiments, at least one of the one or more deposition cycles of the cyclic deposition process further includes: exposing at least a portion of the substrate surface to a halogen reactant. In some embodiments, the one or more deposition cycles further include: exposing at least a portion of the substrate surface to a halogen reactant, wherein exposing at least a portion of the substrate surface to the halogen reactant occurs after exposing at least a portion of the substrate surface to the metal precursor and before exposing at least a portion of the substrate surface to the phosphorus precursor.

[0010] In some embodiments, the method for forming a metal- and phosphorus-containing film further includes exposing at least a portion of the substrate surface to an oxygen reactant. In some embodiments, at least one of the one or more deposition cycles of the cyclic deposition process further includes exposing at least a portion of the substrate surface to an oxygen reactant.

[0011] In some embodiments, the method further includes maintaining the temperature of the substrate at an elevated temperature. In some embodiments, the temperature of the substrate is maintained at at least about 40 °C to no more than about 500 °C, or at least about 100 °C to no more than about 450 °C, or at least about 100 °C to no more than about 400 °C, or at least about 100 °C to no more than about 350 °C, or at least about 200 °C to no more than about 450 °C, or at least about 200 °C to no more than about 400 °C, or at least about 200 °C to no more than about 350 °C.

[0012] In some embodiments, the method is carried out under thermal conditions. In these embodiments, the deposition process does not include using plasma to form activated species. For example, in any process step, the cyclic deposition process may not include the use of plasma, may not include the formation or use of excited species, and / or may not include the formation or use of free radicals.

[0013] In some embodiments, the method further includes annealing a substrate including a film containing metal and phosphorus. The annealing can be carried out by heating the substrate including the film containing metal and phosphorus to an annealing temperature ranging from at least about 300 °C to not exceeding about 1200 °C for a set period of time. In some of these embodiments, the annealing is performed by heating the substrate including the film containing metal and phosphorus to an annealing temperature ranging from at least about 600 °C to not exceeding about 1200 °C. In other embodiments, the annealing is performed by heating the substrate including the film containing metal and phosphorus to an annealing temperature ranging from at least about 300 °C to not exceeding about 600 °C.

[0014] Another aspect of the present disclosure relates to a system for forming a film of a material containing metal and phosphorus, such as a semiconductor processing device. The system for forming a film of a material containing metal and phosphorus can be used to form a structure including a threshold voltage offset layer, the threshold voltage offset layer including a material containing metal and phosphorus. Accordingly, the present disclosure also relates to a system for forming a semiconductor device structure including a threshold voltage offset layer, the threshold voltage offset layer including a material containing metal and phosphorus. In some embodiments, the system includes: a reaction space for accommodating a substrate; a metal precursor source for providing a metal precursor that is in gas communication with the reaction space via a metal precursor source valve; a phosphorus precursor source for providing a phosphorus precursor that is in gas communication with the reaction space via a phosphorus precursor source valve; an exhaust device; and a controller operably connected to the metal precursor source valve and the phosphorus precursor source valve, wherein the controller is configured and programmed to perform at least one deposition cycle of a cyclic deposition process. The controller can be configured and programmed to perform at least one deposition cycle of the cyclic deposition process by sequentially controlling: opening one of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; closing one of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; opening the other of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; and closing the other of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source.

[0015] In some embodiments, the system further includes a halogen reactant source for providing a halogen reactant that is in gas communication with the reaction space via a halogen reactant source valve, and the controller is also operably connected to the halogen reactant source valve and is configured and programmed to control: opening the halogen reactant source valve leading to the halogen reactant source; and closing the halogen reactant source valve leading to the halogen reactant source. In some embodiments, the controller is further programmed to open the halogen reactant source valve leading to the halogen reactant source and then close the halogen reactant source valve after closing at least one of the metal precursor source valves leading to the metal precursor source or after closing at least one of the phosphorus precursor source valves leading to the phosphorus precursor source. In some embodiments, the controller is also programmed to open the halogen reactant source valve leading to a third one and then close the halogen reactant source valve after each closing of the metal precursor source valve leading to the metal precursor source.

[0016] In some embodiments, the system further includes an oxygen reactant source for providing an oxygen reactant that is in gas communication with the reaction space via an oxygen reactant source valve, and the controller is also operably connected to the oxygen reactant source valve and is configured and programmed to control: opening the oxygen reactant source valve leading to the oxygen reactant source; and closing the oxygen reactant source valve leading to the oxygen reactant source. In some embodiments, the controller is also programmed to open the oxygen reactant source valve leading to the oxygen reactant source and then close the oxygen reactant source valve after closing at least one of the metal precursor source valves leading to the metal precursor source or after closing at least one of the phosphorus precursor source valves leading to the phosphorus precursor source.

[0017] In some embodiments, the system further includes one or more heating elements and one or more thermocouples, and the controller is also operably connected to the one or more heating elements and the one or more thermocouples and is configured and programmed to measure and control the temperature of at least one heating element to maintain the temperature of the substrate at an elevated temperature. In some embodiments, the temperature of the substrate is maintained at at least about 40 °C to no more than about 500 °C, or at least about 100 °C to no more than about 450 °C, or at least about 100 °C to no more than about 400 °C, or at least about 100 °C to no more than about 350 °C, or at least about 200 °C to no more than about 450 °C, or at least about 200 °C to no more than about 400 °C, or at least about 200 °C to no more than about 350 °C.

[0018] In the aspects disclosed above related to the method and system, in some embodiments, the phosphorus precursor is selected from phosphine (PH 3 ), tetraphosphorus (P 4 ), 1,2-diphosphinoethane (C 2 H 8 P 2 ), methylphosphine (PH 2Me), trimethylphosphine (PMe 3 ), ethylphosphine (PH 2 Et), triethylphosphine (PEt 3 ), isopropylphosphine (PH 2 i Pr), isobutylphosphine (PH 2 i Bu), tert-butylphosphine (PH 2 t Bu), dichloromethylphosphine (MePCl 2 ), dichloroethylphosphine (PCl 2 Et), dichloropropylphosphine (PCl 2 n Pr), dichloroisopropylphosphine (PCl 2 i Pr), dichlorobutylphosphine (PCl 2 n Bu), dichlorotert-butylphosphine (PCl 2 t Bu), chloro(diisopropyl)phosphine (PCl i Pr 2 ), chloro(dimethyl)phosphine (PClMe 2 ), chloro(diethyl)phosphine (PClEt 2 ), chloro(di-sec-butyl)phosphine (PCl s Bu 2 ), chloro(di-tert-butyl)phosphine (PCl t Bu 2 ), bromo(di-sec-butyl)phosphine (PBr t Bu 2 ), chloro(tert-butyl)(methyl)phosphine (PCl t BuMe), cyclohexylphosphine (PH 2 (C 6 H 11 )), phenylphosphine (PH 2 Ph), 1,2-diphosphinobenzene, tris(1-pyrrolidinyl)phosphine (P(C 4 H 8 N) 3 ), dimethylaminophosphine (PH 2 (NMe 2 ) 2 ), bis(dimethylamino)phosphine (PH(NMe 2 )), dimethylamino(methyl)phosphine (PMe(NMe 2 ) 2 ), tris(dimethylamino)phosphine (P(NMe 2 ) 3 ), tris(diethylamino)phosphine (P(NEt 2 ))3 ) Chlorobis(dimethylamino)phosphine (PCl(NMe 2 )) 2 ) Dichloro(dimethylamino)phosphine (PCl 2 (NMe 2 )) 2 Dichloro(diethylamino)phosphine (PCl 2 (NEt 2 )) 2 Chlorobis(diethylamino)phosphine (PCl(NEt i )) 2 ) 2 Chlorobis(diisopropylamino)phosphine (PCl(N 2 (N i Pr 2 )) 2 ) 3 Tris(dimethylamino)phosphine (P(NMe 3 )) 3 Trimethylsilylphosphine (P(SiH 3 )) 3 ) 3 Tris(trimethylsilyl)phosphine (P(SiMe 3 )) 3 ) 3 Tris(trimethylsilyloxy)phosphine (P(OSiMe 3 )) 3 ) 2 Trimethyl phosphite (POMe 5 )) 3 Trimethyl phosphate (P(O)OMe 3 )) 3 Phosphorus pentoxide (P 5 O 5 )) 3 Phosphorus trichloride (PCl 3 ))

[0019] In the above - disclosed aspects related to methods and systems, in some embodiments, the metal precursor comprises a metal and one or more ligands selected from halides, carbonyls, oxo, alkyls, cyclopentadienyls, η 6 -arenes, alkoxides, imines, alkylamides, silylamides, β - diketonates, amidines, diazadienes, and triazenes.

[0020] In the above - disclosed aspects related to methods and systems, in some embodiments, the halogen reactant is selected from carbon tetrafluoride (CF 4 ), carbon tetrachloride (CCl 4 ), carbon tetrabromide (CBr 4 ), bis(trichloromethyl) carbonate (C 3 C1 6 O 3 ), diiodomethane (CH 2 I 2 ), diiodoethane (C 2 H 4 I 2 ), acetyl chloride (CH 3 COCl), oxalyl chloride (CO 2 Cl 2 ), sulfur tetrafluoride (SF 4 ), sulfur hexafluoride (SF 6 ), sulfur dichloride (SCl 2 ), disulfur dichloride (S 2 Cl 2 ), thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), xenon difluoride (XeF 2 ), selenium tetrafluoride (SeF 4 ), selenium hexafluoride (SeF 6 ), selenium dichloride (SeCl 2 ), selenium tetrachloride (SeCl 4 ), selenium dichloride (Se 2 Cl 2 ), tellurium hexafluoride (TeF 6 ), silicon tetrachloride (SiC1 4 ), antimony pentafluoride (SbF 5 ), antimony trichloride (SbC1 3 ), antimony pentachloride (SbCl 5 ), boron trichloride (BCl 3 ), germanium tetrachloride (GeCl 4 ), nitrogen trifluoride (NF 3 ), nitrogen chloride fluoride (NC1 2 F and / or NF 2 Cl), nitrosyl fluoride (NOF), nitryl fluoride (NO 2 F), phosphorus trichloride (PCl 3 ), phosphorus pentachloride (PCl 5 ), phosphoryl chloride (POCl 3 ), phosphorus tribromide (PBr 3 ), phosphorus pentabromide (PBr 5) Phosphorus bromide (POBr 3 ) Hydrogen fluoride (HF), hydrogen chloride (HCl), fluorine (F 2 ) Chlorine (Cl 2 ) Bromine (Br 2 ) Titanium tetrafluoride (TiF 4 ) Titanium tetrachloride (TiCl 4 ) Tungsten hexafluoride (WF 6 ) Niobium pentafluoride (NbF 5 ) and niobium pentachloride (NbCl 5 ). In some embodiments, the halogen reactant includes chlorine.

[0021] In the above - disclosed aspects related to the methods and systems, in some embodiments, the oxygen reactant is selected from oxygen, ozone, water, hydrogen peroxide, organic peroxides, alcohols, nitrogen dioxide, nitrous oxide, nitric oxide, dinitrogen pentoxide, pyridine oxide, amine oxide, and combinations thereof. In some embodiments, the oxygen - containing reactant is oxygen, ozone, nitrous oxide, or a combination thereof.

[0022] In the above - disclosed aspects, in some embodiments, the metal - and - phosphorus - containing material includes metals selected from rare - earth metals, Group 4 metals, Group 5 metals, Group 6 metals, Group 13 metals, and combinations thereof. In some embodiments, the metal in the metal - and - phosphorus - containing material is selected from scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, boron, aluminum, gallium, indium, and combinations thereof.

[0023] In the above - disclosed aspects, in some embodiments, the metal - and - phosphorus - containing material includes metal phosphide materials. In some embodiments, the metal - and - phosphorus - containing material is a metal phosphide material. The metal phosphide materials can be selected from rare - earth metal phosphides, Group 4 metal phosphides, Group 5 metal phosphides, Group 6 metal phosphides, Group 13 metal phosphides, and combinations thereof.

[0024] In the above - disclosed aspects, in some embodiments, the metal - and - phosphorus - containing material includes rare - earth metal phosphides. In some embodiments, the metal - and - phosphorus - containing material is a rare - earth metal phosphide. The rare - earth metal phosphides can be selected from scandium phosphide, yttrium phosphide, lanthanum phosphide, cerium phosphide, praseodymium phosphide, neodymium phosphide, promethium phosphide, samarium phosphide, europium phosphide, gadolinium phosphide, terbium phosphide, dysprosium phosphide, holmium phosphide, erbium phosphide, thulium phosphide, ytterbium phosphide, lutetium phosphide, and combinations thereof. In some embodiments, the rare - earth metal phosphides can be selected from scandium phosphide, yttrium phosphide, lanthanum phosphide, cerium phosphide, and combinations thereof.

[0025] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 4 metal phosphide. In some embodiments, the metal- and phosphorus-containing material is a Group 4 metal phosphide. The Group 4 metal phosphide can be selected from vanadium phosphide, niobium phosphide, tantalum phosphide, and combinations thereof.

[0026] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 5 metal phosphide. In some embodiments, the metal- and phosphorus-containing material is a Group 5 metal phosphide. The Group 5 metal phosphide can be selected from titanium phosphide, zirconium phosphide, hafnium phosphide, and combinations thereof.

[0027] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 6 metal phosphide. In some embodiments, the metal- and phosphorus-containing material is a Group 6 metal phosphide. The Group 6 metal phosphide can be selected from chromium phosphide, molybdenum phosphide, tungsten phosphide, and combinations thereof.

[0028] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 13 metal phosphide. In some embodiments, the metal- and phosphorus-containing material is a Group 13 metal phosphide. The Group 13 metal phosphide can be selected from boron phosphide, aluminum phosphide, gallium phosphide, indium phosphide, and combinations thereof.

[0029] In the aspects disclosed above, in certain embodiments, the metal- and phosphorus-containing material further comprises oxygen. In some of these embodiments, the metal- and phosphorus-containing material is a metal phosphide material or a metal oxyphosphide material further comprising oxygen. The metal oxyphosphide material can be selected from rare earth metal oxyphosphides, Group 4 metal oxyphosphides, Group 5 metal oxyphosphides, Group 6 metal oxyphosphides, Group 13 metal oxyphosphides, and combinations thereof.

[0030] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a rare earth metal oxyphosphide. In some embodiments, the metal- and phosphorus-containing material is a rare earth metal oxyphosphide. The rare earth metal phosphide can be selected from scandium oxyphosphide, yttrium oxyphosphide, lanthanum oxyphosphide, cerium oxyphosphide, praseodymium oxyphosphide, neodymium oxyphosphide, promethium oxyphosphide, samarium oxyphosphide, europium oxyphosphide, gadolinium oxyphosphide, terbium oxyphosphide, dysprosium oxyphosphide, holmium oxyphosphide, erbium oxyphosphide, thulium oxyphosphide, ytterbium oxyphosphide, lutetium oxyphosphide, and combinations thereof. In some embodiments, the rare earth metal phosphide can be selected from scandium oxyphosphide, yttrium oxyphosphide, lanthanum oxyphosphide, cerium oxyphosphide, and combinations thereof.

[0031] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 4 metal oxyphosphide. In some embodiments, the metal- and phosphorus-containing material is a Group 4 metal oxyphosphide. The Group 4 metal oxyphosphide can be selected from vanadium oxyphosphide, niobium oxyphosphide, tantalum oxyphosphide, and combinations thereof.

[0032] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 5 metal oxypnictide. In some embodiments, the metal- and phosphorus-containing material is a Group 5 metal oxypnictide. The Group 5 metal oxypnictide may be selected from titanium oxypnictide, zirconium oxypnictide, hafnium oxypnictide, and combinations thereof.

[0033] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 6 metal oxypnictide. In some embodiments, the metal- and phosphorus-containing material is a Group 6 metal oxypnictide. The Group 6 metal oxypnictide may be selected from chromium oxypnictide, molybdenum oxypnictide, tungsten oxypnictide, and combinations thereof.

[0034] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material comprises a Group 13 metal oxypnictide. In some embodiments, the metal- and phosphorus-containing material is a Group 13 metal oxypnictide. The Group 13 metal oxypnictide may be selected from boron oxypnictide, aluminum oxypnictide, gallium oxypnictide, indium oxypnictide, and combinations thereof.

[0035] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing film comprises a metal phosphide material or a metal oxypnictide material, which comprises a metal selected from rare earth metals, titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), chromium (Cr), tungsten (W), and mixtures thereof.

[0036] In the aspects disclosed above, in certain embodiments, the metal- and phosphorus-containing material does not contain or substantially does not contain oxygen. In some embodiments, the oxygen content of the metal- and phosphorus-containing material is less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%.

[0037] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material does not contain or substantially does not contain carbon. In some embodiments, the carbon content of the metal- and phosphorus-containing material is less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%.

[0038] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material does not contain or substantially does not contain non-phosphide phosphorus. In some embodiments, the non-phosphide phosphorus content of the metal- and phosphorus-containing material is less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%.

[0039] In the aspects disclosed above, in some embodiments, the metal- and phosphorus-containing material film has a thickness of about 0.01 nm or greater to about 2 nm or less, typically about 0.01 nm or greater to about 1 nm or less. In some embodiments, the thickness is about 2 nm or less, or about 1 nm or less, or about 0.5 nm or less, or about 0.1 nm or less.

[0040] In the various aspects disclosed above, in certain embodiments, the substrate includes a threshold voltage offset layer that includes a metal and phosphorus-containing material and at least one of an intermediate layer and a high-k dielectric layer. In some embodiments, the substrate includes an intermediate layer, and the threshold voltage offset layer is formed on the intermediate layer. The threshold voltage offset layer may be formed directly on the intermediate layer. In other embodiments, the substrate includes a high-k dielectric layer, and the threshold voltage offset layer is formed on the high-k dielectric layer. The threshold voltage offset layer may be formed directly on the high-k dielectric layer. In some embodiments, the substrate includes one or more work function layers or metal layers, and the threshold voltage offset layer is formed on at least a portion or above at least a portion of one or more work function layers or metal layers. In some cases, the metal and the threshold voltage offset layer are formed directly on at least a portion or above at least a portion of one of the one or more work function layers or metal layers.

[0041] These and other embodiments will become apparent to those skilled in the art from the following detailed description of certain embodiments with reference to the accompanying drawings. The present invention is not limited to any particular embodiment disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The drawings form a part of the specification. The drawings are included to provide a further understanding of the present disclosure and, together with the description, explain certain principles of the present disclosure. The drawings illustrate how exemplary embodiments of the present disclosure may be made and used and should not be construed as limiting the present disclosure to the examples shown and described. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations for describing embodiments of the present disclosure. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. As will be apparent from the more detailed description of the various aspects, embodiments, and configurations of the present disclosure below, further features and advantages will become apparent with reference to the drawings below.

[0043] Figure 1 is a process diagram of a cyclic deposition process 100 according to an embodiment of the present disclosure, where the deposition cycle of the cyclic deposition process includes contacting at least a portion of the substrate surface with one of a metal precursor and a phosphorus precursor 101, and then contacting at least a portion of the substrate surface with the other of the metal precursor and the phosphorus precursor 103. The dashed lines illustrate other optional steps.

[0044] Figure 2 is a process diagram of a cyclic deposition process 200 according to an embodiment of the present disclosure, where the deposition cycle of the cyclic deposition process includes contacting at least a portion of the substrate surface with a metal precursor 201, a halogen reactant 203, and a phosphorus precursor 205. The dashed lines illustrate other optional steps.

[0045] Figure 3 is a process diagram of a cyclic deposition process 300 according to an embodiment of the present disclosure, wherein the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with a phosphorus precursor 301, a metal precursor 303, and a halogen reactant 305. The dashed lines illustrate other optional steps.

[0046] Figure 4 is a process diagram of a cyclic deposition process 400 according to an embodiment of the present disclosure, wherein the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with one of a metal precursor and a phosphorus precursor 401, and then contacting at least a portion of the substrate surface with the other of the metal precursor and the phosphorus precursor 403. The cyclic deposition process may further include, optionally, contacting at least a portion of the substrate surface with a halogen reactant 405. The dashed lines illustrate other optional steps.

[0047] Figure 5 is a process diagram of a cyclic deposition process 500 according to an embodiment of the present disclosure, wherein the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with one of a metal precursor and a phosphorus precursor 501, and then contacting at least a portion of the substrate surface with the other of the metal precursor and the phosphorus precursor 503. The cyclic deposition process may further include, optionally, contacting at least a portion of the substrate surface with an oxygen reactant 505. The dashed lines illustrate other optional steps.

[0048] Figure 6 is a process diagram of a cyclic deposition process 600 according to an embodiment of the present disclosure, wherein the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with a metal precursor 601, a halogen reactant 603, and a phosphorus precursor 605. The cyclic deposition process may further include, optionally, contacting at least a portion of the substrate surface with an oxygen reactant 607. The dashed lines illustrate other optional steps.

[0049] Figure 7 is a process diagram of a cyclic deposition process 700 according to an embodiment of the present disclosure, wherein the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with a phosphorus precursor 701, a metal precursor 703, and a halogen reactant 705. The cyclic deposition process further includes, optionally, contacting at least a portion of the substrate surface with an oxygen reactant 707. The dashed lines illustrate other optional steps.

[0050] Figure 8FIG. 800 is a process diagram of a cyclic deposition process 800 in accordance with an embodiment of the present disclosure, where the deposition cycle of the cyclic deposition process includes contacting at least a portion of a substrate surface with one of a metal precursor and a phosphorus precursor 801, and then contacting at least a portion of the substrate surface with the other of the metal precursor and the phosphorus precursor 803. The cyclic deposition process may further include optionally contacting at least a portion of the substrate surface with one of a halogen reactant and an oxygen reactant 805, and then optionally contacting at least a portion of the substrate surface with the other of the halogen reactant and the oxygen reactant 807. The dashed lines illustrate additional optional steps.

[0051] Figure 9 FIG. 900 is a schematic diagram of a semiconductor processing apparatus 900 in accordance with an embodiment of the present disclosure. DETAILED DESCRIPTION

[0052] The following description of embodiments of compositions, methods, systems, and structures provided herein is merely exemplary and for illustrative purposes only. The following description is not intended to limit the scope of the present disclosure or the claims. Additionally, the recitation of multiple embodiments with the indicated features is not intended to exclude other embodiments having additional features or other embodiments combining different combinations of the recited features. Unless otherwise stated, the exemplary embodiments or their components may be combined or may be applied separately from one another. The headings provided herein (if any) are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.

[0053] Definition

[0054] As used herein, "atomic layer deposition," abbreviated as "ALD," refers to a vapor deposition process in which deposition cycles (e.g., multiple consecutive deposition cycles) are performed in a reaction space (i.e., one or more reaction chambers). Generally, in an ALD process, during each deposition cycle, a precursor is introduced into the reaction space and adsorbed onto a substrate surface, which may include previously deposited material from a previous deposition cycle or other material, to form at most a monolayer of the precursor that does not readily react with an additional excess of the precursor (i.e., a self-limiting reaction). Thereafter, in some cases, another precursor or reactant may be introduced into the reaction space to convert the adsorbed precursor into the desired material on the substrate surface. As used herein, ALD may also mean a process designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or organometallic MBE, as well as chemical beam epitaxy when performed with alternating pulses of reactants.

[0055] As used herein, "cyclic deposition process" refers to a method or process that includes sequentially introducing reactants into a reaction space to deposit a layer or film on or above a substrate, and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include an ALD component and a cyclic CVD component. In a preferred embodiment, the cyclic deposition process disclosed herein refers to an atomic layer deposition process.

[0056] As used herein, "film" or "layer", which are used interchangeably, refers to a continuous, substantially continuous, or discontinuous material that extends in a direction perpendicular to the thickness direction to cover at least a portion of a surface. The film can be located on the side surfaces and / or sidewalls of recessed features of the surface. The thin film can include two-dimensional materials, three-dimensional materials, nanoparticles, partial or complete molecular layers, partial or complete atomic layers, and / or atomic or molecular clusters. The film can be composed of one or more indistinguishable monolayers or sub-monolayers to produce a uniform or substantially uniform material, where the number of monolayers or sub-monolayers affects the thickness of the material.

[0057] As used herein, "gas" refers to a state of matter composed of atoms or molecules that have neither a definite volume nor a definite shape. The gas includes evaporated solids and / or liquids, and can be composed of a single gas or a gas mixture, depending on the context.

[0058] As used herein, the term "independently", when used in the context of describing one or more substituents (which can be represented as "R"), means that a given R group is independently selected relative to other R groups with the same or different subscripts or superscripts and those groups that lack subscripts or superscripts, but also independently of any other species of the same R group. For example, in the formula CR n (NR 2 ) 4-n where n is 0, 1, 2, or 3, each R is an independently selected substituent, and it should be understood that each R group can be different, or two or more R groups can be the same as each other. More specifically, when n = 3, the formula can be written as C(R 1 )(R 2 )(R 3 )(NR 5 R 6 ), and each of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be different from each other, or each of R 1 , R 2 , R 3 , R 4 , R 5 and R6 Two or more of them can be the same as each other, while the others are different from each other.

[0059] As used herein, "precursor" refers to a compound that participates in a chemical reaction to form another compound or element, where a part of the precursor (an element or group in the precursor) is incorporated into the compound or element produced by the chemical reaction. The compound or element produced by the chemical reaction can be a layer and / or film formed on the surface of a substrate.

[0060] "Reactant" as used herein refers to a compound that participates in a chemical reaction to form another compound or element. In some cases, the reactant is a precursor. In other cases, the compound or element produced by the chemical reaction does not contain a part of the reactant (an element or group in the reactant), so the reactant is not a precursor.

[0061] As used herein, "substrate" refers to one or more underlying materials on or which can be used to form devices, circuits, materials, or material layers. The substrate can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. The substrate can be in any form, such as powder, wafer, plate, or workpiece. A wafer-form substrate can extend beyond the boundaries of the processing / reaction chamber where the deposition process occurs and, in some cases, move through the chamber such that the process continues until the end of the substrate is reached. A plate-like substrate can include wafers of various shapes and sizes. The substrate can be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. The substrate can include one or more layers covering a bulk material, for example, the substrate can include nitrides such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or other metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single-crystalline materials. The substrate can include various topologies, such as spaces between gaps, depressions, lines, trenches, vias, holes, or raised portions (such as fins) formed in or on at least a part of the layers of the substrate.

[0062] As used herein, "structure" can be or include a substrate as described herein. The structure can include one or more layers covering the substrate, such as one or more layers formed according to the methods described herein. A device portion can be or include a structure. Similarly, an intermediate device portion can be or include a structure.

[0063] As used herein, "substituent" refers to an atom or group of atoms that replaces one or more atoms (such as a hydrogen atom) or groups of atoms in a parent compound, thereby becoming a new group in the resulting new compound. The substituent replaces the original atom or group of atoms in the parent molecule. For simplicity, the substituent can be represented as an "R" group in a chemical formula, and each "R" group in the compound can be independently selected. Examples of substituents include, but are not limited to: a hydrogen atom (H); an "alkyl" group having the general formula C n H 2n+1 , where n is an integer, such as a saturated straight-chain or branched-chain C 1 to C 10 alkyl group, preferably a C 1 to C 4 alkyl group (such as methyl (Me), ethyl (Et), n-propyl ( n Pr), isopropyl ( 1 Pr), n-butyl ( n Bu), isobutyl ( i Bu), sec-butyl ( s Bu) and tert-butyl ( t Bu)); a "cycloalkyl" group having the general formula C n H 2n-1 , where n is an integer, such as a C 3 to C 6 cycloalkyl group (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl); an "alkenyl" group, such as a C 2 to C 6 straight-chain or branched-chain unsaturated hydrocarbon with one less hydrogen atom (such as vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, ethynyl, propargyl, butynyl, pentynyl and hexynyl); an "aryl" group, such as phenyl, benzyl, tolyl, xylyl, naphthyl, cyclopentadienyl (Cp) and methyl, dimethyl or ethyl cyclopentadienyl; a hydroxyl group (OH); an "alkoxy" group having the general formula C n H 2n+1 O, where n is an integer, such as a straight-chain or branched-chain C 1 to C 10 alkoxy group, usually a C 1 to C 4 alkoxy group (such as methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy and tert-butoxy); a "hydroxyalkyl" group having the general formula C n H 2n OH, where n is an integer, such as a straight-chain or branched-chain C 1 to C 10 hydroxyalkyl group, usually a straight-chain or branched-chain C 1 to C 4Hydroxyalkyl groups (such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl); "alkoxycarbonyl", such as straight-chain or branched C 1 to C 6 carbonyl hydrocarbons (such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, and hexyloxycarbonyl); mercapto group (SH); having the general formula C n H 2n SH "alkylthiol group", where n is an integer, such as straight-chain or branched C 1 to C 6 alkylthiol groups (such as thiolmethyl, thiolethyl, thiolpropyl, thiolbutyl, thiolpentyl, and thiolhexyl); silyl group (SiR’ 3 ), where each R’ is independently an H atom, an organic group such as an alkyl or aryl group; amino group (NR’ 2 ), where each R’ is independently an H atom, an organic group such as an alkyl or aryl group, or a silyl group; halide (X), such as fluoride (F), chloride (Cl), bromide (Br), and iodide (I); "haloxide" (OX), such as fluoroxide (OF), chloroxide (OCl), bromoxide (OBr), and iodoxide (OI); "haloalkyl", where one or more hydrogen atoms on the alkyl or cycloalkyl are replaced by a halogen, such as straight-chain or branched C 1 to C 6 haloalkyls (such as iodomethyl, bromomethyl, chloromethyl, fluoromethyl, trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl); and "haloaryl", where one or more hydrogen atoms on the aryl are replaced by a halogen, such as fluorobenzyl. The substituent itself may be substituted. For example, a hydroxyalkyl is a substituted alkyl where the H atom on the alkyl is replaced by an OH group.

[0064] As used herein, the term "threshold voltage", abbreviated as "Vt", refers to the minimum gate voltage required to create a conduction path between the source and drain terminals of a field-effect transistor (FET).

[0065] As used herein, the term "threshold voltage offset layer" or "Vt offset layer" refers to a layer that can be used in the gate stack of a field-effect transistor and can change the threshold voltage of that field-effect transistor. When used herein, the term "threshold voltage offset layer" may be equivalent to similar terms, such as "threshold voltage adjustment layer", "work function adjustment layer", "work function offset layer", "flat band voltage adjustment layer", "flat band voltage offset layer", "dipole layer", or simply "layer".

[0066] The article "a" or "an" refers to a substance or a genus that includes multiple substances, depending on the context. Thus, the terms "a / an", "one or more", and "at least one" may be used interchangeably herein.

[0067] The terms "comprising", "including", and "having" are open-ended and do not exclude the presence of other elements or components, unless the context clearly indicates otherwise. Comprising, including, and having may be used interchangeably and include the meaning of "consisting of". However, the phrase "consisting of" means that no other features or components exist in addition to the features or components mentioned, unless the context clearly shows otherwise.

[0068] The term "about" as applied to a numerical value generally refers to a numerical range that is considered equivalent to the stated numerical value (e.g., having the same function or result). In some cases, the term "about" may include a numerical value rounded to the nearest significant digit.

[0069] The term "substantially" as applied to a composition, method, system, or structure generally means that additional components do not substantially change the properties and / or functions of the composition, method, system, or structure.

[0070] The term "substantially" as applied to a composition, method, system, or structure generally means a proportion of a value, property, characteristic, etc., or conversely the lack thereof, i.e., at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or higher, or any proportion between about 70% and 100%. In some embodiments, the term "substantially" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0071] The terms "on" or "above" may be used to describe a relative positional relationship. For example, an element, film, or layer may be directly positioned on or above at least a portion of another element, film, or layer and in physical contact therewith; or alternatively, one element, film, or layer may be on or above another element, film, or layer, but there is one or more intervening elements, films, or layers therebetween. Thus, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it should be understood that the terms "under", "below", or "beneath" describe a relative positional relationship and should be interpreted as relative concepts.

[0072] The terms "at least one", "one or more", and "and / or" are open-ended expressions and are both conjunctive and disjunctive in operation. For example, each of the expressions "at least one of A, B, and C", "at least one of A, B, or C", "one or more of A, B, and C", "one or more of A, B, or C", and "A, B, and / or C" means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together. When each of A, B, and C in the above expressions represents an element (e.g., X, Y, and Z) or a category of elements (e.g., X 1 -X n ,Y 1 -Y m and Z 1 -Z o ), the phrase is intended to mean a single element selected from X, Y, and Z, a combination of elements selected from the same category (e.g., X 1 and X 2 ), and a combination of elements selected from two or more categories (e.g., Y 1 and Z 1 ).

[0073] It should be understood that every numerical range given throughout the disclosure is considered to include the upper and lower limits, as well as every narrower numerical range falling within such broader numerical range, as if such narrower numerical ranges were all clearly written herein. By way of example, the phrase "from about 2 to about 4" or "from 2 to 4" includes 2 and 4, as well as integers and / or integer ranges from about 2 to about 3, from about 3 to about 4, and every possible range based on real numbers (e.g., irrational and / or rational numbers), such as from about 2.1 to about 3.9, from about 2.1 to about 3.4, etc.

[0074] Unless otherwise specified, a group of elements in the periodic table refers to the elements within a given column of the periodic table. The group numbers are based on the International Union of Pure and Applied Chemistry (IUPAC) standards established in 1988 and in effect since then. For example, Group 4 elements in the periodic table include titanium (Ti), zirconium (Zr), hafnium (Hf), and rutherfordium (Rf); Group 5 elements in the periodic table include vanadium (V), niobium (Nb), tantalum (Ta), and dubnium (Db); Group 6 elements in the periodic table include chromium (Cr), molybdenum (Mo), tungsten (W), and seaborgium (Sg). The Group 4, 5, and 6 elements are transition metals. In another example, Group 13 elements in the periodic table include boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), and nihonium (Nh). It should be noted that boron (B) is a metalloid; however, for the purposes of this disclosure, in some places in this disclosure, boron may be referred to as a metal and is included with the other Group 13 elements as a Group 13 metal.

[0075] In certain places throughout the disclosure, chemical compounds, functional groups of chemical compounds, or substituents or ligands may be represented by chemical names (e.g., IUPAC names or common names), abbreviated molecular formulas, structures in which hydrogen atoms may be omitted for simplicity, or two or all of the above. If there is a conflict between the chemical name and the molecular formula and structure, and a person of ordinary skill in the art cannot clearly determine the identity of the chemical compound, functional group, or substituent or ligand, the molecular formula shall prevail, followed by the structure, and then the chemical name.

[0076] In the present disclosure, the meaning of any definition does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0077] Description

[0078] A metal-oxide-semiconductor field-effect transistor (MOSFET) is a transistor having a source terminal, an insulating gate, and a drain terminal on a body. Applying a voltage to the gate changes the conductivity of the channel material between the source terminal and the drain terminal, creating a conduction path that allows current (e.g., electrons for an n-type metal-oxide semiconductor (NMOS) and holes for a p-type metal-oxide semiconductor (PMOS)) to flow between the source and the drain. Thus, an electrical signal can be turned on or off depending on the voltage applied to the gate. The minimum gate voltage required to create or terminate the conduction path between the source terminal and the drain terminal is called the threshold voltage (Vt). Historically, MOSFETs have utilized a SiO 2 layer as the gate dielectric and a polysilicon layer as the gate electrode to form the gate stack. However, the continued scaling of MOSFETs requires replacing SiO 2 with a high-κ material as the gate dielectric and replacing polysilicon with a metal as the gate electrode. The gate stack may also include other layers, such as a threshold voltage offset layer, to shift the effective work function of the gate towards the Si conduction band in the case of NMOS or towards the Si valence band in the case of PMOS, thereby allowing independent control and / or offset of the threshold voltage.

[0079] Multi-threshold complementary metal-oxide-semiconductor (CMOS) technology relies on transistors having multiple threshold voltages to optimize delay or power. For advanced CMOS devices, such as central processing units (CPUs) and systems-on-chip (SoCs), multi-Vt offset is essential. However, as scaling continues, the reduced size of the gate cavity will only allow thin layers of dielectric stack materials, including threshold voltage offset materials. Therefore, methods for obtaining very thin films of novel materials for threshold voltage offset are of great interest.

[0080] The present disclosure generally relates to thin films of materials comprising one or more metals (M) and phosphorus (P), and to methods and systems for fabricating such films, and to semiconductor device structures comprising such films. In some embodiments, the metal- and phosphorus-containing film is a metal phosphide film. In some embodiments, the metal- and phosphorus-containing film is substantially free of oxygen and / or carbon. In some embodiments, the average thickness of the metal- and phosphorus-containing film is less than about 1 nm, and even less than about 0.1 nm. Such a film can advantageously be used as a threshold voltage shift layer in the gate stack of a field effect transistor (FET). In particular, in some embodiments, the disclosed metal- and phosphorus-containing film can be used to reduce the voltage for a p-type MOSFET to switch from an off state to an on state, with minimal contribution to the equivalent oxide thickness (EOT) of the gate dielectric stack. In other embodiments, the disclosed metal- and phosphorus-containing film can be used to increase the voltage for an n-type MOSFET to switch from an off state to an on state. These and other advantages will become apparent from the disclosure of the various aspects, embodiments, and configurations contained herein.

[0081] One aspect of the present disclosure relates to a thin film or layer of a material comprising one or more metals (M) and phosphorus (P). Throughout the disclosure in various places, a film or layer comprising one or more metals and phosphorus may be referred to as a metal- and phosphorus-containing film. In some embodiments, a metal- and phosphorus-containing film comprises one or more metals and phosphorus; thus, the film may contain other elements, such as oxygen. In some embodiments, a metal- and phosphorus-containing film consists of or consists essentially of one or more metals and phosphorus. In some embodiments, a metal- and phosphorus-containing film does not contain or contains essentially no oxygen; thus, the metal- and phosphorus-containing film may be considered oxygen-free. The lack or substantial lack of oxygen content or even a low oxygen content (e.g., oxygen content less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%) in the film can advantageously reduce the EOT of the film. In other embodiments, a metal- and phosphorus-containing film further comprises oxygen. In some embodiments, a metal- and phosphorus-containing film comprises, consists essentially of, or consists of one or more metals, phosphorus, and oxygen. Oxygen may be present in the film as an impurity, introduced during the deposition process (e.g., from one or more of a metal precursor, a phosphorus precursor, and a halogen reactant), and / or it may be present as a result of oxygen migrating into the film from an adjacent layer; alternatively, oxygen may be intentionally introduced into the film during the deposition process. In any case, the oxygen content of the film may be greater than about 5% (atomic %), or greater than about 10%, or greater than about 20%, or greater than about 30%, or greater than about 40%, or greater than about 50%. In some embodiments, a metal- and phosphorus-containing film does not contain or contains essentially no carbon; thus, the metal- and phosphorus-containing film may be referred to as carbon-free. The lack or substantial lack of carbon content or even a low carbon content (e.g., carbon content less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%) in the film can advantageously reduce the number of defects in the film, resulting in improved performance. In some embodiments, a metal- and phosphorus-containing film does not contain or contains essentially no elemental phosphorus; thus, the metal- and phosphorus-containing film may be referred to as elemental-phosphorus-free. The lack or substantial lack or even a low elemental phosphorus content (e.g., elemental phosphorus content less than about 5.0% (atomic %), or less than about 1.0%, or less than about 0.1%) in the film can advantageously reduce the number of defects in the film, resulting in improved performance. In some embodiments, a metal- and phosphorus-containing film contains certain elements as impurities, such as one or more of hydrogen, carbon, nitrogen, oxygen, elemental phosphorus, and halogen. In some embodiments, a metal- and phosphorus-containing film may have a purity of at least about 90% (atomic ratio), or at least about 95%, or at least about 98%, or at least about 99%, or at least about 99.5%, or at least about 99.9%, or at least about 99.99%.

[0082] In some embodiments, the metal- and phosphorus-containing film includes a metal phosphide. In some embodiments, the metal- and phosphorus-containing film consists of or consists essentially of a metal phosphide. A metal phosphide is a material that contains M-P bonds, where some, most, or all of the phosphorus has an oxidation state of -3. A metal phosphide can be represented by the general formula MP x where "x" is a variable ranging from about 0.1 to about 3, or more typically from about 0.5 to about 2, depending on the oxidation state of the metal and the process conditions used to form the metal phosphide material. In some embodiments, the metal in the metal phosphide film is one or more of a transition state metal and a Group 13 metal (including boron). For example, in some embodiments, the metal is one or more of a rare earth metal, a Group 4 metal, a Group 5 metal, a Group 6 metal, and a Group 13 metal. In various embodiments, the metal in the metal phosphide material can have an oxidation state of +2, or +3, or +4, or +5, or +6. Thus, in some embodiments, x is about 2 / 3, or about 1, or about 4 / 3, or about 5 / 3, or about 2. In other embodiments, the value of x may not be reasonable.

[0083] In some embodiments, the metal- and phosphorus-containing film further contains oxygen. In some embodiments, the metal- and phosphorus-containing film includes a metal oxyphosphide. In some embodiments, the metal- and phosphorus-containing film consists of or consists essentially of a metal oxyphosphide. A metal oxyphosphide is a material that contains M-O bonds and M-P bonds, where some, most, or all of the phosphorus has an oxidation state of -3. In some embodiments, the metal oxyphosphide includes M-O bonds and M-P bonds, but does not include or substantially does not include P-O bonds. In some embodiments, the metal oxyphosphide includes M-O bonds, M-P bonds, and P-O bonds. In some embodiments, the metal oxyphosphide material is a mixture of a metal oxide material and a metal phosphide material. It can also be said that the metal oxyphosphide material is a metal phosphide material further containing oxygen. The metal oxyphosphide can be represented by the general formula MP x O yIt is represented that "x" is a variable ranging from about 0.1 to about 3, or more typically from about 0.5 to about 2, and "y" is a variable ranging from about 0.05 to about 3.5, more typically from about 0.1 to about 2, or more typically from about 0.2 to about 1, depending on the oxidation state of the metal and the process conditions for forming the metal oxyphosphide material. In some embodiments, the metal in the metal oxyphosphide film is one or more of a transition state metal and a Group 13 metal (including boron). For example, in some embodiments, the metal is one or more of a rare earth metal, a Group 4 metal, a Group 5 metal, a Group 6 metal, and a Group 13 metal. In some embodiments, x is about 1 / 2, y is about 1 / 4, or x is about 2 / 3, y is about 1 / 2, or x is about 1, y is about 1 / 2, or x is about 2 / 3, y is about 1, or x is about 4 / 3, y is about 1 / 2, or x is about 1, y is about 1, or x is about 2 / 3, y is about 3 / 2, or x is about 5 / 3, y is about 1 / 2, or x is about 4 / 3, y is about 1, or x is about 2 / 3, y is about 2, or x is about 1, y is about 3 / 2. Other combinations of x and y are also possible. In some embodiments, the values of x and / or y may be unreasonable. In some embodiments, the oxidation state of the metal can vary across the thickness of the film, and thus the values of x and y can also vary across the thickness of the film.

[0084] In some embodiments, the metal- and phosphorus-containing film comprises a material having the general formula MP x where "x" is a variable ranging from about 0.1 to about 3, or more typically from about 0.5 to about 2. In other embodiments, the metal- and phosphorus-containing film comprises a material having the general formula MP x O y where "x" is a variable ranging from about 0.1 to about 3, or more typically from about 0.5 to about 2, and "y" is a variable ranging from about 0.05 to about 3.5, more typically from about 0.1 to about 2, or more typically from about 0.2 to about 1. The above general formulas (i.e., MP x and MP x O y) The metal (M) therein may be selected from rare earth metals, Group 4 metals, Group 5 metals, Group 6 metals, Group 13 metals, and combinations thereof. In some embodiments, the metal (M) in the above general formula may be selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), boron (B), aluminum (Al), gallium (Ga), indium (In), and combinations thereof. In some embodiments, the metal and phosphorus-containing film includes rare earth metals. For example, the metal in the metal and phosphorus-containing film may be selected from scandium (Sc), yttrium (Y), or lanthanide elements. More specifically, the metal in the metal and phosphorus-containing film may be selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations and mixtures thereof. In some embodiments, the metal in the metal and phosphorus-containing film may be selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), and lutetium (Lu). In some embodiments, the metal and phosphorus-containing film includes a rare earth metal phosphide film. For example, the metal and phosphorus-containing film may include, consist essentially of, or consist of one or more of scandium phosphide, yttrium phosphide, lanthanum phosphide, cerium phosphide, praseodymium phosphide, neodymium phosphide, promethium phosphide, samarium phosphide, europium phosphide, gadolinium phosphide, terbium phosphide, dysprosium phosphide, holmium phosphide, erbium phosphide, thulium phosphide, ytterbium phosphide, lutetium phosphide, and combinations and mixtures thereof. In other embodiments, the metal and phosphorus-containing film includes a rare earth metal oxyphosphide film. For example, the metal and phosphorus-containing film may include, consist essentially of, or consist of one or more of scandium oxyphosphide, yttrium oxyphosphide, lanthanum oxyphosphide, cerium oxyphosphide, praseodymium oxyphosphide, neodymium oxyphosphide, promethium oxyphosphide, samarium oxyphosphide, europium oxyphosphide, gadolinium oxyphosphide, terbium oxyphosphide, dysprosium oxyphosphide, holmium oxyphosphide, erbium oxyphosphide, thulium oxyphosphide, ytterbium oxyphosphide, lutetium oxyphosphide, and combinations and mixtures thereof.

[0085] In some embodiments, the metal and phosphorus-containing film includes Group 4 elements. For example, the metal in the metal and phosphorus-containing film may be selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and combinations and mixtures thereof. In some embodiments, the metal and phosphorus-containing film includes a Group 4 metal phosphide film. For example, the metal and phosphorus-containing film may include, consist essentially of, or consist of one or more of titanium phosphide, zirconium phosphide, hafnium phosphide, and combinations and mixtures thereof. In other embodiments, the metal and phosphorus-containing film includes a Group 4 metal oxyphosphide film. For example, the metal and phosphorus-containing film may include, consist essentially of, or consist of one or more of titanium oxyphosphide, zirconium oxyphosphide, hafnium oxyphosphide, and combinations and mixtures thereof.

[0086] In some embodiments, the metal- and phosphorus-containing film comprises a Group 5 element. For example, the metal in the metal- and phosphorus-containing film can be selected from vanadium (V), niobium (Nb), tantalum (Ta), and combinations and mixtures thereof. In some embodiments, the metal- and phosphorus-containing film comprises a Group 5 metal phosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of vanadium phosphide, niobium phosphide, tantalum phosphide, and combinations and mixtures thereof. In other embodiments, the metal- and phosphorus-containing film comprises a Group 5 metal oxophosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of vanadium oxophosphide, niobium oxophosphide, tantalum oxophosphide, and combinations and mixtures thereof.

[0087] In some embodiments, the metal- and phosphorus-containing film comprises a Group 6 element. For example, the metal in the metal- and phosphorus-containing film can be selected from chromium (Cr), molybdenum (Mo), tungsten (W), and combinations and mixtures thereof. In some embodiments, the metal- and phosphorus-containing film is a Group 6 metal phosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of chromium phosphide, molybdenum phosphide, tungsten phosphide, and combinations and mixtures thereof. In other embodiments, the metal- and phosphorus-containing film is a Group 6 metal oxophosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of chromium oxophosphide, molybdenum oxophosphide, tungsten oxophosphide, and combinations and mixtures thereof.

[0088] In some embodiments, the metal- and phosphorus-containing film comprises a Group 13 element. For example, the metal in the metal- and phosphorus-containing film can be selected from boron (B), aluminum (Al), gallium (Ga), indium (In), and combinations and mixtures thereof. In some embodiments, the metal- and phosphorus-containing film is a Group 13 metal phosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of boron phosphide, aluminum phosphide, gallium phosphide, indium phosphide, and combinations and mixtures thereof. In other embodiments, the metal- and phosphorus-containing film is a Group 13 metal oxophosphide film. For example, the metal- and phosphorus-containing film can comprise, consist essentially of, or consist of one or more of boron oxophosphide, aluminum oxophosphide, gallium oxophosphide, indium oxophosphide, and combinations and mixtures thereof.

[0089] A film containing metal and phosphorus can be located on or above at least a portion of the substrate surface, or directly on the substrate, or on one or more other layers on the substrate, or can be inserted between two or more other layers on the substrate. The substrate is not particularly limited and can be a semiconductor wafer or multiple semiconductor wafers. In addition to the layer containing metal and phosphorus, the substrate can include one or more material layers, such as dielectric layers, insulating layers, metal layers, sacrificial layers, etc. The substrate can include various topological features, such as gaps, depressions, lines, trenches, vias, holes, or spaces between raised portions formed within or on at least a portion of the layers of the substrate. The film containing metal and phosphorus can cover the entire surface of the substrate or only a portion of the substrate surface, and can be present on the side surfaces and / or vertical surfaces or sidewalls of various topological features (if any). In some embodiments, the substrate is a silicon wafer. The silicon wafer can be a single-crystalline silicon wafer (e.g., a p-type single-crystalline silicon wafer). Alternatively, the silicon wafer can include silicon germanium (SiGe). In some embodiments, the substrate further includes a dielectric layer. The dielectric layer can be substantially a single material layer, or it can include multiple thinner material layers of two or more materials. The dielectric layer can include silicon oxide. Additionally or alternatively, the dielectric layer can include a high-κ material. In some embodiments, the substrate further includes one or more of a metal layer and a capping layer. Different material layers can form structures on the surface of the substrate. The structure can be or form part of a CMOS structure, such as one or more PMOS and NMOS structures, or other device structures.

[0090] The metal- and phosphorus-containing film can be a bulk material and / or a layer of a homogeneous material, or can be a thin film of a non-uniform and even discontinuous material. The thickness of the metal- and phosphorus-containing film is not particularly limited. As used herein, "thickness" can be the average thickness measured over a defined area of the film. Generally, the thickness of the metal- and phosphorus-containing film is between about 0.1 nm and about 100 nm, typically between about 0.1 nm and about 50 nm, or more typically between about 0.1 nm and about 10 nm. However, in certain embodiments, due to the dimensions of the semiconductor device structure, only very thin layers of the metal- and phosphorus-containing material are desired or permitted. Many electronic applications may require thin layers of material, including affecting the work function and / or threshold voltage adjustment in transistors, and such thin layers of material may have different properties compared to thicker or bulk material layers. In these embodiments, the film can be continuous and uniform; alternatively, the thin film can be discontinuous. In these embodiments, the average thickness of the metal- and phosphorus-containing film can be about 0.1 nm or greater up to about 2 nm or less, preferably about 0.1 nm or greater up to about 1 nm or less. In some embodiments, the thickness of the metal- and phosphorus-containing film is about 0.1, or about 0.2 nm, or about 0.3 nm, or about 0.4 nm, or about 0.5 nm, or about 0.6 nm, or about 0.7 nm, or about 0.8 nm, or about 0.9 nm, or about 1 nm, or about 1.1 nm, or about 1.2 nm, or about 1.3 nm, or about 1.4 nm, or about 1.5 nm, or about 1.6 nm, or about 1.6 nm, or about 1.8 nm, or about 1.9 nm, or about 2 nm, or any intermediate thickness between about 0.1 nm and 2 nm, or a narrower range of any two of these thicknesses. In some embodiments, the thickness of the metal- and phosphorus-containing film is less than about 2 nm, or less than about 1.9 nm, or less than about 1.8 nm, or less than about 1.7 nm, or less than about 1.6 nm, or less than about 1.5 nm, or less than about 1.4 nm, or less than about 1.3 nm, or less than about 1.2 nm, or less than about 1.1 nm, or less than about 1 nm, or less than about 0.9 nm, or less than about 0.8 nm, or less than about 0.7 nm, or less than about 0.6 nm, or less than about 0.5 nm, or less than about 0.4 nm, or less than about 0.3 nm, or less than about 0.2 nm, or less than about 0.1 nm.

[0091] In some embodiments, the metal- and phosphorus-containing film is a threshold voltage offset layer in a semiconductor device structure. For example, the metal- and phosphorus-containing film can be a threshold voltage offset layer in the gate stack of a FET such as a MOSFET. In these embodiments, the metal- and phosphorus-containing film can be disposed on or above a substrate including a dielectric layer, such as SiO 2a layer and / or a high-κ material layer. In these embodiments, the metal- and phosphorus-containing film may alternatively or additionally be disposed on or over a substrate including an intermediate layer or an interface layer. In these embodiments, the thickness of the metal- and phosphorus-containing film is generally less than 2 nm, or more typically less than 1 nm, or even less than 0.1 nm. Additionally, the metal- and phosphorus-containing film may have a low oxygen content or no oxygen. Alternatively or additionally, the metal- and phosphorus-containing film may have a low carbon content or no carbon. Alternatively or additionally, the metal- and phosphorus-containing film may be free or substantially free of elemental phosphorus.

[0092] Another aspect of the present disclosure relates to a method of forming a metal- and phosphorus-containing film disclosed herein. The method for forming a metal- and phosphorus-containing film can be used to form a structure including a threshold voltage shift layer comprising a metal- and phosphorus-containing material. In some embodiments, the metal- and phosphorus-containing film comprises a metal phosphide material or a metal oxyphosphide material. The method includes providing a substrate in a reaction space (i.e., one or more reaction chambers) and performing one or more deposition cycles of a cyclic deposition process, including sequentially exposing at least a portion of the substrate surface to a metal precursor and a phosphorus precursor to form a metal- and phosphorus-containing film on at least a portion of the substrate surface. The cyclic deposition process may include one or more of an atomic layer deposition (ALD) process and a cyclic chemical vapor deposition (CVD) process.

[0093] In some embodiments, the method for forming a metal- and phosphorus-containing film includes providing a substrate in a reaction space and performing one or more deposition cycles of a cyclic deposition process 100, as Figure 1 shown, including: exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor 101; and exposing at least a portion of the substrate surface to the other of the metal precursor and the phosphorus precursor 103 to form a metal- and phosphorus-containing film on at least a portion of the substrate surface. For example, at least a portion of the substrate surface may be exposed to the metal precursor and then to the phosphorus precursor. Alternatively or additionally, at least a portion of the substrate surface may be exposed to the phosphorus precursor and then to the metal precursor. The cyclic deposition process may further include purging the reaction space (102 and 104) between the exposure steps. Steps 101 and 103 and optional steps 102 and 104 constitute one deposition cycle. The method may include repeating 105 the deposition cycle one or more (n) times during the cyclic deposition process to increase the uniformity and / or thickness of the metal- and phosphorus-containing film on at least a portion of the substrate surface. Once the desired uniformity and / or thickness of the metal- and phosphorus-containing film has been achieved, the cyclic deposition process may be terminated 106.

[0094] In some embodiments, a method for forming a metal- and phosphorus-containing film further comprises exposing at least a portion of a substrate surface to a halogen reactant. The method may include providing a substrate in a reaction chamber and performing one or more deposition cycles of a cyclic deposition process 200, as Figure 2 shown, including: exposing at least a portion of the substrate surface to a metal precursor 201; exposing at least a portion of the substrate surface to a halogen reactant 203; and exposing at least a portion of the substrate surface to a phosphorus precursor 205, thereby forming a metal- and phosphorus-containing film on at least a portion of the substrate surface. Additionally or alternatively, in some of these embodiments, a method for forming a metal- and phosphorus-containing film includes providing a substrate in a reaction chamber and performing one or more deposition cycles of a cyclic deposition process 300, as Figure 3 shown, including: exposing at least a portion of the substrate surface to a phosphorus precursor 301; exposing at least a portion of the substrate surface to a metal precursor 303; and exposing at least a portion of the substrate surface to a halogen reactant 305, thereby forming a metal- and phosphorus-containing film on at least a portion of the substrate surface. In any of these embodiments, a deposition cycle may further include purging the reaction chamber between exposure steps ( Figure 2 202, 204, and 206 in Figure 3 and Figure 2 302, 304, and 306 in Figure 3 ). Steps 201, 203, and 205 and optional purge steps 202, 204, and 206 constitute one deposition cycle; similarly, steps 301, 303, and 305 and optional purge steps 302, 304, and 306 constitute one deposition cycle. In any of these embodiments, the method may further include repeating ( Figure 2 207 in Figure 3 and

[0095] 307 in Figure 1 , Figure 2 , and Figure 3occurs as a final step after the cyclic deposition process shown in any of the figures, or may alternatively occur. Additionally or alternatively, the step of exposing at least a portion of the substrate surface to a halogen reactant may occur intermittently during the cyclic deposition process, or periodically during the cyclic deposition. For example, in some of these embodiments, the method includes providing a substrate in a reaction space and performing one or more deposition cycles of the cyclic deposition process 400, as Figure 4 shown, including: exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor 401; exposing at least a portion of the substrate surface to the other of the metal precursor and the phosphorus precursor 403; and optionally exposing at least a portion of the substrate surface to a halogen reactant 405, thereby forming a metal- and phosphorus-containing film on at least a portion of the substrate surface. For example, at least a portion of the substrate surface may be exposed to the metal precursor, then to the phosphorus precursor, and then optionally to the halogen reactant. Additionally or alternatively, at least a portion of the substrate surface may be exposed to the phosphorus precursor, then to the metal precursor, and then optionally to the halogen reactant. The cyclic deposition process may further include purging the reaction space (402, 404, and 406) between the respective exposure steps. The method may include repeating the exposure of at least a portion of the substrate surface to the metal precursor and the phosphorus precursor one or more (n) times 407, and exposing at least a portion of the substrate surface to the halogen reactant at least once and one or more (m) times 408 to increase the uniformity and / or thickness of the metal- and phosphorus-containing film on at least a portion of the substrate surface. In some cases, the number of times (m) of the repeated halogen reactant exposure steps may be equal to the number of times (n) of the repeated metal precursor and phosphorus precursor exposure steps (i.e., m = n). (Note that in some cases where m = n, the method is also described by the Figure 2 or Figure 3 shown process diagrams.) In other cases, the number of times (m) of the repeated halogen reactant exposure steps may be less than the number of times (n) of the repeated metal precursor exposure and phosphorus precursor exposure steps (i.e., m < n); thus, only some of the deposition cycles include the step 405 of exposing at least a portion of the substrate surface to the halogen reactant. For example, at least a portion of the substrate surface may be exposed to the halogen reactant every other deposition cycle or every few deposition cycles, or only once, as a final exposure step before terminating the process (i.e., m = 0). Once the desired uniformity and / or thickness of the metal- and phosphorus-containing film has been achieved, the cyclic deposition process may be terminated 409.

[0096] In certain embodiments, the method for forming a metal- and phosphorus-containing film further includes exposing at least a portion of the substrate surface to an oxygen reactant. The step of exposing at least a portion of the substrate surface to the oxygen reactant may be performed upon termination Figure 1 、 Figure 2 、 Figure 3 and Figure 4is performed as a final step after the cyclic deposition process shown in any of the figures. Additionally or alternatively, the step of exposing at least a portion of the substrate surface to an oxygen reactant can occur intermittently during the cyclic deposition process, or periodically during the cyclic deposition. For example, in some of these embodiments, the method includes providing a substrate in a reaction space and performing one or more deposition cycles of the cyclic deposition process 500, as Figure 5 shown, including: exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor 501; exposing at least a portion of the substrate surface to the other of the metal precursor and the phosphorus precursor 503; and optionally exposing at least a portion of the substrate surface to an oxygen reactant 505, thereby forming a metal- and phosphorus-containing film further comprising oxygen on at least a portion of the substrate surface. For example, at least a portion of the substrate surface can be exposed to the metal precursor, then to the phosphorus precursor, and then optionally to the oxygen reactant. Additionally or alternatively, at least a portion of the substrate surface can be exposed to the phosphorus precursor, then to the metal precursor, and then optionally to the oxygen reactant. The cyclic deposition process can further include purging the reaction space (502, 504, and 506) between the respective exposure steps. The method can further include repeating the exposure of at least a portion of the substrate surface to the metal precursor and the phosphorus precursor one or more times (n) 507, and exposing at least a portion of the substrate surface to the oxygen reactant at least once, and then one or more times (m) 508, to increase the uniformity and / or thickness of the metal- and phosphorus-containing film on at least a portion of the substrate surface. In some cases, the number of times (m) of the repeated oxygen reactant exposure steps can be equal to the number of times (n) of the repeated metal precursor and phosphorus precursor exposure steps (i.e., m = n). In other cases, the number of times (m) of the repeated oxygen reactant exposure steps can be less than the number of times (n) of the repeated metal precursor and phosphorus precursor exposure steps (i.e., m < n); thus, only some of the deposition cycles include the step of exposing at least a portion of the substrate surface to the oxygen reactant 505. For example, at least a portion of the substrate surface can be exposed to the oxygen reactant every other deposition cycle or every few deposition cycles, or only once, as a final exposure step before terminating the process (i.e., m = 0). Once the desired uniformity and / or thickness of the metal- and phosphorus-containing film has been achieved, the cyclic deposition process can be terminated 509.

[0097] Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5The process flow diagrams shown and described above illustrate exemplary embodiments of the methods disclosed herein for forming metal and phosphorus-containing films. However, those skilled in the art will readily understand that certain process steps in one embodiment can be appropriately combined with certain other process steps in another embodiment to obtain additional embodiments of the disclosed methods. For example, certain process steps from Figure 2 and Figure 5 The illustrated embodiments can be combined to obtain Figure 6 The illustrated embodiment. In another example, certain process steps from Figure 3 and Figure 5 The illustrated embodiments can be combined to obtain Figure 7 The illustrated embodiment. In yet another example, Figure 4 and Figure 5 The illustrated embodiments can be combined to obtain Figure 8 The illustrated embodiment. Additionally, those skilled in the art will readily understand that, as appropriate, other process steps not shown can be inserted during, before, or after the cyclic deposition process. For example, other reaction steps, activation steps, passivation steps, curing steps, and / or cleaning steps can be performed between, before, or after the individual steps. In another example, annealing steps can be performed periodically between deposition cycles or after the cyclic deposition process is completed.

[0098] In embodiments of the present disclosure, a substrate is provided to a reaction space (i.e., one or more reaction chambers). The substrate is not particularly limited and has been generally described above along with certain specific and preferred embodiments. The reaction space is also not particularly limited and can include one or more reaction chambers of a semiconductor processing apparatus. In some embodiments, the semiconductor processing apparatus is a cluster tool. In some embodiments, one or more reaction chambers in a flow-type reactor can be utilized. In some embodiments, one or more reaction chambers in a showerhead-type reactor can be utilized. In some embodiments, one or more reaction chambers in a spatially separated reactor can be utilized. In some embodiments, one or more reaction chambers in a single-wafer reactor with high-volume manufacturing capabilities can be utilized. In other embodiments, one or more reaction chambers in a batch reactor can be utilized. For embodiments using a batch reactor, the reaction chamber can accommodate multiple wafers, for example, the number of wafers can be in the range of 10 to 200, or 50 to 150, or even 100 to 150.

[0099] In some embodiments, the method further includes purging the reaction space between the respective exposure steps. For example, an optional purging step is shown in the process flow diagrams shown below: Figure 1 102 and 104 in

[0100] Figure 2 202, 204, and 206 in Figure 3 302, 304, and 306 in Figure 4 402, 404, and 406 in Figure 5 502, 504, and 506 in Figure 6 602, 604, 606, and 608 in Figure 7 702, 704, 706, and 708 in; and Figure 8 802, 804, 806, and 808 in. As used herein, "purge" means to remove, eliminate, or replace certain gaseous and volatile substances from the reaction space. For example, purging can be carried out by evacuating the reaction space with a vacuum pump and / or by replacing the gas in the reaction space with an inert or substantially inert gas such as argon or nitrogen. In some cases, the purge step can be implemented between two gas pulses that react with each other (e.g., reactants and / or precursors), or in other cases, the purge can be implemented between two gas pulses that do not react with each other. Purging can avoid or at least reduce the gas-phase interaction between two gases that react with each other. Purging can be used to remove volatile or gas-phase reaction products from the substrate surface. It should be understood that purging can be carried out in time or in space, or both. For example, in the case of time purging, the purge step can be used in chronological order, i.e., a first reactant is supplied to the reaction chamber, a purge gas is supplied to the reaction chamber, and then a second reactant is supplied to the reaction chamber, where the substrate on which the material is deposited does not move. For example, in the case of space purging, the purge step can include moving the substrate from a first position to a second position, a first reactant is continuously supplied to the first position, and through a purge gas curtain, a second reactant is continuously supplied to the second position.

[0101] Various process steps can be repeated one or more times to grow a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. As an example, referring to Figure 1 the embodiment shown, the method can include repeating step 101 and 103 of 107 one or more (n) times, or repeating step 101, 102, 103, and 104 of 107 one or more (n) times, to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, referring to Figure 2 the embodiment shown, the method can include repeating step 201, 203, and 205 of 207 one or more (n) times, or repeating step 201, 202, 203, 204, 205, and 206 of 207 one or more (n) times, to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, referring to Figure 3In the illustrated embodiment, the method may include repeating steps 301, 303, and 305 of 307 one or more (n) times, or repeating steps 301, 302, 303, 304, 305, and 306 of 307 one or more (n) times to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, refer to Figure 4 In the illustrated embodiment, the method may include repeating steps 401 and 403 of 407 one or more (n) times, or repeating steps 401, 402, 403, and 404 of 407 one or more (n) times, and optionally repeating step 405 of 408 one or more (m) times, or steps 405 and 406 one or more (m) times to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, refer to Figure 5 In the illustrated embodiment, the method may include repeating steps 501 and 503 of 507 one or more (n) times, or repeating steps 501, 502, 503, and 504 of 507 one or more (n) times, and optionally repeating step 505 of 508 one or more (m) times, or steps 505 and 506 one or more (m) times to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, refer to Figure 6 In the illustrated embodiment, the method may include repeating steps 601, 603, 605 of 610 one or more times (n), or repeating steps 601, 602, 603, 604, 605, and 606 of 610 one or more (n) times, and optionally repeating step 607 of 611 one or more (m) times, or steps 607 and 608 one or more (m) times to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, refer to Figure 7 In the illustrated embodiment, the method may include repeating steps 701, 703, 705 of 710 one or more (n) times, or repeating steps 701, 702, 703, 704, and 705 of 710 one or more (n) times, and optionally repeating step 707 of 711 one or more (m) times, or steps 707 and 708 one or more (m) times to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In another example, refer to Figure 8In the illustrated embodiment, the method can include repeating step 801 and 803 one or more (n) times, or repeating step 801, 802, 803, and 804 one or more (n) times, and optionally repeating step 805 one or more (m1) times, or step 805 and 806 one or more (m1) times, and optionally repeating step 807 one or more (m2) times, or step 807 and 808 to form a metal- and phosphorus-containing film having a target thickness and / or uniformity on at least a portion of the substrate surface. In any of these embodiments, other pulse sequences are possible. For example, the substrate can be exposed to two or more pulses of a metal precursor and then to a phosphorus precursor; or conversely, the substrate can be exposed to two or more pulses of a phosphorus precursor and then to a metal precursor.

[0102] The number of repeat cycles (n) is not particularly limited and depends on the growth per cycle (GPC) rate of the metal- and phosphorus-containing material and the target thickness and / or uniformity of the film. The GPC of the metal- and phosphorus-containing film can be less than / cycle, between about 0.01 and / cycle, or between about 0.05 and about / cycle, or between about 0.05 and / cycle, or between about 0.05 and / cycle. A lower GPC is beneficial because it helps to achieve the desired precision in film thickness and / or film uniformity. The number of repeat cycles (n) can be between 1 and about 1000, typically between 1 and about 500, or between 1 and about 200, or between 1 and about 100, or between 1 and about 50, or between 1 and about 10. The halogen reactant and / or oxygen reactant exposure step (if present) can optionally be repeated m times, periodically between different n cycles (m < n) or before each cycle (m = n). The number of repetitions (m) of the halogen reactant and / or oxygen reactant exposure step can be equal to or less than the number of repeat cycles (n), typically m is about n / 2, about n / 5, about n / 10, or about n / 25. In some embodiments, the halogen reactant and / or oxygen reactant exposure step occurs only once (m = 0).

[0103] According to some embodiments of the present disclosure, the cyclic deposition process is a thermal deposition process. In these cases, the deposition process does not include using a plasma to form an activated species for the deposition process. For example, in any process step, the cyclic deposition process may not include the use of a plasma, may not include the formation or use of an excited species, and / or may not include the formation or use of free radicals. In other embodiments, at least one process step in the cyclic deposition process uses a plasma to excite one or more precursors, one or more reactants, and / or one or more inert gases. In other words, the plasma is used to excite one or more precursors, one or more reactants, and / or one or more inert gases. For example, one or more of a metal precursor, a phosphorus precursor, a halogen reactant, an oxygen reactant, and an inert gas may be supplied by a plasma source to form an excited or activated species. In some embodiments, one or more of a phosphorus precursor, a halogen reactant, and an oxygen reactant may be provided by a plasma source to form an excited or activated species. In some of these embodiments, one or more of the phosphorus precursor, the halogen reactant, and the oxygen reactant include a plasma species.

[0104] The method may further include maintaining the temperature of the substrate at an elevated temperature (i.e., above room temperature). In some embodiments, the method further includes heating the substrate to a temperature of at least about 40°C to no more than about 500°C. In some embodiments, the method includes maintaining the substrate temperature at at least about 40°C to no more than about 500°C, typically at least about 100°C to no more than about 450°C, or at least about 100°C to no more than about 425°C, or at least about 100°C to no more than about 400°C, or at least about 100°C to no more than about 375°C, or at least about 100°C to no more than about 350°C, or at least about 100°C to no more than about 325°C, or at least about 100°C to no more than about 300°C, or at least about 100°C to no more than about 275°C, or at least about 100°C to no more than about 250°C, or at least about 200°C to no more than about 450°C, or at least about 200°C to no more than about 425°C, or at least about 200°C to no more than about 400°C, or at least about 200°C to no more than about 375°C, or at least about 200°C to no more than about 350°C. In some embodiments, the method is carried out while maintaining the substrate at a temperature below about 450°C, or below about 425°C, or below about 400°C, or below about 375°C, or below about 350°C, or below about 325°C, or below about 300°C, or below about 275°C, or below about 250°C, or below about 225°C, or below about 200°C. In some embodiments, the method includes maintaining the substrate temperature at about 50°C, or about 75°C, or about 100°C, or about 125°C, or about 150°C, or about 175°C, or about 200°C, or about 225°C, or about 250°C, or about 275°C, or about 300°C, or about 325°C, or about 350°C, or about 375°C, or about 400°C, or about 425°C, or about 450°C, or about 475°C, or about 500°C

[0105] In certain embodiments, the method may further include annealing a substrate including a film containing metal and phosphorus. Typically, once the cyclic deposition process is completed, the annealing step is carried out. Annealing may be carried out by heating the substrate including the film containing metal and phosphorus to an annealing temperature of from at least about 300°C to no more than about 1200°C for a set period of time, typically from at least about 300°C to no more than about 600°C for low-temperature annealing and from at least about 600°C to no more than about 1200°C for high-temperature annealing, more typically from at least about 700°C to no more than about 900°C. Annealing may be carried out in the same reaction chamber in which the cyclic deposition process takes place, or in a reaction chamber separate from the reaction chamber in which the cyclic deposition process takes place. Annealing may be carried out in an inert environment (e.g., by flowing one or more of He, Ar, and N 2 into the chamber), an oxidizing environment (e.g., by flowing O 2 into the chamber), or a reducing environment (e.g., by flowing H 2(Inflow chamber) and a nitriding environment (e.g., by introducing NH 3 It is carried out in one or more of the inflow chambers). The time length of the annealing step can vary widely, from dozens of seconds to several hours. In addition, more than one annealing step can be performed. One or more annealing steps can be performed to remove impurities in the film, such as reducing the oxygen and / or carbon content in the film, and / or changing the morphology of the film. Additionally or alternatively, high-temperature annealing can be performed as part of the final gate fabrication to drive all or part of the metal- and phosphorus-containing layer and / or other material layers on the substrate into one or more of the insulating layer, intermediate layer, or high-κ dielectric layer.

[0106] In addition to controlling the temperature of the substrate, the method of the present disclosure can be carried out in a reduced-pressure environment. In some embodiments, the method further includes controlling the pressure inside the reaction space. The pressure inside the reaction space can be between about 1 millitorr and about 760 torr, or between about 0.5 torr and about 30 torr, such as about 10 torr, or about 15 torr, or about 20 torr. In some embodiments, the pressure inside the reaction space during the cyclic deposition process is less than about 500 torr, or the pressure inside the reaction chamber during the cyclic deposition process is between about 0.1 torr and about 500 torr, or between about 1 torr and about 100 torr, or between about 1 torr and about 20 torr. In some embodiments, the pressure inside the reaction chamber during the cyclic deposition process is less than about 10 torr, less than about 50 torr, less than about 100 torr, or less than about 300 torr.

[0107] In the method disclosed herein, at least a portion of the substrate surface is exposed to a phosphorus precursor. The phosphorus precursor is introduced into the reaction space, and at least a portion of the substrate surface contacts the phosphorus precursor. The phosphorus precursor can be in gaseous form, or it can be a liquid or solid, but it should have a sufficient vapor pressure at room temperature or near room temperature such that it can be introduced into the reaction space and transported to the substrate surface. Additionally or alternatively, the phosphorus precursor can be heated to provide a sufficient vapor pressure (generally between 1 - 20 torr) and / or be entrained in an inert carrier gas stream (such as nitrogen and / or noble gases, like helium (He) and argon (Ar)) and introduced into the reaction space. In some embodiments, the substrate is exposed to the phosphorus precursor under thermal conditions. In other words, the phosphorus precursor does not contain plasma species, and the substrate is not exposed to plasma species (such as ionic species, radical species, atoms, metastable species, and / or excited species). In other embodiments, the phosphorus precursor is provided by a plasma source to form plasma species. In some of these embodiments, the phosphorus precursor includes plasma species.

[0108] Many suitable phosphorus precursors can be used in the method disclosed herein. The phosphorus precursor contains at least one phosphorus atom and one or more substituents. In some embodiments, the phosphorus precursor has PR 3 (or PR 1 R2 R 3 ) general structure, where each R is an independently selected substituent. For example, each substituent can be independently selected from a hydrogen atom; a halogen; an alkyl group; an aryl group; an alkyl halide group, an aryl halide group, an alkoxy group (i.e., OR’ where R’ is a substituent selected from a hydrogen atom, an alkyl group, and an aryl group); an amino group (i.e., NR’ 2 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an aryl group, and a silyl group); a silyl group (i.e., SiR’ 3 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an alkyl halide, an aryl group, an aryl halide, and a halide); and a silyloxy group (i.e., OSiR’ 3 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an alkyl halide, an aryl group, and an aryl halide). In some embodiments, the phosphorus precursor has P(=O)R 3 (or P(=O)R 1 R 2 R 3 ) general structure, where each R is an independently selected substituent. For example, each substituent can be independently selected from a hydrogen atom; a halogen; an alkyl group; an aryl group; an alkyl halide group, an aryl halide group, an alkoxy group (i.e., OR’, where R’ is a substituent selected from a hydrogen atom, an alkyl group, and an aryl group); an amino group (i.e., NR’ 2 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an aryl group, and a silyl group); a silyl group (i.e., SiR’ 3 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an alkyl halide, an aryl group, and an aryl halide); and a silyloxy group (i.e., OSiR’ 3 , where each R’ is an independently selected substituent from a hydrogen atom, an alkyl group, an alkyl halide, an aryl group, and an aryl halide).

[0109] In some embodiments, the phosphorus precursor is selected from tetraphosphorus (P 4 ); phosphorus pentoxide (P 2 O 5 ); phosphine (PH 3 ); organophosphine (PH 3-n R n , where each R is an independently selected substituent from an alkyl group, an alkyl halide, an aryl group, and an aryl halide, and n is 1, 2, or 3), for example, alkylphosphine or arylphosphine, more specifically, for example, PR 3 , PHR 2 and PH 2 R, where each R is independently selected from Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu,t Bu and Ph; aminophosphines (PR 3-n (NR 3 ) n , where each R is a substituent independently selected from a hydrogen atom, an alkyl group, and an aryl group, and n is 1, 2, or 3), e.g., PH 2 (NR 2 ), PH(NR 2 ) 2 and P(NR 2 ) 3 , where each R is independently selected from Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and PH; phosphoramidates (P(O)(NR 2 ) n (OR) 3-n , where each R is a substituent independently selected from a hydrogen atom, an alkyl group, and an aryl group, and n is 1, 2, or 3), e.g., P(O)(NR 2 ) 3 , P(O)(NR 2 ) 2 (OR) and P(O)(NR 2 )(OR) 2 , where each R is independently selected from H, Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; silylphosphides PR 3-n (SiR 3 ) n , where each R is a substituent independently selected from a hydrogen atom, an alkyl group, an alkyl halide group, an aryl group, and an aryl halide group, and n is 1, 2, or 3), e.g., P(SiR 3 ) 3 , PR(SiR 3 ) 2 , PR 2 (SiR 3 ), where each R is independently selected from H, Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; silyl phosphites (P(OSiR 3 ) n (OR)3-n , where each R is independently a substituent selected from a hydrogen atom, an alkyl group, an alkyl halide group, an aryl group, and an aryl halide group, and n is 1, 2, or 3), for example, P(OSiR 3 ) 3 , where each R is independently selected from H, Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; silyl phosphate (P(O)(OSiR 3 ) n (OR) 3-n , where each R is independently a substituent selected from a hydrogen atom, an alkyl group, an alkyl halide group, an aryl group, and an aryl halide group, and n is 1, 2, or 3), for example, P(O)(OSiR 3 ) 3 , where each R is independently selected from H, Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; phosphite (PH n-3 (OR) n or PR n-3 (OR) n , where each R is independently a substituent selected from an alkyl group, an alkyl halide group, an aryl group, and an aryl halide group, and n is 1, 2, or 3), for example, P(OR) 3 , where each R is independently selected from Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; phosphate (P(O)H 3-n (OR) n or P(O)R 3-n (OR) n , where each R is independently a substituent selected from an alkyl group, an alkyl halide group, an aryl group, and an aryl halide group, and n is 1, 2, or 3), for example, P(O)(OR) 3 , where each R is independently selected from Me, Et, n Pr, i Pr, n Bu, i Bu, s Bu, t Bu and Ph; phosphorus halide (PX 3 or PX5 , where each X is independently selected from Cl, Br, and I); and phosphorus halide (POX 3 , where each X is independently selected from Cl, Br, and I).

[0110] Suitable phosphorus precursors include, but are not limited to, phosphine (PH 3 ), tetraphosphorus (P 4 ), 1,2-diphosphinoethane (C 2 H 8 P 2 ), methylphosphine (PH 2 Me), trimethylphosphine (PMe 3 ), ethylphosphine (PH 2 Et), triethylphosphine (PEt 3 ), isopropylphosphine (PH 2 i Pr), isobutylphosphine (PH 2 i Bu), tert-butylphosphine (PH 2 t Bu), dichloromethylphosphine (MePCl 2 ), dichloroethylphosphine (PCl 2 Et), dichloropropylphosphine (PCl 2 n Pr), dichloroisopropylphosphine (PCl 2 i Pr), dichlorobutylphosphine (PCl 2 n Bu), dichlorotert-butylphosphine (PCl 2 t Bu), w(PCl i Pr 2 ), chloro(dimethyl)phosphine (PClMe 2 ), chloro(diethyl)phosphine (PClEt 2 ), chloro(di-sec-butyl)phosphine (PCl s Bu 2 ), bromo(di-sec-butyl)phosphine (PBr t Bu 2 ), chloro(di-tert-butyl)phosphine (PCl t Bu 2 ), chloro(tert-butyl)(methyl)phosphine (PCl t BuMe), cyclohexylphosphine (PH 2 (C 6 H 11 ), phenylphosphine (PH 2 Ph), 1,2-diphosphinobenzene, tris(1-pyrrolidino)phosphine (P(C 4 H 8 N)3 ) Dimethylaminophosphine (PH 2 (NMe 2 ) 2 ) Bis(dimethylamino)phosphine (PH(NMe 2 ) Dimethylamino(methyl)phosphine (PMe(NMe 2 ) 2 ) Tris(dimethylamino)phosphine (P(NMe 2 ) 3 ) Tris(diethylamino)phosphine (P(NEt 2 ) 3 ) Chlorobis(dimethylamino)phosphine (PCl(NMe 2 ) 2 ) Dichloro(dimethylamino)phosphine (PCl 2 (NMe 2 )) Dichloro(diethylamino)phosphine (PCl 2 (NEt 2 )) Chlorobis(diethylamino)phosphine (PCl(NEt 2 ) 2 ) Chlorobis(diisopropylamino)phosphine (PCl(N i Pr 2 ) 2 ) Dichloro(diisopropylamino)phosphine (PCl 2 (N i Pr 2 )) Tris(dimethylamino)phosphine (P(NMe 2 ) 3 ) Trimethylsilylphosphine (P(SiH 3 ) 3 ) Tris(trimethylsilyl)phosphine (P(SiMe 3 ) 3 ) Tris(triethylsilyl)phosphine (P(SiEt 3 ) 3 ) Tris(trimethylsilyloxy)phosphine (P(OSiMe 3 ) 3 ) Trimethyl phosphite (POMe 3 ) Trimethyl phosphate (P(O)OMe 3 ) Phosphorus pentoxide (P 2 O 5 ) Phosphorus trichloride (PCl 3 ) Phosphorus tribromide (PBr 3 ) Phosphorus triiodide (PI 3 ) Phosphorus pentachloride (PCl 5 ) Phosphorus pentabromide (PBr 5 ) Phosphoryl chloride (POCl 3 ) and Phosphoryl bromide (POBr3 )。

[0111] In the method disclosed herein, at least a portion of the substrate surface is exposed to a metal precursor. The metal precursor is introduced into the reaction space, and at least a portion of the substrate surface is contacted with the metal precursor. The metal precursor can be in gaseous form, or it can be a liquid or solid, but it should have a sufficient vapor pressure at room temperature or near room temperature such that it can be introduced into the reaction space and transported to the substrate surface. Additionally or alternatively, the metal precursor can be heated to provide a sufficient vapor pressure (generally between 1 - 20 Torr) and / or entrained in an inert carrier gas stream (such as nitrogen and / or noble gases, such as helium (He) and argon (Ar)) and introduced into the reaction space. In some embodiments, the substrate is exposed to the metal precursor under thermal conditions. In other words, the metal precursor does not contain plasma species, and the substrate is not exposed to plasma species (such as ionic species, radical species, atoms, metastable species, and / or excited species). In other embodiments, the metal precursor is provided by a plasma source to form plasma species. In some of these embodiments, the metal precursor includes plasma species.

[0112] Many suitable metal precursors can be used in the method disclosed herein. In some embodiments, the metal in the metal precursor is a transition state metal or a Group 13 element. For example, in some embodiments, the metal is one or more of a rare earth element, a Group 4 element, a Group 5 element, a Group 6 element, and a Group 13 element. In some embodiments, the metal in the metal precursor is selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), boron (B), aluminum (Al), gallium (Ga), indium (In), and combinations and mixtures thereof. In some embodiments, the metal in the metal precursor is selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), boron (B), aluminum (Al), gallium (Ga), indium (In), and combinations and mixtures thereof.

[0113] In some embodiments, the metal precursor includes a metal and one or more ligands coordinated around the metal (ML n)。The number of ligands in the metal precursor depends on the oxidation state of the metal, which can vary in different embodiments of the present disclosure and can be +2, or +3, or +4, or +5, or +6. Suitable ligands include, but are not limited to, halides, carbonyls, oxo, alkyls, cyclopentadienyls, η 6 -arenes, alkoxides, imido, alkylamides, silylamides, β-diketonates, amidinates, diazadienes, and triazenides. In some embodiments, the metal precursor includes one type of ligand (i.e., it is homoleptic), while in other embodiments, the metal precursor includes two types of ligands, or three types of ligands, or more (i.e., it is heteroleptic). In some embodiments, the metal precursor includes one or more halide ligands (generally represented by "X"), such as fluoride (F), chloride (Cl), bromide (Br), or iodide (I) ligands. The halide ligands coordinate to the metal through M-X bonds. In some embodiments, the metal precursor includes one or more carbonyl ligands (CO). The carbonyl ligands coordinate to the metal through M-C bonds. In some embodiments, the metal precursor includes one or more oxo ligands (O 2- ). Coordination of the oxo ligand can occur at one metal center as an M-O bond (usually a double or triple bond), or at two metal centers as an M-O-M bond. In some embodiments, the metal precursor includes one or more alkyl ligands. The alkyl ligand can have a straight-chain or branched-chain structure with the general formula C n H n+1 , where n is an integer, typically between 1 and 10, more typically between 1 and 5. The alkyl ligand coordinates to the metal through M-C bonds. Exemplary alkyl ligands include, but are not limited to, methyl (Me), ethyl (Et), n-propyl ( n Pr), isopropyl ( i Pr), n-butyl ( n Bu), sec-butyl ( s Bu), tert-butyl ( t Bu), neopentyl ( n Pe), and tert-pentyl ( t Pe). In some embodiments, the metal precursor includes one or more cyclopentadienyl ligands. The cyclopentadienyl ligand has the general formula C 5 R 5 , where each R is independently selected substituent, typically selected from hydrogen, alkyl, alkyl halide, or halogen. Coordination of the cyclopentadienyl ligand to the metal typically occurs through a pentahapto (η 5 ) bonding mode. Exemplary cyclopentadienyl ligands include, but are not limited to, cyclopentadienyl (Cp), methylcyclopentadienyl (MeCp), dimethylcyclopentadienyl (Me 2 Cp), ethylcyclopentadienyl (EtCp), isopropylcyclopentadienyl ( i(PrCp), isopropylcyclopentadienyl( i (PrCp), tert-butylcyclopentadienyl( t (BuCp), trimethylsilylcyclopentadienyl (TMSCp), pentamethylcyclopentadienyl (Cp*), 1,2,4-triisopropylcyclopentadienyl( i (Pr 3 (Cp) and 1,2,4-tri-tert-butylcyclopentadienyl( t (Bu 3 (Cp). In some embodiments, the metal precursor comprises one or more η 6 -arene ligands. The simplest η 6 -arene ligand is benzene (C 6 H 6 ), and substituted benzenes have the general formula C 6 R 6 , where each R is an independently selected substituent, typically selected from hydrogen, alkyl, haloalkyl, and halogen. Coordination of the η 6 -arene ligand to the metal typically occurs via a hexahapto (η 6 ) bonding mode. Examples of benzene ligands include, but are not limited to, benzene (Ben), toluene (MeBen), and ethylbenzene (EtBen). In some embodiments, the metal precursor comprises one or more alkoxide ligands. Alkoxide ligands have the general formula RO - , where R is a substituent, typically selected from alkyl, alkyl halide, aryl, aryl halide, alkenyl, alkynyl, and alkylsilyl. The alkoxide ligand coordinates to the metal via an M-O bond. Examples of alkoxide ligands include, but are not limited to, methoxide (MeO), ethoxide (EtO), n-propoxide( n (PrO), isopropoxide( i (PrO), n-butoxide( n (BuO), sec-butoxide( s (BuO), tert-butoxide( t (BuO), 1-methoxy-2-methyl-2-propoxide (mmp), 1-dimethylamino-2-propoxide (dmap), 1-dimethylamino-2-methyl-2-propoxide (dmamp), and 1-dimethylamino-2-methyl-2-butoxide (dmamb), and phenoxide (PhO). In some embodiments, the metal precursor comprises one or more imido ligands. Imide ligands have the general formula N-R, where R is a substituent, typically selected from alkyl, alkyl halo, aryl, aryl halo, alkenyl, alkynyl, and alkylsilyl. The imido ligand coordinates to the metal via an M=N bond. Examples of imide ligands include, but are not limited to, imido (NH), methylimido (NMe), ethylimido (NEt), isopropylimido (N i (Pr), tert-butylimido (N t(Bu) and phenylimino (NPh). In some embodiments, the metal precursor comprises one or more organic amino ligands. The organic amido ligand has the general formula NHR or NR 2 , where each R is an independently selected substituent, typically selected from alkyl, alkyl halide, aryl, aryl halide, alkenyl, and alkynyl. Coordination of the organic amide ligand to the metal occurs through an M-N bond. Examples of organic amide ligands include, but are not limited to, methylamido (NHMe), dimethylamido (NMe 2 ), ethylamido (NHEt), diethylamido (NEt 2 ), ethylmethylamido (NMeEt), isopropylamido (NH i Pr), diisopropylamido (N i Pr 2 ), tert-butylamido (NH t Bu) and phenylamido (NHPh). In some embodiments, the metal precursor includes one or more silylamide ligands. The silylamide ligand has the general formula NH(SiR 3 ) or N(SiR 3 ) 2 , where each R is an independently selected substituent, typically selected from alkyl, alkyl halide, aryl, aryl halide, alkenyl, and alkynyl. The silylamino ligand coordinates to the metal through an M-N bond. Example silylamide ligands include, but are not limited to, bis(trimethylsilyl)amido (N(SiMe 3 ) 2 , abbreviated as "hmds"). In some embodiments, the metal precursor includes one or more β-diketone ligands. The β-diketone ligand has the general formula structure of RC(O)C(R)C(O)R, where each R is an independently selected substituent, typically selected from hydrogen, alkyl, alkyl halide, aryl, aryl halide, alkenyl, alkynyl, alkylsilyl, and halogen. Additionally or alternatively, two or more R groups may be linked to form one or more fused ring structures. Coordination of the β-diketone ligand to the metal typically occurs through two M-O bonds to form a six-membered chelate ring. Examples of β-diketone ligands include, but are not limited to, acetylacetonate (CH 3 C(O)CHC(O)CH 3 , abbreviated as "acac"), hexafluoroacetylacetonate (CF 3 C(O)CHC(O)CF 3 , abbreviated as "hfac") and 2,2,6,6-tetramethyl-3,5-heptanedionate ((CH 3 ) 3 CC(O)CHC(O)C(CH 3 ) 3, abbreviated as "thd"). In some embodiments, the metal precursor includes one or more amidine ligands (abbreviated as AMD). The amidine ligand has a general formula structure NRC(R)NR - , where each R is an independently selected substituent, typically selected from hydrogen, alkyl, alkyl halide groups, aryl, aryl halide groups, alkenyl, alkynyl, alkyl silyl, and halogen. Additionally or alternatively, two or more R groups may be linked to form one or more fused ring structures. The coordination of the amidine ligand to the metal typically forms a four-membered chelate ring through two M-N bonds. Examples of amidinated ligands include, but are not limited to, N,N'-diisopropylformamidine (CH 3 CH(CH 3 )NC(H)NCH(CH 3 )CH 3 , abbreviated as " i PrFMD"), N,N'-di-tert-butylformamidine (CH 3 C(CH 3 ) 2 NC(H)NC(CH 3 ) 2 CH 3 , abbreviated as " t BuFMD"), N,N'-diisopropylethylamidine (CH 3 CH(CH 3 )NC(CH 3 )NCH(CH 3 )CH 3 , abbreviated as " i PrAMD"), N,N'-di-tert-butylethylamidine (CH 3 C(CH 3 ) 2 NC(CH 3 )NC(CH 3 ) 2 CH 3 , abbreviated as " t BuAMD") and N,N'-di-sec-butylethylamidine (CH 3 CH 2 CH(CH 3 )NC(CH 3 )NCH(CH 3 )CH 2 CH 3 , abbreviated as " sBuAMD”). In some embodiments, the metal precursor includes one or more 1,4-diaza-1,3-diene ligands (abbreviated as “DAD”). The 1,4-diaza-1,3-diene ligand has the general structure NRC(R)C(R)NR and can be in neutral, anionic, or dianionic form, where each R is an independently selected substituent, typically selected from hydrogen, alkyl, haloalkyl, aryl, haloaryl, alkenyl, alkynyl, trialkylsilyl, and halogen. Additionally or alternatively, two or more R groups can be linked to form one or more fused ring structures, such as the structure of a bipyridine ligand (abbreviated as “bpy”) or a terpyridine ligand (abbreviated as “tpy”). Coordination of the DAD ligand to the metal typically forms a five-membered chelate ring through two M-N bonds. Examples of DAD ligands include, but are not limited to, 1,4-di-tert-butyl-1,4-diaza-1,3-butadiene (tBu 2 DAD), 1,4-diisopropyl-1,4-diaza-1,3-butadiene( i Pr 2 DAD), 1,4-di-sec-butyl-1,4-diaza-1,3-butadiene( s Bu 2 DAD), and 1,4-di-tert-pentyl-1,4-diaza-1,3-butadiene( t Pn 2 DAD). In some embodiments, the metal precursor includes one or more β-diketonimine ligands (abbreviated as “NacNac”). The β-diketonimine ligand has the general formula structure NRC(R)C(R)C(R)NR, where each R is an independently selected substituent, typically selected from hydrogen, alkyl, haloalkyl, aryl, haloaryl, alkenyl, alkynyl, trialkylsilyl, and halogen. Additionally or alternatively, two or more R groups can be linked to form one or more fused ring structures. Coordination of the β-diketonimine ligand to the metal typically forms a six-membered chelate ring through two M-N bonds. In some embodiments, the metal precursor includes one or more triazene ligands. The triazene ligand has the general formula structure RNNNR, where each R is an independently selected substituent, typically selected from hydrogen, alkyl, haloalkyl, aryl, haloaryl, alkenyl, alkynyl, trialkylsilyl, and halogen. Coordination of the triazene ligand to the metal typically forms a four-membered chelate ring through two M-N bonds. An example triazene ligand is 1,3-diphenyltriazene (PhNNNPh).

[0114] In some embodiments, the metal precursor includes a rare earth metal. For example, the metal in the metal precursor can be selected from scandium (Sc), yttrium (Y), or lanthanide elements. More specifically, the metal in the metal precursor can be selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and combinations and mixtures thereof. Examples of metal precursors containing scandium include, but are not limited to, tris(cyclopentadienyl)scandium(III) (Sc(MeCp) 3 ), tris(isopropylcyclopentadienyl)scandium(III) (Sc( i PrCp) 3 ), bis(cyclopentadienyl)-3,5-dimethylpyrazolylscandium(III) (Sc(MeCp) 2 (Me 2 pz)), bis(ethylcyclopentadienyl)-N,N'-diisopropylethylamido scandium(III) (Sc(EtCp) 2 ( i PrAMD)), tris(N,N'-diisopropylformamido)scandium(III) (Sc( i PrFMD) 3 ), tris(N,N'-diisopropylethylamido)scandium(III) (Sc( i PrAMD) 3 ), and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)scandium(III) (Sc(thd) 3 ). Examples of metal precursors containing yttrium include, but are not limited to, tris(cyclopentadienyl)yttrium(III) (Y(MeCp) 3 ), tris(isopropylcyclopentadienyl)yttrium(III) (Y( i PrCp) 3 ), bis(ethylcyclopentadienyl)-N,N'-diisopropylethanimidoyl yttrium(III) (Y(EtCp) 2 ( i PrAMD)), tris(N,N'-diisopropylformimidoyl)yttrium(III) (Y( i Pr 2 FMD) 3 ), tris(N,N'-diisopropylethanimidoyl)yttrium(III) (Y( i Pr 2 AMD) 3 ), tris(N,N'-diisopropyl-2-dimethylaminoguanidino)yttrium(III) (Y(dpguan) 3 ), and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)yttrium(III) (Y(thd) 3 ). Examples of metal precursors containing lanthanum include, but are not limited to, tris(cyclopentadienyl)lanthanum(III) (La(MeCp)3 ), tris(isopropylcyclopentadienyl)lanthanum (La( i PrCp) 3 ), bis(ethylcyclopentadienyl)-N,N'-diisopropylethylamidinato lanthanum (La(EtCp) 2 ( i PrAMD)), lanthanum formate (La(FMD) 3 ), tris(N,N'-diisopropylformamidinato)lanthanum (La( i PrFMD) 3 ), tris(N,N'-diisopropylethylamidinato)lanthanum (La( i PrAMD) 3 ), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)lanthanum (La(thd) 3 ), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)(N,N'-dimethylethylenediamido)lanthanum (La(thd) 3 (dmea)) and tris(bis(trimethylsilyl)amino)lanthanum (La(N(SiMe 3 )) 2 . Examples of metal precursors containing cerium include, but are not limited to, tris(methylcyclopentadienyl)cerium (Ce(MeCp) 3 ), tris(isopropylcyclopentadienyl)cerium (Ce( i PrCp) 3 ), bis(isopropylcyclopentadienyl)-N,N'-diisopropylethanamidato cerium (Ce( i PrCp) 2 ( i PrAMD)), cerium acetylacetonate (Ce(acac) 4 ), tetrakis(1,1,1,5,5,5-hexafluoropentanedionato)cerium (Ce(hfac) 4 ), tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium (Ce(thd) 4 ), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)-1,10-phenanthroline cerium (Ce(thd) 3 (phen)), tris(N,N'-diisopropylformamide)cerium (Ce( i PrFMD) 3 ), tris(N,N'-diisopropylethylamide)cerium (Ce( i Pr 2 AMD) 3 ), tetrakis(1-(methoxy)-2-methyl-2-propanolato)cerium (Ce(mmp) 4 ), tris(N,N'-diisopropyl-2-dimethylaminoguanidino)cerium (Ce(dpguan)3 ), and tris(bis(trimethylsilylamino))cerium Ce(N(SiMe 3 ) 2 ) 3 . Other metal precursors containing rare earth metals are known in the art. Those skilled in the art will recognize other rare earth metal ligand combinations suitable for the methods disclosed herein.

[0115] In some embodiments, the metal precursor comprises a Group 4 element. For example, the metal in the metal precursor can be selected from titanium (Ti), zirconium (Zr), hafnium (Hf), and combinations and mixtures thereof. Examples of metal precursors containing titanium include, but are not limited to, titanium tetrafluoride (TiF 4 ), titanium tetrachloride (TiCl 4 ), titanium tetrabromide (TiBr 4 ), titanium tetraiodide (TiI 4 ), titanium tetraethoxide (Ti(OMe) 4 ), titanium tetraethoxide (Ti(OEt) 4 ), titanium tetraisopropoxide (Ti(O i Pr) 4 ), tetrakis(dimethylamino)titanium (Ti(NMe 2 ), 4 tetrakis(diethylamino)titanium (Ti(NEt 2 ), 4 ), and tris(dimethylamino)methylcyclopentadienyltitanium (Ti(MeCp)(NMe 2 ). 3 Examples of metal precursors containing zirconium include, but are not limited to, zirconium tetrachloride (ZrCl 4 ), zirconium tetrabromide (ZrBr 4 ), zirconium tetramethoxide (Zr(OMe) 4 ), zirconium tetraethoxide (Zr(OEt) 4 ), zirconium tetra-tert-butoxide (Zr(O t Bu) 4 ), tetrakis(dimethylamino)zirconium (Zr(NMe 2 ), 4 tetrakis(ethylmethylamino)zirconium (Zr(N(Me)(Et)) 4 ), dichlorodicyclopentadienylzirconium (ZrCl 2 Cp 2 ), (dicyclopentadienyl)(dimethyl)zirconium (ZrMe 2 Cp 2 ), cyclopentadienyltris(dimethylamino)zirconium (ZrCp(NMe 2 ), 3 ), and tris(N,N'-diisopropylethylamidine)zirconium (Zr( i Pr2 AMD) 3 ) Examples of metal precursors containing hafnium include, but are not limited to, hafnium tetrachloride (HfCl 4 ), hafnium tetrabromide (HfBr 4 ), hafnium tetra(1-methoxy-2-methyl-2-propoxy) (Hf(OC(CH 3 )) 2 CH 2 OCH 3 )) 4 ), hafnium tetra(tert-butoxide) (Hf(O t Bu) 4 ), hafnium tetra(dimethylamino) (Hf(NMe 2 )) 4 ), hafnium tetra(diethylamino) (Hf(NEt 2 )) 4 ), hafnium tetra(ethylmethylamino) (Hf(N(Me)(Et)) 4 ), hafnium tetra(1-methoxy-2-methyl-2-propoxy) (Hf(mmp) 4 ), and hafnium tris(dimethylamino)cyclopentadienyl (HfCp(NMe 2 )) 3 ). Other metal precursors containing titanium, zirconium, and / or hafnium are known in the art. Those skilled in the art will recognize other Group 4 metal ligand combinations suitable for the methods disclosed herein.

[0116] In some embodiments, the metal precursor includes a Group 5 element. For example, the metal in the metal precursor can be selected from vanadium (V), niobium (Nb), tantalum (Ta), and combinations and mixtures thereof. Examples of metal precursors containing vanadium include, but are not limited to, vanadium pentafluoride (VF 5 ), vanadium pentabromide (VBr 5 ), vanadium tetrachloride (VCl 4 ), vanadium trioxide (VOCl 3 ), vanadium tris(isopropoxide)oxo (VO(O i Pr) 3 ), vanadium tetra(ethylmethylamino) (V(NEtMe) 4 ), vanadium tris(N,N'-diethylacetimidato) (V(Et 2 AMD) 3 ), vanadium tris(N,N'-diisopropylacetimidato) (V( i Pr 2 AMD) 3 ), vanadium tris(N,N'-diisopropylacetimidato) (V(acac) 3 ). Examples of metal precursors containing niobium include, but are not limited to, niobium pentafluoride (NbF 5) Niobium pentachloride (NbCl 5 ) Niobium pentaiodide (NbI 5 ) Niobium pentabromide (NbBr 5 ) Niobium pentaethoxide (Nb(OEt) 5 ) Tris(2,2,6,6-tetramethylheptane-3,5-dionato)niobium (Nb(thd) 4 ) Niobium pentakis(dimethylamino) (Nb(NMe 2 ) 5 ) Niobium pentakis(diethylamino) (Nb(NEt 2 ) 5 ) Tris(diethylamido)(tert-butylimido)niobium (Nb(N t Bu)(NEt 2 ) 3 ) Tris(dimethylamido)(tert-butylimido)niobium (Nb(N t Bu)(NMe 2 ) 3 ) Tris(ethylmethylamido)(tert-butylimido)niobium (Nb(N t Bu)(NEtMe) 3 ) and (tert-Amylimido)tris(tert-butoxy)niobium (Nb(N t Amyl)(O t Bu) 3 ) Examples of metal precursors containing tantalum include, but are not limited to, tantalum pentachloride (TaCl 5 ) Tantalum pentabromide (TaBr 5 ) Tantalum pentaiodide (TaI 5 ) Tantalum pentakis(dimethylamino) (Ta(NMe 2 ) 5 ) Tantalum pentaethoxide (Ta(OEt) 5 ) Tantalum pentakis(diethylamino) (Ta(NEt 2 ) 5 ) Tris(diethylamido)(tert-butylimido)tantalum (Ta(N t Bu)(NEt 2 ) 3 ) Tris(dimethylamido)(tert-butylimido)tantalum (Ta(NtBu)(NMe 2 ) 3 ) Tris(ethylmethylamido)(tert-butylimido)tantalum (Ta(N t Bu)(NEtMe) 3 ) Tris(dimethylamido)(tert-amylimido)tantalum (Ta(NtAmyl)(NMe 2 ) 3) Bis(diethylamino)cyclopentadienyl(tert-butylimido)tantalum (TaCp(N t Bu)(NEt 2 )) 2 ) (Dimethylamino)bis(N,N’-isopropylethamidinato)(tert-butylimido)tantalum (Ta(N t Bu)( i PrAMD) 2 (NMe 2 )) (tert-Butylimino)tris(3,5-di-tert-butylpyrazolyl) (Ta(N t Bu)( t Bu 2 pz) 3 ) tantalum, (Isopropylimino)tris(tert-butoxide) tantalum (Ta(N i Pr)(O t Bu) 3 ) and (tert-Butylimino)tris(tert-butoxide) tantalum (Ta(N t Bu)(O t Bu) 3 ) Other metal precursors containing vanadium, niobium or tantalum are known in the art. Those skilled in the art will recognize other Group 5 metal ligand combinations suitable for the methods disclosed herein.

[0117] In some embodiments, the metal precursor includes a Group 6 element. For example, the metal in the metal precursor can be selected from chromium (Cr), molybdenum (Mo), tungsten (W), and combinations and mixtures thereof. Examples of metal precursors containing chromium include, but are not limited to, tris(2,2,6,6-tetramethyl-3,5-heptanedionato)chromium (Cr(thd) 3 ), chromium chloride (CrO 2 Cl 2 ), bis(cyclopentadienyl)chromium (CrCp 2 ), bis(ethylbenzene)chromium (CrEtBz), chromium acetylacetonate (Cr(acac) 3 ), and chromium hexacarbonyl (Cr(CO) 6 ). Examples of metal precursors containing molybdenum include, but are not limited to: molybdenum pentachloride (MoCl 5 ), molybdenum dichloride dioxide (MoO 2 Cl 2 ), tetrakis(dimethylamide)molybdenum (Mo(NMe 2 ) 4 ), tetrakis(diethylamide)molybdenum (Mo(NEt 2 ) 4 ), bis(tert-butylimino)bis(tert-butoxide)molybdenum (Mo(tBuN) 2 (NMe 2 ) 2) Bis(tert-butylimino)bis(ethoxy)molybdenum (Mo( t BuN) 2 (NEt 2 ) 2 ) 2,2,6,6-Tetramethylheptane-3,5-diylmolybdenum (Mo(thd) 3 ) Acetylacetonato molybdenum Mo(acac) 3 Hexacarbonylmolybdenum (Mo(CO) 6 ) Dicyclopentadienyldihydromolybdenum Mo(Cp) 2 H 2 Bis(isopropyl)cyclopentadienyldihydromolybdenum (Mo( i PrCp) 2 H 2 ) Bis(N,N’-isopropylethylamidinato)(tert-butylimino)molybdenum (Mo(N t Bu) 2 ( i PrAMD) 2 ) and bis(ethylbenzene)molybdenum (Mo(η 6 -EtBz) 2 . Examples of metal precursors containing tungsten include, but are not limited to, tungsten pentachloride (WCl 5 ) tungsten hexafluoride (WF 6 ) tungsten hexacarbonyl (W(CO) 6 ) bis(tert-butylimino)bis(dimethylamino)tungsten (W(N t Bu) 2 (NMe 2 )) bis(N,N’-isopropylethylamidinate)(tert-butylimino)tungsten (W(N t Bu) 2 ( i PrAMD) 2 ) and bis(isopropyl)cyclopentadienyldihydrowolfram (W( i PrCp) 2 H 2 ). Other metal precursors containing chromium, molybdenum, or tungsten are known in the art. Those skilled in the art will recognize other Group 6 metal ligand combinations suitable for the methods disclosed herein.

[0118] In other embodiments, the metal precursor includes a Group 13 element. For example, the metal in the metal precursor can be selected from boron (B), aluminum (Al), gallium (Ga), indium (In), and combinations and mixtures thereof. Examples of metal precursors containing boron include, but are not limited to, trimethyl borate (B(OMe) 3 ) trimethyl borane (BMe 3 ) triethyl borane (BEt 3 ) tris(dimethylamino)borane (B(NMe2 ) 3 ), boron tribromide (BBr 3 ), boron trichloride (BCl 3 ), boron triiodide (BI 3 ), borazine (B 3 H 4 N 3 ), and trichloroborazine (B 3 Cl 3 H 3 N 3 ). Examples of metal precursors containing aluminum include, but are not limited to, aluminum trichloride (AlCl 3 ), aluminum tribromide (AlBr 3 ), aluminum triiodide (AlI 3 ), trimethylaluminum (AlMe 3 ), triethylaluminum (AlEt 3 ), bis(tert-butyl)methylaluminum ( t Bu 2 AlMe), triisobutylaluminum (Al( i Bu) 3 ), triisopentylaluminum (Al( n Pe) 3 ), dimethylaluminum hydride (AlHMe 2 ), aluminum methoxide (Al(OMe) 3 ), aluminum ethoxide (Al(OEt) 3 ), aluminum isopropoxide (Al(O i Pr) 3 ), dimethylaluminum isopropoxide (AlMe 2 O i Pr), dimethylaluminum chloride (AlMe 2 Cl), tris(dimethylamino)aluminum Al(NMe 2 ) 3 , tris(diethylamino)aluminum (Al(NEt 2 ) 3 ), diethyl-(N,N’-diisopropylamidinato)aluminum (Al( i PrAMD)Et 2 ), 3-(dimethylamino)propylaluminum (Al(DMP) 3 ), tris(1-dimethylamino-2-methyl-2-propoxy)aluminum (Al(dmamp) 3 ), tris(1-methoxy-2-methyl-2-propoxy)aluminum (Al(mmp) 3 ), dimethyl-3-(dimethylamino)propylaluminum (AlMe 2 (DMP)), bis-(diisopropylamino)(3-dimethylamino)propylaluminum (Al(Ni Pr 2 )(DMP)), tris(N,N'-diisopropyl-2-dimethylaminoguanidino)aluminum (Al(dpguan) 3 ), tris(neopentyl)aluminum (Al( n Pe) 3 ), and aluminum acetylacetonate (Al(acac) 3 ). Examples of gallium-containing metal precursors include but are not limited to gallium trichloride (GaCl 3 ), gallium tribromide (GaBr 3 ), gallium triiodide (GaI 3 ), trimethylgallium (GaMe 3 ), triethylgallium (GaEt) 3 , tri-n-pentylgallium (Ga( n Pe) 3 ), gallium acetylacetonate (Ga(acac) 3 ), tris-2,2,6,6-tetramethyl-heptane-3,5-dionato gallium (Ga(thd) 3 ), tris(1-dimethylamino-2-methyl-2-propoxy)gallium (Ga(dmamp) 3 ), tris(1,3-diisopropyltriazene)gallium (Ga(triaz) 3 ), dimethylethylgallium (GaEtMe 2 ), tris(N,N'-diisopropylamidinato)gallium (Ga( i PrAMD) 3 ), tris(N,N'-diisopropylformamidato)gallium (Ga( i PrFMD) 3 ), and diethylbis(trimethylsilyl)aminogallium (Ga(N(SiMe 3 )) 2 )Et 2 ). Examples of indium-containing metal precursors include but are not limited to trimethylindium (InMe 3 ), triethylindium (InEt 3 ), dimethylethylindium (InEtMe 2 ). Tri-n-pentylindium (In( n Pe) 3 ), dimethylindium chloride (InClMe 2 ), indium trichloride (InCl 3 ), indium tribromide (InBr 3 ), indium triiodide (InI 3 ), indium acetylacetonate (In(acac) 3 ), tris(dimethylamino-2-methyl-2-propoxy)indium (In(dmamp)3 , (isopropanol)bis(dimethylamino-2-methyl-2-propoxy)indium (In(dmamp) 2 (O i Pr)), ethylcyclopentadienylindium (In(EtCp)), 1-methylbutylcyclopentadienylindium (In(Cp(Me)(Bu)), tris(N,N’-diisopropylformamidato)indium (In( i PrFMD) 3 , tris(N,N’-diisopropylamidinato)indium (In(iPrAMD) 3 ), diethyl[bis(trimethylsilyl)amido]indium (In(N(SiMe 3 )) 2 )Et 2 ), tris-2,2,6,6-tetramethyl-heptane-3,5-dionatoindium (In(thd) 3 ), tris(1,3-diisopropyltriazenido)indium (In(triaz) 3 ), dimethyl(N-ethoxy-2,2-dimethylpropanamidato)indium (InMe 2 (edpa)), dimethyl-(N-(tert-butyl)-2-methoxy-2-methylpropan-1-amine)indium (InMe 2 (N t Bu(CH 2 )(CH 3 )) 2 , trimethyl-(N-(tert-butyl)-2-methoxy-2-methylpropan-1-amine)indium (InMe 2 (N t Bu(CH 2 )(CH 3 )) 2 OMe) and tris(N,N’-diisopropyl-2-dimethylaminoguanidino)indium (In(dpguan) 3 ). Other metal precursors containing boron, aluminum, gallium or indium are known in the art. Those skilled in the art will recognize other Group 13 element ligand combinations suitable for the methods disclosed herein.

[0119] In certain embodiments of the methods disclosed herein, the substrate is exposed to a halogen reactant. The halogen reactant is introduced into the reaction space, and at least a portion of the substrate surface is contacted with the halogen reactant. The halogen reactant can be in gaseous form, or it can be a liquid or solid, but it should have a sufficient vapor pressure (generally between 1 - 20 Torr) at room temperature or near room temperature such that it can be introduced into the reaction space and transported to the substrate surface. Additionally or alternatively, the halogen reactant can be heated to provide a sufficient vapor pressure and / or be carried and introduced into the reaction space by an inert carrier gas (such as nitrogen and / or noble gases like helium (He) and argon (Ar)).

[0120] In some embodiments, the halogen reactant includes one or more bonds selected from C - X bonds, P - X bonds, N - X bonds, and S - X bonds, where X is a halogen atom selected from F, Cl, Br, and I. Suitable halogen reactants include, but are not limited to, carbon tetrafluoride (CF 4 ), carbon tetrachloride (CCl 4 ), carbon tetrabromide (CBr 4 ), bis(trichloromethyl) carbonate (C 3 C1 6 O 3 ), diiodomethane (CH 2 I 2 ), diiodoethane (C 2 H 4 I 2 ), acetyl chloride (CH 3 COCl), oxalyl chloride (CO 2 Cl 2 ), sulfur trifluoride (SF 4 ), sulfur hexafluoride (SF 6 ), sulfur dichloride (SCl 2 ), sulfur dichloride (S 2 Cl 2 ), thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), xenon difluoride (XeF 2 ), selenium tetrafluoride (SeF 4 ), selenium hexafluoride (SeF 6 ), selenium dichloride (SeCl 2 ), selenium tetrachloride (SeCl 4 ), selenium dichloride (Se 2 Cl 2 ), tellurium hexafluoride (TeF 6 ), silicon tetrachloride (SiC1 4 ), antimony pentafluoride (SbF 5 ), antimony trichloride (SbC1 3)、Antimony pentachloride (SbCl 5 )、Boron trichloride (BCl 3 )、Germanium tetrachloride (GeCl 4 )、Nitrogen trifluoride (NF 3 )、Nitrogen chloride fluoride (NC1 2 F and / or NF 2 Cl), Nitrosyl fluoride (NOF), Nitryl fluoride (NO 2 F), Phosphorus trichloride (PCl 3 )、Phosphorus pentachloride (PCl 5 )、Phosphoryl chloride (POCl 3 )、Phosphorus tribromide (PBr 3 )、Phosphorus pentabromide (PBr 5 )、Phosphoryl bromide (POBr 3 )、Hydrogen fluoride (HF), Hydrogen chloride (HCl), Fluorine (F 2 )、Chlorine (Cl 2 )、Bromine (Br 2 ) and metal halides. Exemplary metal halides include but are not limited to Titanium tetrafluoride (TiF 4 )、Titanium tetrachloride (TiCl 4 )、Tungsten hexafluoride (WF 6 )、Niobium pentafluoride (NbF 5 ) and Niobium pentachloride (NbCl 5 ). In some embodiments, the halogen reactant includes chlorine. In some embodiments, the substrate is exposed to the halogen reactant under thermal conditions. In other words, the halogen reactant does not contain plasma species, and the substrate is not exposed to plasma species (such as ionic species, radical species, atoms, metastable species, and / or excited species). In other embodiments, the halogen reactant is supplied through a plasma source to form plasma species. In some of these embodiments, the halogen reactant includes plasma species.

[0121] In some embodiments, after introducing the metal precursor and before introducing the phosphorus precursor, the halogen reactant is introduced into the reaction space (see, for example, Figure 2 203 in and Figure 3In these embodiments, the metal- and phosphorus-containing film can be formed by a three-step process. Without being bound by a particular mechanism, it is hypothesized that the halogen reactant converts the ligands of the adsorbed metal precursor into halide ligands via an exchange reaction, thereby increasing the reactivity of the adsorbed metal precursor towards certain phosphorus precursors. This three-step process can be particularly useful in cases where suitable metal halide metal precursors are not available. For example, many metal halides are solids and do not have sufficient vapor pressure and / or sufficient thermal stability to be used in a vapor deposition process. This is the case for rare earth metal halides and many other metal halides. Using a halide ligand exchange reaction allows for the formation of surface-adsorbed metal halide precursors, which can then facilitate subsequent reactions with certain phosphorus precursors, such as trimethylsilylphosphine (P(SiH 3 ) 3 ), tris(trimethylsilyl)phosphine (P(SiMe 3 ) 3 ), tris(triethylsilyl)phosphine (P(SiEt 3 ) 3 ), and tris(triisopropylsilyl)phosphine (P(Si i Pr 3 ) 3 ).

[0122] In other embodiments, the halogen reactant can be used to remove certain impurities (such as carbon and / or oxygen) from the metal- and phosphorus-containing film. For example, by reacting with the impurities to form volatile reaction products, the halogen reactant can be used to reduce the amount of carbon, nitrogen, oxygen, and / or elemental phosphorus impurities in the film, thereby improving the quality of the metal- and phosphorus-containing film. In these embodiments, the halogen reactant can be introduced into the reaction space at the end of the cyclic deposition process as a final step; or intermittently or periodically during the cyclic deposition (see, for example, Figure 2 203 in Figure 3 305 in Figure 4 405 in Figure 6 603 in Figure 7 705 in Figure 8 805 or 807 in

[0123] In certain embodiments, the substrate is exposed to an oxygen reactant. The oxygen reactant is introduced into the reaction space and at least a portion of the substrate surface is in contact with the oxygen reactant. Suitable oxygen reactants include, but are not limited to, oxygen (O 2 ), ozone (O 3 ), water (H 2 O), deuterated water (D 2 O), hydrogen peroxide (H 2 O 2)), organic peroxides (ROOH, where R is an alkyl or aryl group), alcohols (ROH, where R is an alkyl or aryl group), nitrogen dioxide (NO 2 ), dinitrogen monoxide (N 2 O), nitric oxide (NO), dinitrogen pentoxide (N 2 O 5 ), pyridine N-oxide (C 5 H 5 NO), amine oxides (R 3 NO, where each R is independently an alkyl or aryl group and / or two or more R groups may be bonded to each other to form a ring structure), and combinations thereof. In some embodiments, the oxygen-containing reactant is oxygen, ozone, dinitrogen monoxide, or a combination thereof. In some embodiments, the substrate is exposed to the oxygen reactant under thermal conditions. In other words, the oxygen reactant does not contain plasma species, and the substrate is not exposed to plasma species (e.g., ionic species, radical species, atoms, metastable species, and / or excited species). In other embodiments, the oxygen reactant is supplied by a plasma source to form plasma species. In some of these embodiments, the oxygen reactant includes plasma species.

[0124] Another aspect of the present disclosure relates to a system for forming a metal- and phosphorus-containing film disclosed herein using the methods disclosed herein. The system for forming a metal- and phosphorus-containing film can be used to form a structure including a threshold voltage offset layer, the threshold voltage offset layer including a metal- and phosphorus-containing material. In some embodiments, the system is a semiconductor processing apparatus including a reaction space (i.e., at least one reaction chamber) for accommodating a substrate. The semiconductor processing apparatus can include one reaction chamber, two reaction chambers, three reaction chambers, four reaction chambers, or more. In some embodiments, the semiconductor processing apparatus is a combination tool. In some embodiments, one or more reaction chambers in a flow-type reactor can be utilized. In some embodiments, one or more reaction chambers in a showerhead-type reactor can be utilized. In some embodiments, one or more reaction chambers in a spatially-separated reactor can be utilized. In some embodiments, one or more reaction chambers in a single-wafer reactor with high-volume manufacturing capabilities can be utilized. In other embodiments, one or more reaction chambers in a batch reactor can be utilized. The semiconductor processing apparatus further includes means for exposing at least a portion of the substrate surface to a metal precursor and a phosphorus precursor, and optionally means for purging the reaction space between exposure steps. The semiconductor processing apparatus can further include means for optionally exposing at least a portion of the substrate surface to a halogen reactant and / or an oxygen reactant.

[0125] Figure 9FIG. shows a schematic diagram of an exemplary embodiment of a semiconductor processing apparatus 900 in accordance with the present disclosure. Gaseous reactants are provided into a reaction space 901 through an injector system 902. The injector system 902 is configured to provide a metal precursor from a metal precursor source 903 coupled to a metal precursor source valve 908, a phosphorus precursor from a phosphorus precursor source 904 coupled to a phosphorus precursor source valve 909, optionally a halogen reactant from a halogen reactant source 905 coupled to a halogen reactant source valve 910, and optionally an oxygen reactant from an oxygen reactant source 906 coupled to an oxygen source valve 911. The injector system 902 may further include one or more other gas sources from source 907, such as for providing purge gas and carrier gas (e.g., nitrogen and / or noble gases such as He, Ne, Ar, Kr, Xe, and combinations thereof) to the reaction space 901, and means (if needed) for heating the various reactant sources and corresponding gas lines (not shown) to facilitate their introduction into the reaction space 901. The various gases flow into the reaction space 901 that houses a substrate 913 located on a pedestal 914. In Figure 9 this case, the various gases flow into the reaction space 901 from the top of the reaction space above the substrate 913; however, those skilled in the art will recognize that other flow configurations and / or other mechanisms for housing the substrate may be utilized. In some embodiments, the reaction space further includes one or more heating elements (not shown) in thermal communication with the substrate 913 and one or more thermocouples (not shown) to measure the temperature of the substrate 913 and maintain it at a set temperature. Unreacted gases and gaseous reaction by-products leave the reaction chamber 901 through an exhaust line 915, which is optionally coupled to a vacuum pump 916. The semiconductor processing apparatus further includes a controller 917 that is operatively connected to components of the injector system 902, such as the metal precursor source valve 908 and the phosphorus precursor source valve 909, the optional halogen reactant source valve 910 and the oxygen reactant source valve 911, and other components (not shown). The controller 917 is configured and programmed to independently control (e.g., open and close, etc.) the supply of the various gases (e.g., metal precursor, phosphorus precursor, optional halogen reactant, optional oxygen reactant, and optional carrier gas and purge gas, etc.) and other ingredients to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913.

[0126] In some embodiments, the controller 917 is configured and programmed to perform a cyclic deposition process that includes a first operation and a second operation (e.g., according to Figure 1) of at least one deposition cycle. In a first operation, the controller 917 opens the metal precursor source valve 908 to allow the metal precursor to flow from the metal precursor source 903 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the metal precursor, and after a set time period, the controller 907 closes the metal precursor source valve 908 leading to the metal precursor source 903. In a second operation, the controller 917 opens the phosphorus precursor source valve 909 to allow the phosphorus precursor to flow from the phosphorus precursor source 904 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the phosphorus precursor, and after a set time period, the controller 917 closes the phosphorus precursor source valve 909 leading to the phosphorus precursor source 904. In some embodiments, the controller 917 is programmed to perform the first operation and the second operation, and vice versa, wherein at least a portion of the first operation overlaps with at least a portion of the second operation such that the metal precursor flowing into the reaction space 901 overlaps at least partially with the phosphorus precursor flowing into the reaction space 901 to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913. In some other embodiments, the controller 917 is programmed to perform the first operation sequentially, followed by the second operation, or vice versa, such that the flow of the metal precursor into the reaction space 901 and the flow of the phosphorus precursor into the reaction space 901 do not overlap one or more times to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913.

[0127] In other embodiments, the controller 917 is configured and programmed to perform a cyclic deposition process (e.g., according to Figure 2 , Figure 3 or Figure 4) at least one deposition cycle, including a first operation, a second operation, and an optional third operation, etc. In the first operation, the controller 917 opens the metal precursor source valve 908 to allow the metal precursor to flow from the metal precursor source 903 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the metal precursor, and after a set time period, the controller 907 closes the metal precursor source valve 908 leading to the metal precursor source 903. In the second operation, the controller 917 opens the phosphorus precursor source valve 909 to allow the phosphorus precursor to flow from the phosphorus precursor source 904 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the phosphorus precursor, and after a set time period, the controller 917 closes the phosphorus precursor source valve 909 leading to the phosphorus precursor source 904. In the third operation, the controller 917 opens the halogen reactant source valve 910 to allow the halogen reactant to flow from the halogen reactant source 905 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the halogen reactant, and after a set time period, the controller 917 closes the halogen reactant source valve 910 leading to the halogen reactant source 905. In certain embodiments, the controller 917 is programmed to sequentially perform the first operation, the third operation, and the second operation one or more (n) times to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913 (e.g., see Figure 2 ); or alternatively, the controller 917 is programmed to sequentially perform the second operation, the first operation, and the third operation one or more (n) times to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913 (e.g., see Figure 3 ). In certain other embodiments, the controller 917 is programmed to sequentially perform the first operation, followed by the second operation, or vice versa, one or more (n) times, and perform the third operation at least once and optionally one or more (m) times to form a metal- and phosphorus-containing film on at least a portion of the surface of the substrate 913 (e.g., see Figure 4 ). In some cases, the number of times (m) the third operation is performed may be equal to the number of times (n) the first and second operations are performed (i.e., m = n). In other cases, the number of times (m) the third operation is performed may be less than the number of times (n) the first and second operations are performed (i.e., m < n). For example, the third operation may be performed once every other deposition cycle, or once every several deposition cycles, or only once at the end of the cyclic deposition process as a final step (i.e., m = 0).

[0128] In other embodiments, the controller 917 is configured and programmed to perform a cyclic deposition process (e.g., according to Figure 5) at least one deposition cycle, including a first operation, a second operation, and an optional third operation, etc. In the first operation, the controller 917 opens the metal precursor source valve 908 to allow the metal precursor to flow from the metal precursor source 903 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the metal precursor, and after a set time period, the controller 907 closes the metal precursor source valve 908 leading to the metal precursor source 903. In the second operation, the controller 917 opens the phosphorus precursor source valve 909 to allow the phosphorus precursor to flow from the phosphorus precursor source 904 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the phosphorus precursor, and after a set time period, the controller 917 closes the phosphorus precursor source valve 909 leading to the phosphorus precursor source 904. In the third operation, the controller 917 opens the oxygen reactant source valve 911 to allow the oxygen reactant to flow from the oxygen reactant source 906 into the reaction space 901, thereby exposing at least a portion of the substrate surface to the oxygen reactant, and after a set time period, the controller 917 closes the oxygen reactant source valve 911 leading to the oxygen reactant source 906. In some embodiments, the controller 917 is programmed to sequentially perform the first operation, followed by the second operation, and vice versa, one or more (n) times, and perform the third operation at least once, optionally one or more (m) times, to form a metal- and phosphorus-containing film further containing oxygen on the surface of the substrate 913. In some cases, the number of times (m) of performing the third operation may be equal to the number of times (n) of performing the first and second operations (i.e., m = n). In other cases, the number of times (m) of performing the third operation may be less than the number of times (n) of performing the first and second operations (i.e., m < n). For example, the third operation may be performed once every other deposition cycle, or once every several deposition cycles, or only once at the end of the cyclic deposition process (i.e., m = 0).

[0129] As will be understood by those skilled in the art, the controller can be configured and programmed to perform other embodiments of the present disclosure, such as Figure 6 , Figure 7 and Figure 8 those shown in. Similarly, the controller 917 can be further configured and programmed to perform other operations. For example, the controller 917 can be operably connected to a purge gas source 907 and be configured and programmed to open the valve 912 leading to the purge gas source to allow the purge gas to flow into the reaction space 901, and after a set time period, close the valve 912 leading to the purge gas source. In another example, the controller 917 can be operably connected to one or more heating elements (not shown) and one or more thermocouples (not shown), and be configured and programmed to measure and control the temperature of at least one heating element to maintain the temperature of the substrate 913 at a set temperature.

[0130] In some embodiments, a system for forming a metal and phosphorus-containing film on at least a portion of a substrate surface includes: a reaction space for accommodating the substrate; a metal precursor source for providing a metal precursor that is in gas communication with the reaction space via a metal precursor source valve; a phosphorus precursor source for providing a phosphorus precursor that is in gas communication with the reaction space via a phosphorus precursor source valve; and a controller operably connected to the metal precursor source valve and the phosphorus precursor source valve, the controller being configured and programmed to perform the methods disclosed herein. The controller can be configured and programmed to sequentially control: opening one of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; closing one of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; opening the other of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source; and closing the other of the metal precursor source valve leading to the metal precursor source and the phosphorus precursor source valve leading to the phosphorus precursor source. For example, the controller can be configured and programmed to perform at least one deposition cycle of a cyclic deposition process, including sequentially controlling: opening the metal precursor source valve leading to the metal precursor source to supply the metal precursor into the reaction space; closing the metal precursor source valve leading to the metal precursor source to stop supplying the metal precursor into the reaction space; opening the phosphorus precursor source valve leading to the phosphorus precursor source to supply the phosphorus precursor into the reaction space; and closing the phosphorus precursor source valve leading to the phosphorus precursor source to stop supplying the phosphorus precursor into the reaction space. Additionally or alternatively, the controller can be configured and programmed to perform at least one deposition cycle of a cyclic deposition process, including sequentially controlling: opening the phosphorus precursor source valve of the phosphorus precursor source to supply the phosphorus precursor into the reaction space; closing the phosphorus precursor source valve leading to the phosphorus precursor source to stop supplying the phosphorus precursor into the reaction space; opening the metal precursor source valve leading to the metal precursor source to supply the metal precursor into the reaction space; and closing the metal precursor source valve leading to the metal precursor source to stop supplying the metal precursor into the reaction space. The controller can also be programmed to sequentially repeat opening the metal precursor source valve leading to the metal precursor source and then closing the metal precursor source valve leading to the metal precursor source, opening the phosphorus precursor source valve leading to the phosphorus precursor source and then closing the phosphorus precursor source valve leading to the phosphorus precursor source, or vice versa, to form a metal and phosphorus-containing film on at least a portion of the substrate surface.

[0131] In some embodiments, the system further includes a halogen reactant source for providing a halogen reactant that is in gas communication with the reaction space via a halogen reactant source valve, and the controller is also operably connected to the halogen reactant source valve and is configured and programmed to control: opening the halogen reactant source valve leading to the halogen reactant source to supply the halogen reactant into the reaction space; and closing the halogen reactant source valve leading to the halogen reactant source to stop supplying the halogen reactant to the reaction space. In certain embodiments, the controller is further programmed to open the halogen reactant source valve leading to the halogen reactant source and then close the halogen reactant source valve leading to the halogen reactant source after each closing of the metal precursor source valve leading to the metal precursor source. In certain other embodiments, the controller is further programmed to open the halogen reactant source valve leading to the halogen reactant source and close the halogen reactant source valve leading to the halogen reactant source after closing at least one of the metal precursor source valves leading to the metal precursor source or after closing at least one of the phosphorus precursor source valves leading to the phosphorus precursor source. In certain other embodiments, the controller is further programmed to open the halogen reactant source valve leading to the halogen reactant source and close the halogen reactant source valve leading to the halogen reactant source after the final step of closing the metal precursor source valve leading to the metal precursor source or after the final step of closing the phosphorus precursor source valve leading to the phosphorus precursor source.

[0132] In some embodiments, the system further includes an oxygen reactant source for providing an oxygen reactant that is in gas communication with the reaction space via an oxygen reactant source valve, and the controller is also operably connected to the oxygen reactant source valve and is configured and programmed to control: opening the oxygen reactant source valve leading to the oxygen reactant source to supply the oxygen reactant into the reaction space; and closing the oxygen reactant source valve leading to the oxygen reactant source to stop supplying the oxygen reactant to the reaction space. In certain embodiments, the controller is further programmed to open the oxygen reactant source valve leading to the oxygen reactant source and close the oxygen reactant source valve leading to the oxygen reactant source after closing at least one of the metal precursor source valves leading to the metal precursor source or after closing at least one of the phosphorus precursor source valves leading to the phosphorus precursor source. In certain other embodiments, the controller is further programmed to open the oxygen reactant source valve leading to the oxygen reactant source and close the oxygen reactant source valve leading to the oxygen reactant source after each closing of the metal precursor source valve leading to the metal precursor source or after each closing of the phosphorus precursor source valve leading to the phosphorus precursor source. In certain other embodiments, the controller is further programmed to open the oxygen reactant source valve leading to the oxygen reactant source and close the oxygen reactant source valve leading to the oxygen reactant source after the final step of closing the metal precursor source valve leading to the metal precursor source or after the final step of closing the phosphorus precursor source valve leading to the phosphorus precursor source.

[0133] Another aspect of the present disclosure relates to a semiconductor device structure that includes a metal- and phosphorus-containing film disclosed herein formed using the methods and systems disclosed herein. In particular, the metal- and phosphorus-containing film can be used as a threshold voltage shift layer in a semiconductor device structure such as a FET. Using the metal- and phosphorus-containing film as a threshold voltage shift layer causes the effective work function of the gate electrode in the FET to shift towards the Si conduction band in the case of an n-type FET, or towards the Si valence band in the case of a p-type FET. According to some embodiments of the present disclosure, a gate stack including a threshold voltage shift layer comprising a metal- and phosphorus-containing material disclosed herein can have an effective work function ranging from about 4.0 eV to about 5.1 eV, where the shift in the effective work function is from about 10 meV to about 400 meV, or from about 30 meV to about 300 meV, or from about 50 meV to about 200 meV. The thickness of the threshold voltage shift layer including the metal- and phosphorus-containing material can be customized to adjust the shift in the effective work function and thereby adjust Vt. Thus, in various embodiments, the thickness of the threshold voltage shift layer including the metal- and phosphorus-containing material can vary between about 0.01 nm and about 2 nm. In some embodiments, the thickness is about 2 nm or less, or about 1.9 nm or less, or about 1.8 nm or less, or about 1.7 nm or less, or about 1.6 nm or less, or about 1.5 nm or less, or about 1.4 nm or less, or about 1.3 nm or less, or about 1.2 nm or less, or about 1.1 nm or less, or about 1 nm or less, or about 0.9 nm or less, or about 0.8 nm or less, or about 0.7 nm or less, or about 0.6 nm or less, or about 0.5 nm or less, or about 0.4 nm or less, or about 0.3 nm or less, or about 0.2 nm or less, or about 0.1 nm or less. In some embodiments, the thickness is about 2 nm, or about 1.9 nm, or about 1.8 nm, or about 1.7 nm, or about 1.6 nm, or about 1.5 nm, or about 1.4 nm, or about 1.3 nm, or about 1.2 nm, or about 1.1 nm, or about 1 nm, or about 0.9 nm, or about 0.8 nm, or about 0.7 nm, or about 0.6 nm, or about 0.5 nm, or about 0.4 nm, or about 0.3 nm, or about 0.2 nm, or about 0.1 nm, or any intermediate thickness between about 0.01 nm and about 2 nm or a narrower range of any two of those thicknesses. Additionally, the composition of the threshold voltage shift layer including the metal- and phosphorus-containing material can be customized to adjust the shift in the effective work function and thereby adjust Vt, and / or reduce the EOT of the layer. Thus, in some embodiments, the threshold voltage shift layer including the metal- and phosphorus-containing material has a low oxygen content or is oxygen-free. Additionally or alternatively, in some embodiments, the threshold voltage shift layer including the metal- and phosphorus-containing material has one or more of a low carbon content and a low elemental phosphorus content, thereby beneficially reducing the number of defects in the layer.

[0134] In some embodiments, a semiconductor device structure includes a substrate; a gate dielectric including a high-κ dielectric layer on at least a portion of the surface of the substrate; and a threshold voltage shift layer including a metal- and phosphorus-containing material, where the threshold voltage shift layer is located under the high-κ dielectric layer or on at least a portion of the surface of the substrate above the high-κ dielectric layer. The high-κ dielectric layer may include a high-κ material having a dielectric constant greater than that of silicon dioxide, typically higher than about 7. Non-limiting examples of high-κ materials include hafnium oxide (HfO 2 ) tantalum oxide (Ta 2 O 5 ), zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), hafnium silicate (HfSiO x ), aluminum oxide (Al 2 O 3 ), lanthanum oxide (La 2 O 3 ) and combinations and mixtures thereof. Additionally or alternatively, the semiconductor device structure may include an intermediate layer (or interface layer) on at least a portion of the surface of the substrate under the high-κ dielectric layer and the threshold voltage shift layer. The intermediate layer may include silicon dioxide, silicon oxynitride, germanium oxynitride, tantalum oxynitride, or another suitable material. Additionally or alternatively, the semiconductor device structure may further include a metal layer on at least a portion of the surface of the substrate above the threshold voltage shift layer and above the high-κ dielectric layer. The semiconductor device structure may be or form part of a MOSFET and, in some cases, part of a CMOS device. In some embodiments, the semiconductor device structure may be an intermediate structure, such as an intermediate MOSFET structure. As used herein, an "intermediate structure" refers to a partially formed structure that requires further manufacturing steps to form the final structure.

[0135] A semiconductor device structure including a metal- and phosphorus-containing film can be formed using the methods disclosed herein. A method for forming a semiconductor device structure including a threshold voltage shift layer includes providing a substrate in a reaction space (i.e., one or more reaction chambers) and depositing a metal- and phosphorus-containing layer on at least a portion of the surface of the substrate using the methods disclosed herein. More specifically, a method for forming a semiconductor device structure including a threshold voltage shift layer includes providing a substrate in a reaction space (i.e., one or more reaction chambers) and performing at least one deposition cycle of a cyclic deposition process including sequentially exposing at least a portion of the surface of the substrate to a metal precursor and a phosphorus precursor to form a threshold voltage shift layer including a metal- and phosphorus-containing material on at least a portion of the surface of the substrate. In some embodiments, the method for forming a semiconductor device structure including a threshold voltage shift layer includes: providing a substrate in a reaction space and according to Figure 1 、 Figure 2 、 Figure 3 、Figure 4 , Figure 5 , Figure 6 , Figure 7 and Figure 8 Perform a cyclic deposition process according to the process shown in any one of the above and the above discussion, so as to form a threshold voltage offset layer including a metal- and phosphorus-containing material on at least a portion of the substrate surface. In some of these embodiments, the substrate includes an intermediate layer, and the metal- and phosphorus-containing layer is formed on at least a portion of or above the intermediate layer. In some cases, the metal- and phosphorus-containing layer is directly formed on at least a portion of or above the intermediate layer. In some embodiments, the substrate includes a high-κ dielectric layer, and the metal- and phosphorus-containing layer is formed on at least a portion of or above the high-κ layer. In some cases, the metal- and phosphorus-containing layer is directly formed on at least a portion of or above the high-κ layer. In some embodiments, the substrate includes one or more work function layers or metal layers, and the metal- and phosphorus-containing layer is formed on at least a portion of or above the one or more work function layers or metal layers. In some cases, the metal- and phosphorus-containing layer is directly formed on at least a portion of or above one of the one or more work function layers or metal layers. In some embodiments, the method further includes annealing the substrate. Annealing can be performed by heating the substrate including the metal- and phosphorus-containing film to an annealing temperature from at least about 300 °C to not exceeding about 1000 °C for a set period of time, typically from at least about 300 °C to not exceeding about 600 °C or from at least about 600 °C to not exceeding about 1000 °C. In particular, high-temperature annealing (such as drive-in annealing) can be performed as part of the final gate fabrication to drive the metal- and phosphorus-containing layer and / or other material layers on the substrate into one or more of the insulating layer, intermediate layer, or high-κ dielectric layer.

[0136] The method for forming a semiconductor device structure including a threshold voltage offset layer can be performed using the system disclosed herein, and the threshold voltage offset layer includes a metal- and phosphorus-containing material. In some embodiments, the method for forming a semiconductor device structure including a metal- and phosphorus-containing film is carried out in one or more reaction chambers of a semiconductor combination tool. In some embodiments, the method can be performed in a reaction chamber of a semiconductor combination tool according to the system shown in Figure 9 The other process steps required to form the structure can be carried out in other reaction chambers of the same combination tool. For example, the semiconductor combination tool can additionally include one or more of a reaction chamber for forming an intermediate layer, a reaction chamber for forming a high-κ dielectric layer, and a reaction chamber for forming a metal layer.

[0137] Although certain embodiments and examples are disclosed herein, those skilled in the art will understand that the disclosed compositions, methods, systems, and structures extend beyond the specifically disclosed embodiments and include all novel and non-obvious combinations and sub-combinations of the various compositions, methods, systems, and structures, as well as any and all equivalents thereof. It should be understood that the compositions, methods, systems, and structures described herein are exemplary in nature and that these specific embodiments or examples should not be considered limiting since many variations are possible. The specific methods and systems described herein may represent one or more of any number of processing strategies. Accordingly, the various acts shown may be performed in the order shown, in other orders, or in some cases omitted. In addition, for purposes of simplifying the present disclosure, various features of the present disclosure are combined in one or more aspects, embodiments, and configurations. The features of the aspects, embodiments, and configurations of the present disclosure may be combined in alternative aspects, embodiments, and configurations other than those discussed above. The compositions, methods, systems, and structures of the present disclosure should not be construed as reflecting an intention that the claimed disclosure requires more features than are expressly recited in each claim. Rather, as the following claims reflect, the inventive aspects are less than all of the features of a single foregoing aspect, embodiment, and configuration of the disclosure. Accordingly, the following claims are hereby incorporated into this detailed description, with each claim standing on its own as a separate embodiment of the present disclosure, and the features recited in the various dependent claims may be combined with one another in appropriate combinations as necessary to form other embodiments of the present disclosure.

Claims

1. A method for forming a semiconductor device structure including a threshold voltage shift layer, the method comprising: a. providing a substrate in the reaction space; and b. performing one or more deposition cycles of a cyclic deposition process, comprising: i. exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor; and ii. exposing at least a portion of the substrate surface to the other of a metal precursor and a phosphorus precursor, thereby forming a threshold voltage shifting layer on at least a portion of the substrate surface, The threshold voltage shift layer includes a material containing metal and phosphorus, which includes a metal selected from the following: rare earth metals, Group 4 metals, Group 6 metals, Group 13 metals and combinations thereof.

2. The method according to claim 1, wherein: The substrate includes at least one of an intermediate layer and a high-κ dielectric layer.

3. The method according to claim 2, wherein: The substrate includes the intermediate layer, and the threshold voltage shift layer is formed on the intermediate layer.

4. The method according to claim 2, wherein: The substrate includes a high-κ dielectric layer, and the threshold voltage shift layer is formed on the high-κ dielectric layer.

5. The method according to claim 1, wherein: The method also includes annealing the substrate.

6. The method according to claim 1, wherein: The threshold voltage shift layer has a thickness of about 1 nm or less.

7. The method according to claim 1, wherein: At least one of the one or more deposition cycles of the cyclic deposition process further comprises exposing at least a portion of the substrate surface to a halogen reactant, wherein exposing at least a portion of the substrate surface to the halogen reactant occurs after exposing at least a portion of the substrate surface to the metal precursor.

8. The method according to claim 1, wherein: The metal and phosphorus containing material is substantially free of oxygen.

9. The method according to claim 1, wherein: At least one of the one or more deposition cycles of the cyclic deposition process further comprises exposing at least a portion of the substrate to an oxygen reactant, wherein the metal and phosphorus material further comprises oxygen.

10. The method according to claim 1, wherein: The metal and phosphorus-containing material comprises rare earth metal phosphides, and the rare earth metal phosphides are selected from scandium phosphide, yttrium phosphide, lanthanum phosphide, cerium phosphide and combinations thereof.

11. The method according to claim 1, wherein: The metal and phosphorus containing material comprises a Group 4 metal phosphide selected from the group consisting of titanium phosphide, zirconium phosphide, hafnium phosphide and combinations thereof.

12. The method according to claim 1, wherein: The metal and phosphorus containing material comprises a Group 6 metal phosphide, and the Group 6 metal phosphide is selected from chromium phosphide, molybdenum phosphide, tungsten phosphide and combinations thereof.

13. The method according to claim 1, wherein: The metal and phosphorus containing material comprises a Group 13 metal phosphide, wherein the Group 13 metal phosphide is selected from boron phosphide, aluminum phosphide, gallium phosphide, indium phosphide and combinations thereof.

14. The method according to claim 1, wherein: The metal precursor comprises a metal and one or more ligands selected from the group consisting of halides, carbonyls, oxo groups, alkyl groups, cyclopentadienyl groups, η- 6 -Arenes, alkoxides, imino groups, alkylamides, silylamides, β-diketonates, amidino groups, diazadienes and triazenes.

15. The method according to claim 1, wherein: The cyclic deposition process is performed under thermal conditions, and wherein the method further comprises maintaining the temperature of the substrate at a set temperature not exceeding about 450° C. during the cyclic deposition process.

16. A method of forming a film containing metal and phosphorus, the method comprising: a. providing a substrate in the reaction space; and b. performing one or more deposition cycles of a cyclic deposition process, comprising: i. exposing at least a portion of the substrate surface to one of a metal precursor and a phosphorus precursor; ii. Purge the reaction space; iii. exposing at least a portion of the substrate surface to the other of a metal precursor and a phosphorus precursor; and iv. Purge the reaction space, wherein a film containing metal and phosphorus is formed on at least a portion of the surface of the substrate, Among them, the metal and phosphorus-containing film includes a metal phosphide material or a metal oxyphosphide material, which includes a metal selected from the following: rare earth metals, titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), chromium (Cr), tungsten (W) and mixtures thereof.

17. The method according to claim 16, wherein: The cyclic deposition process further includes exposing at least a portion of the substrate surface to a halogen reactant.

18. The method according to claim 16, wherein: The cyclic deposition process also includes exposing at least a portion of the substrate surface to an oxygen reactant.

19. A semiconductor device structure comprising a threshold voltage shifting layer formed by the method according to claim 1.

20. A semiconductor processing device comprising: A reaction space for accommodating a substrate, A metal precursor source for providing a metal precursor in gas communication with the reaction space via a metal precursor source valve; A phosphorus precursor source, for providing a phosphorus precursor in gas communication with the reaction space via a phosphorus precursor source valve; Exhaust system; as well as a controller operably connected to the metal precursor source valve and the phosphorus precursor source valve, Wherein, the controller is configured and programmed to perform the method according to claim 1.

Images