Methods, apparatus and structures for forming rare earth-containing layers

Abstract

The present disclosure relates to methods, apparatus and structures for forming rare earth-containing layers. The method includes providing a substrate within a processing chamber and depositing a rare earth-containing layer on the substrate. The process of depositing the rare earth-containing layer includes providing a rare earth precursor into a processing chamber, providing a metal precursor into the processing chamber, and providing one or more non-metallic element reactants into the processing chamber. The apparatus includes a processing chamber, a precursor supply unit for supplying a rare earth precursor and a metal precursor into the processing chamber, and a reactant supply unit for supplying one or more non-metallic element reactants into the processing chamber.

Description

Technical Field

[0001] The present disclosure generally relates to methods and systems suitable for forming a layer on a substrate surface, and structures including the layer. More specifically, the present disclosure relates to methods and systems for forming a layer that allow control of the threshold voltage of a metal oxide semiconductor field effect transistor (MOSFET), and to structures formed using the methods and systems. Background Art

[0002] The reduction in size of semiconductor devices, such as complementary metal oxide semiconductor (CMOS) devices, has led to significant increases in the speed and density of integrated circuits. However, conventional device scaling techniques face significant challenges for future technology nodes. For example, one challenge is finding a suitable dielectric stack that forms an insulating barrier between the gate and the channel of a field effect transistor. A particular problem in this regard is controlling the threshold voltage of the field effect transistor.

[0003] Any discussion set forth in this section, including discussion of problems and solutions, has been included in the present disclosure merely to provide context for the present disclosure. Such discussion should not be considered as an admission that any or all of the information is already known. Summary of the invention

[0004] According to a first aspect, a method for forming a rare earth-containing layer is provided. The method includes providing a substrate in a processing chamber and depositing the rare earth-containing layer on the substrate. The process of depositing the rare earth-containing layer includes providing a rare earth precursor into the processing chamber, providing a metal precursor into the processing chamber, and providing one or more non-metallic element reactants into the processing chamber. The rare earth-containing layer includes a rare earth element, a metal element different from the rare earth element, a first non-metallic element, and a second non-metallic element different from the first non-metallic element.

[0005] According to a second aspect, an apparatus is provided, comprising a process chamber, a precursor supply unit for supplying a rare earth precursor and a metal precursor into the process chamber, a reactant supply unit for supplying one or more non-metallic element reactants into the process chamber, and a control unit configured to control at least the precursor supply unit and the reactant supply unit to perform the method according to the first aspect.

[0006] According to a third aspect, a structure is provided. The structure includes a substrate and a rare earth-containing layer on the substrate. The rare earth-containing layer includes a rare earth element, a metal element different from the rare earth element, a first non-metal element, and a second non-metal element different from the first non-metal element.

[0007] The embodiments discussed below may relate to any of the aspects described above, mutatis mutandis.

[0008] In some embodiments, the rare earth element is selected from cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, and yttrium.

[0009] In some embodiments, the rare earth precursor includes at least one of cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, and yttrium.

[0010] In some embodiments, the rare earth precursor includes a rare earth element in an oxidation state +3 or an oxidation state +4.

[0011] In some embodiments, the rare earth precursor comprises a cyclopentadienyl ligand, for example, an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, for example, an isopropylcyclopentadienyl ligand.

[0012] In some embodiments, the metal element is selected from Group 3 metals, such as scandium and yttrium; Group 4 metals, such as titanium and zirconium; Group 5 metals, such as vanadium and niobium; Group 6 metals, such as chromium and molybdenum; Group 7 metals, such as manganese; Group 8 metals, such as iron and ruthenium; Group 9 metals, such as cobalt and rhodium; Group 10 metals, such as nickel and palladium; Group 11 metals, such as copper and silver; Group 12 metals, such as zinc and cadmium; Group 13 metals, such as aluminum, gallium and indium; and lanthanides; such as cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium and ytterbium.

[0013] In some embodiments, the metal precursor includes at least one of: a Group 3 metal such as scandium or yttrium; a Group 4 metal such as titanium or zirconium; a Group 5 metal such as vanadium or niobium; a Group 6 metal such as chromium or molybdenum; a Group 7 metal such as manganese; a Group 8 metal such as iron or ruthenium; a Group 9 metal such as cobalt or rhodium; a Group 10 metal such as nickel or palladium; a Group 11 metal such as copper or silver; a Group 12 metal such as zinc or cadmium; a Group 13 metal such as aluminum, gallium, or indium; and a lanthanide; for example, cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium, or ytterbium.

[0014] In some embodiments, the metal precursor includes a metal element in oxidation state +3 or oxidation state +4.

[0015] In some embodiments, the metal precursor comprises a cyclopentadienyl ligand, for example, an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, for example, an isopropylcyclopentadienyl ligand.

[0016] In some embodiments, the first non-metal element and / or the second non-metal element is selected from boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as fluorine, chlorine, bromine or iodine.

[0017] In some embodiments, providing one or more non-metal element reactants includes providing a first non-metal element reactant and providing a second non-metal element reactant different from the first non-metal element reactant.

[0018] In some embodiments, the first non-metal element reactant includes boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as at least one of fluorine, chlorine, bromine or iodine; the second non-metal element reactant includes boron, a Group 14 non-metal such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as at least another of fluorine, chlorine, bromine or iodine.

[0019] In some embodiments, providing one or more non-metal element reactants includes providing a non-metal multi-element reactant comprising a first non-metal element and a second first non-metal element.

[0020] In some embodiments, the substrate has an outer surface and includes a dielectric layer extending along the outer surface.

[0021] In some embodiments, the dielectric layer includes a high-k dielectric material, such as a high-k silicate, eg, hafnium silicate; a high-k oxide, such as hafnium dioxide, tantalum oxide, or zirconium dioxide; or a mixture thereof, such as a solid solution or a mixed oxide.

[0022] In some embodiments, the method includes forming a first conductive layer before depositing the rare earth-containing layer.

[0023] In some embodiments, the first conductive layer includes a first transition metal compound.

[0024] In some embodiments, the first transition metal compound includes a first non-metal constituent element that is different from the first non-metal element and / or the second first non-metal element.

[0025] In some embodiments, the first transition metal compound includes a first transition metal element different from the rare earth element and / or the metal element.

[0026] In some embodiments, the first transition metal compound is implemented as a first transition metal carbide and / or a first transition metal nitride.

[0027] In some embodiments, the thickness of the first conductive layer is greater than or equal to 0.1 nm, or 0.5 nm, or 0.8 nm and / or less than or equal to 8 nm, or 6 nm, or 5 nm.

[0028] In some embodiments, the method includes forming a second conductive layer after depositing the rare earth-containing layer.

[0029] In some embodiments, the second conductive layer includes a second transition metal compound.

[0030] In some embodiments, the second transition metal compound includes a second non-metal constituent element that is different from the first non-metal element and / or the second first non-metal element.

[0031] In some embodiments, the second transition metal compound includes a second transition metal element different from the rare earth element and / or the metal element.

[0032] In some embodiments, the second transition metal compound is implemented as a second transition metal carbide and / or a second transition metal nitride.

[0033] In some embodiments, the thickness of the second conductive layer is greater than or equal to 0.5 nm, or 1 nm, or 2 nm and / or less than or equal to 40 nm, or 30 nm, or 20 nm.

[0034] In some embodiments, the process of depositing the rare earth-containing layer includes providing a first hydrogen-containing species after the process of providing a rare earth precursor and / or providing a second hydrogen-containing species after the process of providing a metal precursor.

[0035] In some embodiments, the first hydrogen-containing species and / or the second hydrogen-containing species include hydrogen gas.

[0036] In some embodiments, the rare earth-containing layer is formed at a deposition temperature greater than or equal to 100°C, or 200°C, or 300°C, or 350°C and / or less than or equal to 550°C, or 500°C, or 450°C, or 400°C.

[0037] In some embodiments, the thickness of the rare earth-containing layer is greater than or equal to 0.1 nm, or 0.5 nm, or 1 nm, or 2 nm and / or less than or equal to 10 nm, or 8 nm, or 5 nm.

[0038] In some embodiments, the rare earth-containing layer is formed in a cross-flow processing chamber, a showerhead processing chamber, or a hot wall processing chamber.

[0039] In some embodiments, the process of providing a rare earth precursor includes maintaining the rare earth precursor in a rare earth precursor container and delivering the rare earth precursor to a processing chamber using a rare earth precursor carrier gas, and / or the process of providing a metal precursor includes maintaining the metal precursor in a metal precursor container and delivering the metal precursor to a processing chamber using a metal precursor carrier gas.

[0040] In some embodiments, the rare earth precursor carrier gas and / or the metal precursor carrier gas are independently selected from nitrogen, helium, neon, argon, krypton, xenon, radon, and mixtures thereof.

[0041] In some embodiments, the rare earth precursor and / or metal precursor is maintained at a container temperature greater than or equal to 20°C, or 50°C, or 70°C, or 350°C and / or less than or equal to 200°C, or 150°C, or 130°C.

[0042] In some embodiments, the process of depositing the rare earth containing layer is implemented as a chemical vapor deposition process, such as a cyclic chemical vapor deposition process, such as an atomic layer deposition process, such as a timed atomic layer deposition process.

[0043] In some embodiments, the process of depositing the rare earth-containing layer is implemented as a thermal deposition process or an active species enhanced deposition process, such as a free radical enhanced deposition process.

[0044] In some embodiments, the structure forms at least a portion of a semiconductor device, such as a semiconductor transistor, such as a metal oxide semiconductor field effect transistor.

[0045] In some embodiments, the structure is formed using a method according to the first aspect.

[0046] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] A more complete understanding of embodiments of the present disclosure may be obtained by referring to the detailed description and claims when considered in conjunction with the following illustrative drawings:

[0048] Figure 1A A method for forming a rare earth-containing layer is shown.

[0049] Figure 1B Another method for forming a rare earth-containing layer is shown.

[0050] Figure 2 A device is depicted, and

[0051] Figure 3 A structure of a semiconductor device is shown.

[0052] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0053] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specifically disclosed embodiments described below.

[0054] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device but are merely idealized representations used to describe embodiments of the present disclosure.

[0055] The specific embodiments shown and described are illustrations of the present invention and its best mode and are not intended to limit the scope of these aspects and embodiments in any way. In fact, for the sake of brevity, the traditional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems, and / or may not exist in some embodiments.

[0056] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

[0057] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

[0058] In this specification, a "process" may refer to a series of one or more steps leading to an end result. In addition, a "step" may refer to an action taken to achieve one or more predefined end results. In general, a process may be a single-step or multi-step process. In addition, a process may be divided into multiple sub-processes, wherein each of these multiple sub-processes may or may not share common steps.

[0059] In this specification, a "chemical vapor deposition process" or "CVD process" may refer to a coating process in which one or more gaseous compounds decompose to deposit a layer on a substrate. In addition, a "cyclic chemical vapor deposition process" or "cyclic CVD process" may refer to a CVD process that includes sequentially and / or cyclically providing precursors, and / or reactants, and / or reactive species to deposit the layer onto the substrate.

[0060] Throughout this specification, an "atomic layer deposition process" or "ALD process" may refer to a cyclic CVD process including purging a process chamber or processing station between providing precursors and / or reactants and / or active substances. Typically, purging can be accomplished by flushing the process chamber or processing station with an inert gas. Additionally or alternatively, an "atomic layer deposition process" or "ALD process" may refer to a cyclic CVD process suitable for or configured to deposit a conformal layer on a substrate, such as a layer having a step coverage (SC) of at least 95%, or 99%, or about 100% for features having an aspect ratio (AR) of 3:1, or 5:1, or 10:1. The term "atomic layer deposition" as used herein may or may not refer to a process designated by a related term, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor / reactive gas and purge gas (e.g., inert carrier gas). Furthermore, a "timed atomic layer process" or "timed ALD process" may refer to an ALD process in which the process of purging a process station includes a timed purge step during which the supply of precursors, and / or reactants, and / or reactive species is stopped. Additionally or alternatively, a "timed atomic layer process" or "timed ALD process" may refer to an ALD process in which the substrate on which the layer is deposited remains stationary during deposition.

[0061] Typically, for an ALD process, during each cycle, a precursor is introduced into a processing chamber or processing station and is chemically adsorbed onto a deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other material) and forms a material, such as around a monolayer or sub-monolayer of material, or multiple monolayers of material, or multiple monolayers of material, that is not susceptible to reaction with additional precursors (i.e., a self-limiting reaction). Thereafter, in some cases, a reactant (e.g., another precursor or a reactive gas) may subsequently be introduced into the processing chamber for converting the chemically adsorbed precursor to the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more cycles, such as after each step of each cycle, a purge step may be utilized to remove any excess precursor from the processing chamber or processing station and / or to remove any excess reactant and / or reaction byproducts from the processing chamber or processing station.

[0062] In the present disclosure, an "active species enhanced" deposition process may refer to a CVD process, wherein during the deposition process, one or more gaseous compounds that decompose to deposit a layer are exposed to active species, while a "thermal deposition process" may refer to an inactive species enhanced CVD process. In this article, "active species" may refer to unstable molecular entities formed in a plasma by interaction with a catalytic material at high temperature and / or by other suitable means. In addition or alternatively, active species may refer to ions and / or (free) radicals. Furthermore, "ions" may refer to atoms or molecular particles having a net charge, and / or "radicals" may refer to atoms or molecular particles having unpaired electrons. In some embodiments, an active species enhanced deposition process may be implemented as a free radical enhanced deposition process, wherein the active species into which one or more gaseous compounds decompose may include, mainly include, significantly include, substantially include, mainly consist of, substantially consist of, or consist of free radicals.

[0063] In the present disclosure, a "layer" or "film" may refer to a structure having a certain thickness formed on a surface. A layer may be continuous or discontinuous. A film or layer may or may not be composed of a discrete single film or layer or a plurality of films or layers having certain properties. The boundaries between adjacent films or layers may or may not be clear and may or may not be established based on the physical, chemical and / or any other characteristics, formation process or sequence and / or function or purpose of adjacent films or layers. A layer or film may or may not contain pinholes. A layer of film may or may not be porous.

[0064] In the present disclosure, "substrate" may refer to any one or more underlying materials that may be used to form or on which a device, circuit, or film may be formed. The substrate may include a bulk material, such as silicon (e.g., single crystal silicon), other Group IV materials, such as germanium, or a compound semiconductor material, such as GaAs, and may include one or more layers overlying or underlying the bulk material. In addition, the substrate may include various structures, such as grooves, through holes, lines, etc., formed in or on at least a portion of the substrate layer.

[0065] Here, a "processing chamber" may refer to a chamber adapted or configured to be able to perform a process on a substrate. Additionally or alternatively, a processing chamber may refer to a vacuum chamber in which a process may be performed. A processing chamber may include one or more processing stations.

[0066] Here, "processing station" may refer to a position suitable for or configured to hold a substrate so that a process can be performed on the substrate. Additionally or alternatively, a processing station may refer to a part of a processing chamber. In some embodiments, when one or more substrates are processed in one or more separate processing stations, the various processing stations of the processing chamber may be arranged to be gas-isolated from each other or configured to be gas-isolated from each other. In such embodiments, the various processing stations of the processing chamber may be arranged to be gas-isolated by physical barriers, and / or gas bearings, and / or gas curtains. In some embodiments, after or while the substrate is placed in the processing station, the processing station may be arranged to be gas-isolated. In some embodiments, after the substrate has been processed in the processing station, the processing station may be separated from gas isolation so that the substrate can be removed from the processing station. Typically, a plurality of substrates may be placed in a shared intermediate space of a processing chamber for moving each of the plurality of substrates from a processing station to another processing station.

[0067] Throughout this specification, "control unit" may refer to any combination of a separate controller device and a processing electronic device that can be integrated with or connected to other devices. In some embodiments, the control unit may include a centralized controller that controls the operation of multiple devices or components. In some embodiments, the control unit may be understood as including multiple distributed controllers that control the operation of one or more devices or components. Typically, the control sequence may be hardwired or programmed into the control unit. The storage device of the control unit may include a non-transitory computer-readable medium, such as a physical computer memory, including a hard drive, a solid-state memory, a random access memory (RAM), a read-only memory (ROM), an optical disk, a volatile or non-volatile memory, a combination thereof, and the like. The non-transitory computer-readable medium may provide instructions to one or more processors. It should be understood that instructions may be used for any action described herein so that the processing of the instructions by one or more processors causes the semiconductor processing equipment to perform those actions.

[0068] In the present disclosure, "gas" may refer to a material that is a gas, an evaporating solid, and / or an evaporating liquid at normal temperature and pressure (NTP). The term "gas" may refer to a gas consisting of a single chemical substance or a mixture of chemical substances. Gases other than process gases, i.e., gases that are not introduced through a gas distribution assembly, other gas distribution devices, etc., may be used, for example, in sealed processing stations and may include sealing gases, such as rare gases.

[0069] In this specification, "precursor" or "reactant" may refer to a compound that participates in a chemical reaction to produce another compound, such as a compound that constitutes a membrane matrix or a membrane backbone.

[0070] The following abbreviations may be used in the present disclosure: RE-M may refer to rare earth metal, Cp may refer to cyclopentadienyl, MeCp may refer to methylcyclopentadienyl, EtCp may refer to ethylcyclopentadienyl, iPrCp may refer to isopropylcyclopentadienyl, nPrCp may refer to n-propylcyclopentadienyl, tBuCp may refer to tert-butylcyclopentadienyl, TMSCp may refer to trimethylsilylcyclopentadienyl. Me may refer to methyl; Et may refer to ethyl; iPr may refer to isopropyl; nPr may refer to n-propyl; nBu may refer to n-butyl; acac may refer to acetylacetonate; hfac may refer to hexafluoroacetylacetonate; when R is equal to R′, N R,R’ R”-amd” or N R R″-amd refers to an amidine ligand [R—N—C(R″)═N—R′], wherein R, R′ and R″ are C1-C5 hydrocarbon groups, such as C1-C5 hydrocarbon groups; R2-fmd” may refer to an amidine ligand, wherein R is equal to R′ and R″ is equal to H; R2-amd” may refer to an amidine ligand, wherein R is equal to R′ and R″ is equal to CH3; thd may refer to 2,2,6,6-tetramethylheptane-3,5-diacid ester; phen may refer to phenanthroline.

[0071] The method and device described at present can be used to control the threshold voltage of field effect transistor. In some embodiments, the method and device can be used to control the threshold voltage of n-channel field effect transistor, such as n-channel metal oxide semiconductor field effect transistor, such as n-channel full gate metal oxide semiconductor field effect transistor. In some embodiments, the method and device can be used to control the threshold voltage of p-channel field effect transistor, such as p-channel metal oxide semiconductor field effect transistor, such as p-channel full gate metal oxide semiconductor field effect transistor. In some embodiments, the method and device can be used to induce the negative flat band voltage offset of metal oxide semiconductor field effect transistor (MOSFET). Therefore, the method and device may be particularly useful for reducing the gate voltage that generates a conductive channel between the source and drain of n-MOSFET. For example, n-MOSFET can be included in a CMOS-based integrated circuit. In addition or alternatively, the method and device can be particularly used to increase the gate voltage that generates a conductive channel between the source and drain of p-MOSFET. For example, p-MOSFET can be included in a CMOS-based integrated circuit. In other words, the present method and device are particularly useful for reducing the voltage at which an n-MOSFET switches from an off state to an on state and increasing the voltage at which a p-MOSFET switches from an off state to an on state. Similarly, the present method and device may be particularly useful for reducing the flatband voltage of an n-MOSFET and increasing the flatband voltage of a p-MOSFET. The present method and device may be particularly useful for manufacturing n-MOSFETs and p-MOSFETs with a full-gate architecture. Additionally or alternatively, the present method and device may be particularly useful in the context of a system-on-chip.

[0072] In some embodiments, the present method and device can be used to induce a positive flatband voltage shift of a metal oxide semiconductor field effect transistor (MOSFET). Therefore, the present method and device can be used to increase the gate voltage at which a conductive channel is generated between the source and drain of an n-MOSFET. For example, an n-MOSFET can be included in a CMOS-based integrated circuit. Additionally or alternatively, the present method and device are particularly useful for reducing the gate voltage that generates a conductive channel between the source and drain of a p-MOSFET. For example, a p-MOSFET can be included in a CMOS-based integrated circuit. In other words, the present method and device are particularly useful for increasing the voltage at which an n-MOSFET switches from an off state to an on state, and for reducing the voltage at which a p-MOSFET switches from an off state to an on state. Similarly, the present method and device may be particularly useful for increasing the flatband voltage of an n-MOSFET and reducing the flatband voltage of a p-MOSFET. The presently described method and device may be particularly useful for manufacturing n-MOSFETs and p-MOSFETs having a surround gate architecture. Additionally or alternatively, the present method and device may be particularly useful in the context of a system on a chip.

[0073] Throughout this specification, material compositions are abbreviated by chemical formulas, which may or may not refer to the material having a stoichiometric composition. In some embodiments, a chemical formula may refer to a stoichiometric composition inferred from the chemical formula. In other embodiments, a chemical formula may refer to a stoichiometric composition different from that inferred from the chemical formula. In other embodiments, a chemical formula may refer to a non-stoichiometric composition. For example, when titanium nitride is abbreviated as "TiN", the term TiN may refer to a material containing titanium and nitrogen, wherein the titanium and nitrogen are present in a ratio of 1:1, or in any other suitable ratio, such as 0.8:1, 0.9:1, 0.95:1, 1:1.05, 1:1.1, 1.2, 1.5, etc.

[0074] A method for forming a rare earth-containing layer is described herein. The method includes providing a substrate in a processing chamber. Suitable substrates include single crystal silicon wafers, such as p-type single crystal silicon wafers. The method also includes depositing the rare earth-containing layer on the substrate. The process of depositing the rare earth-containing layer includes providing a rare earth precursor into the processing chamber, providing a metal precursor into the processing chamber, and providing one or more non-metallic element reactants into the processing chamber. The rare earth-containing layer includes a rare earth element, a metal element different from the rare earth element, a first non-metallic element; and a second non-metallic element different from the first non-metallic element.

[0075] In some embodiments, providing a rare earth precursor and / or providing a metal precursor precedes at least a portion of the process of providing one or more non-metallic element reactants. Nevertheless, in other embodiments, the process of providing one or more non-metallic element reactants may be at least partially prior to the process of providing a rare earth precursor and / or providing a metal precursor.

[0076] In some embodiments, the rare earth element is selected from cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, and yttrium.

[0077] In some embodiments, the rare earth precursor includes at least one of cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium, and yttrium.

[0078] In some embodiments, the rare earth precursor includes a rare earth element in an oxidation state of +3 or an oxidation state of +4. In general, the rare earth precursor may include any suitable oxidation state of the rare earth element, such as +2, +3, or +4. In some embodiments, the rare earth precursor includes RE-M(Cp)3, RE-M(EtCp)3, RE-M(MeCp)3, RE-M(iPrCp)3, RE-M(nPrCp)3, RE-M(nBuCp)3, and / or RE-M(tBuCp)3. In some embodiments, the rare earth precursor includes RE-M(Cp)4, RE-M(EtCp)4, RE-M(MeCp)4, RE-M(iPrCp)4, RE-M(nPrCp)4, RE-M(nBuCp)4, and RE-M(tBuCp)4.

[0079] In certain embodiments, the rare earth precursor comprises a cyclopentadienyl ligand, such as an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, such as an isopropyl cyclopentadienyl ligand. In certain embodiments, the alkylsilyl-substituted cyclopentadienyl ligand is selected from trimethylsilylcyclopentadienyl, triethylsilylcyclopentadienyl and triisopropylsilylcyclopentadienyl. In certain embodiments, the rare earth precursor comprises RE-M (TMSCp) 3. In certain embodiments, the rare earth precursor comprises a C1 to C4 alkyl-substituted cyclopentadienyl ligand, such as EtCp, MeCp, iPrCp, nBuCp or tBuCp.

[0080] In some embodiments, the rare earth precursor comprises a rare earth metal diketonate. In some embodiments, the rare earth precursor comprises a guanidinium ligand. In some embodiments, the rare earth precursor is selected from RE-M(acac)4, RE-M(hfac)3, RE-M(hfac)4, RE-M(thd)3, RE-M(thd)4 and RE-M(thd)3phen.

[0081] In some embodiments, the rare earth precursor comprises an amidine ligand. In some embodiments, the rare earth precursor comprises a formamide (fmd) ligand. In some embodiments, the rare earth precursor comprises an acetamidine (amd) ligand. In some embodiments, the rare earth precursor comprises an amidine ligand selected from R2-amd and R2-fmd, wherein R is a linear or branched C1 to C4 alkyl group. In some embodiments, the rare earth precursor comprises a compound of the form: RE-M (R 1 2-amd)3,RE-M(R 1 2-fmd)3,RE-M(R 2 2Cp)2(R 1 2-amd) and RE-M (R 2 2Cp)2(R 1 2-fmd),RE-M(R 1 2-amd)4,RE-M(R 1 2-fmd)4,RE-M(R 2 2Cp)3(R 1 2-amd),RE-M(R 2 2Cp)2(R 1 2-amd)2,RE-M(R 2 2Cp)(R 1 2-amd)3,RE-M(R 2 2Cp)3(R 1 2-fmd),RE-M(R 2 2Cp)2(R 1 2-fmd)2 and RE-M(R 2 2Cp)(R 1 2-fmd)3, where R 1 and R 2In some embodiments, the rare earth precursor comprises at least one of the following: RE-M(iPr2-amd)3, RE-M(tBu2-amd)3 and RE-M(iPrCp)2(iPr2-amd), RE-M(Cp)2(iPr2-amd), RE-M(MeCp)2(iPr2-amd), RE-M(EtCp)2(iPr2-amd), RE-M(nPrCp)2(i Pr2-amd),RE-M(tBuCp)2(iPr2-amd),RE-M(iPr2-amd)4,RE-M(tBu2-amd)4,RE-M(iPrCp)3(i Pr2-amd),RE-M(iPrCp)2(iPr2-amd)2,RE-M(iPrCp)(iPr2-amd)3,RE-M(Cp)3(iPr2-amd),RE -M(Cp)2(iPr2-amd)2,RE-M(Cp)(iPr2-amd)3,RE-M(MeCp)3(iPr2-amd),RE-M(MECp)2(iPr2- amd)2,RE-M(MeCp)(iPr2-amd)3,RE-M(EtCp)3(iPr2-amd),RE-M(EtCp)2(iPr2-amd)2,RE-M( EtCp)(iPr2-amd)3,RE-M(nPrCp)3(iPr2-amd),RE-M(nPrCp)2(iPr2-amd)2,RE-M(nPrCp)(iP r2-amd)3, RE-M(tBuCp)3(iPr2-amd), RE-M(tBuCp)2(iPr2-amd)2, RE-M(tBuCp)(iPr2-amd)3.In some embodiments, the rare earth precursor includes at least one of the following: RE-M(iPr2-fmd)3, RE-M(tBu2-fmd)3 and RE-M(iPrCp)2(iPr2-fmd), RE-M(Cp)2(iPr2-fmd), RE-M(MeCp)2(iPr2-fmd), RE-M(EtCp)2(iPr2-fmd), RE-M(nPrCp)2(i Pr2-fmd),RE-M(tBuCp)2(iPr2-fmd),RE-M(iPr2-fmd)4,RE-M(tBu2-fmd)4,RE-M(iPrCp)3(i Pr2-fmd),RE-M(iPrCp)2(iPr2-fmd)2,RE-M(iPrCp)(iPr2-fmd)3,RE-M(Cp)3(iPr2-fmd),RE -M(Cp)2(iPr2-fmd)2,RE-M(Cp)(iPr2-fmd)3,RE-M(MeCp)3(iPr2-fmd),RE-M(MECp)2(iPr2- fmd)2,RE-M(MeCp)(iPr2-fmd)3,RE-M(EtCp)3(iPr2-fmd),RE-M(EtCp)2(iPr2-fmd)2,RE-M( EtCp)(iPr2-fmd)3,RE-M(nPrCp)3(iPr2-fmd),RE-M(nPrCp)2(iPr2-fmd)2,RE-M(nPrCp)(iP r2-fmd)3, RE-M(tBuCp)3(iPr2-fmd), RE-M(tBuCp)2(iPr2-fmd)2 and RE-M(tBuCp)(iPr2-fmd)3.

[0082] In some embodiments, the rare earth precursor comprises a rare earth metal alkoxide, such as RE-M(OCMe2CH2OMe)4.

[0083] In some embodiments, the rare earth precursor includes one or more rare earth metal alkylsilylamines. Exemplary alkaline earth metal alkylsilylamines include Ce[N(SiMe3)2]3.

[0084] In some embodiments, the metal element is selected from Group 3 metals, such as scandium and yttrium; Group 4 metals, such as titanium and zirconium; Group 5 metals, such as vanadium and niobium; Group 6 metals, such as chromium and molybdenum; Group 7 metals, such as manganese; Group 8 metals, such as iron and ruthenium; Group 9 metals, such as cobalt and rhodium; Group 10 metals, such as nickel and palladium; Group 11 metals, such as copper and silver; Group 12 metals, such as zinc and cadmium; Group 13 metals, such as aluminum, gallium and indium; and lanthanides; such as cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium and ytterbium.

[0085] In some embodiments, the metal precursor includes at least one of: a Group 3 metal such as scandium or yttrium; a Group 4 metal such as titanium or zirconium; a Group 5 metal such as vanadium or niobium; a Group 6 metal such as chromium or molybdenum; a Group 7 metal such as manganese; a Group 8 metal such as iron or ruthenium; a Group 9 metal such as cobalt or rhodium; a Group 10 metal such as nickel or palladium; a Group 11 metal such as copper or silver; a Group 12 metal such as zinc or cadmium; a Group 13 metal such as aluminum, gallium, or indium; and a lanthanide; for example, cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium, or ytterbium.

[0086] In some embodiments, the metal precursor includes a metal element in an oxidation state of +3 or an oxidation state of +4. In general, the metal precursor may include a metal element in any suitable oxidation state, such as +2, +3, or +4. In some embodiments, the metal precursor includes RE-M(Cp)3, RE-M(EtCp)3, RE-M(MeCp)3, RE-M(iPrCp)3, RE-M(nPrCp)3, RE-M(nBuCp)3, and / or RE-M(tBuCp)3. In some embodiments, the metal precursor includes RE-M(Cp)4, RE-M(EtCp)4, RE-M(MeCp)4, RE-M(iPrCp)4, RE-M(nPrCp)4, RE-M(nBuCp)4, and RE-M(tBuCp)4.

[0087] In certain embodiments, the metal precursor comprises a cyclopentadienyl ligand, such as an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, such as an isopropyl cyclopentadienyl ligand. In certain embodiments, the alkylsilyl-substituted cyclopentadienyl ligand is selected from trimethylsilylcyclopentadienyl, triethylsilylcyclopentadienyl and triisopropylsilylcyclopentadienyl. In certain embodiments, the metal precursor comprises RE-M (TMSCp) 3. In certain embodiments, the metal precursor comprises a C1 to C4 alkyl-substituted cyclopentadienyl ligand, such as EtCp, MeCp, iPrCp, nBuCp or tBuCp.

[0088] In some embodiments, the metal precursor comprises a rare earth metal diketonate. In some embodiments, the metal precursor comprises a guanidinium ligand. In some embodiments, the metal precursor is selected from RE-M(acac)4, RE-M(hfac)3, RE-M(hfac)4, RE-M(thd)3, RE-M(thd)4 and RE-M(thd)3phen.

[0089] In some embodiments, the metal precursor comprises an amidine ligand. In some embodiments, the metal precursor comprises a formamidine (fmd) ligand. In some embodiments, the metal precursor comprises an acetamidine (amd) ligand. In some embodiments, the metal precursor comprises an amidine ligand selected from R2-amd and R2-fmd, wherein R is a linear or branched C1 to C4 alkyl. In some embodiments, the metal precursor comprises a compound of the form: RE-M (R 1 2-amd)3,RE-M(R 1 2-fmd)3,RE-M(R 2 2Cp)2(R 1 2-amd) and RE-M (R 2 2Cp)2(R 1 2-fmd),RE-M(R 1 2-amd)4,RE-M(R 1 2-fmd)4,RE-M(R 2 2Cp)3(R 1 2-amd),RE-M(R 2 2Cp)2(R 1 2-amd)2,RE-M(R 2 2Cp)(R 1 2-amd)3,RE-M(R 2 2Cp)3(R 1 2-fmd),RE-M(R 2 2Cp)2(R 1 2-fmd)2 and RE-M(R 2 2Cp)(R 1 2-fmd)3, where R 1 and R 2In some embodiments, the metal precursor comprises at least one of the following: RE-M(iPr2-amd)3, RE-M(tBu2-amd)3 and RE-M(iPrCp)2(iPr2-amd), RE-M(Cp)2(iPr2-amd), RE-M(MeCp)2(iPr2-amd), RE-M(EtCp)2(iPr2-amd), RE-M(nPrCp)2(i Pr2-amd),RE-M(tBuCp)2(iPr2-amd),RE-M(iPr2-amd)4,RE-M(tBu2-amd)4,RE-M(iPrCp)3(i Pr2-amd),RE-M(iPrCp)2(iPr2-amd)2,RE-M(iPrCp)(iPr2-amd)3,RE-M(Cp)3(iPr2-amd),RE -M(Cp)2(iPr2-amd)2,RE-M(Cp)(iPr2-amd)3,RE-M(MeCp)3(iPr2-amd),RE-M(MECp)2(iPr2- amd)2,RE-M(MeCp)(iPr2-amd)3,RE-M(EtCp)3(iPr2-amd),RE-M(EtCp)2(iPr2-amd)2,RE-M( EtCp)(iPr2-amd)3,RE-M(nPrCp)3(iPr2-amd),RE-M(nPrCp)2(iPr2-amd)2,RE-M(nPrCp)(iP r2-amd)3, RE-M(tBuCp)3(iPr2-amd), RE-M(tBuCp)2(iPr2-amd)2, RE-M(tBuCp)(iPr2-amd)3.In some embodiments, the metal precursor includes at least one of the following: RE-M(iPr2-fmd)3, RE-M(tBu2-fmd)3 and RE-M(iPrCp)2(iPr2-fmd), RE-M(Cp)2(iPr2-fmd), RE-M(MeCp)2(iPr2-fmd), RE-M(EtCp)2(iPr2-fmd), RE-M(nPrCp)2(i Pr2-fmd),RE-M(tBuCp)2(iPr2-fmd),RE-M(iPr2-fmd)4,RE-M(tBu2-fmd)4,RE-M(iPrCp)3(i Pr2-fmd),RE-M(iPrCp)2(iPr2-fmd)2,RE-M(iPrCp)(iPr2-fmd)3,RE-M(Cp)3(iPr2-fmd),RE -M(Cp)2(iPr2-fmd)2,RE-M(Cp)(iPr2-fmd)3,RE-M(MeCp)3(iPr2-fmd),RE-M(MECp)2(iPr2- fmd)2,RE-M(MeCp)(iPr2-fmd)3,RE-M(EtCp)3(iPr2-fmd),RE-M(EtCp)2(iPr2-fmd)2,RE-M( EtCp)(iPr2-fmd)3,RE-M(nPrCp)3(iPr2-fmd),RE-M(nPrCp)2(iPr2-fmd)2,RE-M(nPrCp)(iP r2-fmd)3, RE-M(tBuCp)3(iPr2-fmd), RE-M(tBuCp)2(iPr2-fmd)2 and RE-M(tBuCp)(iPr2-fmd)3.

[0090] In some embodiments, the metal precursor comprises a rare earth metal alkoxide, such as RE-M(OCMe2CH2OMe)4.

[0091] In some embodiments, the metal precursor includes one or more rare earth metal alkylsilylamines. Exemplary alkaline earth metal alkylsilylamines include Ce[N(SiMe3)2]3.

[0092] In some embodiments, the first non-metal element and / or the second non-metal element is selected from boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as fluorine, chlorine, bromine or iodine.

[0093] In some embodiments, providing one or more non-metal element reactants includes providing a first non-metal element reactant and providing a second non-metal element reactant different from the first non-metal element reactant.

[0094] In some embodiments, the first non-metal element reactant includes boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus, or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium, or tellurium; and a Group 17 non-metal, such as at least one of fluorine, chlorine, bromine, or iodine; the second non-metal element reactant includes boron, a Group 14 non-metal such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus, or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium, or tellurium; and a Group 17 non-metal, such as at least another of fluorine, chlorine, bromine, or iodine.

[0095] In some embodiments, the first non-metal element reactant and / or the second non-metal element reactant comprises a halogenated C1 to C6 alkane or alkene. In some embodiments, the first non-metal element reactant and / or the second non-metal element reactant comprises C, H and a halogen. Suitable halogens include F, Cl, Br and I. In some embodiments, the first non-metal element or the second non-metal element comprises a halogenated C1 to C6 alkane or alkene. x H y I z One or more compounds are given, for example C2H5I, C2H4I2, CH2I2, CHI3, CH3I and / or CI4.

[0096] In some embodiments, providing one or more non-metal element reactants includes providing a non-metal multi-element reactant comprising a first non-metal element and a second first non-metal element.

[0097] In some embodiments, the substrate has an outer surface and includes a dielectric layer extending along the outer surface.

[0098] In some embodiments, the dielectric layer includes a high-k dielectric material, such as a high-k silicate, eg, hafnium silicate; a high-k oxide, such as hafnium dioxide, tantalum oxide, or zirconium dioxide; or a mixture thereof, such as a solid solution or a mixed oxide.

[0099] In some embodiments, the method includes forming a first conductive layer before depositing the rare earth-containing layer.

[0100] In some embodiments, the first conductive layer includes a first transition metal compound.

[0101] In some embodiments, the first transition metal compound includes a first non-metal constituent element that is different from the first non-metal element and / or the second first non-metal element.

[0102] In some embodiments, the first transition metal compound includes a first transition metal element different from the rare earth element and / or the metal element.

[0103] In some embodiments, the first transition metal compound is implemented as a first transition metal carbide and / or a first transition metal nitride. Suitable transition metal carbides used as the first transition metal compound include TiC, VC, HfC, TaC, ZrC, ScC, NbC. Suitable transition metal nitrides used as the first transition metal compound include TiN, ZrN, HfN, VN, Mo, NbN, TaN, ScN, CrN, MoN and WN. In some embodiments, the first transition metal compound is implemented as titanium nitride or titanium carbide.

[0104] In some embodiments, the thickness of the first conductive layer is greater than or equal to 0.1 nm, or 0.5 nm, or 0.8 nm and / or less than or equal to 8 nm, or 6 nm, or 5 nm.

[0105] In some embodiments, the method includes forming a second conductive layer after depositing the rare earth-containing layer.

[0106] In some embodiments, the second conductive layer includes a second transition metal compound. In some embodiments, the second transition metal compound is different from the first transition metal compound of the first conductive layer.

[0107] In some embodiments, the second transition metal compound includes a second non-metal constituent element that is different from the first non-metal element and / or the second first non-metal element.

[0108] In some embodiments, the second transition metal compound includes a second transition metal element different from the rare earth element and / or the metal element.

[0109] In some embodiments, the second transition metal compound is implemented as a second transition metal carbide and / or a second transition metal nitride. Suitable transition metal carbides used as the second transition metal compound include TiC, VC, HfC, TaC, ZrC, ScC, NbC. Suitable transition metal nitrides used as the second transition metal compound include TiN, ZrN, HfN, VN, Mo, NbN, TaN, ScN, CrN, MoN and WN. In some embodiments, the second transition metal compound is implemented as titanium nitride or titanium carbide.

[0110] In some embodiments, the first conductive layer and / or the second conductive layer comprises a metal. Suitable metals include Cu, Co, Al, V, Cr, Y, Re, Ru, Mo, W, and Ti.

[0111] It should be understood that when the rare earth-containing layer is deposited on the first conductive layer, and / or when the second conductive layer is deposited on the rare earth-containing layer, internal mixing of the constituent components of these layers may occur, such as by diffusion, surface separation, or another process. In some embodiments, such internal mixing can result in the formation of an intermediate layer comprising both the conductive layer and the rare earth-containing layer. In some embodiments, such internal mixing can result in alloying or doping of the rare earth-containing layer.

[0112] In some embodiments, the thickness of the second conductive layer is greater than or equal to 0.5 nm, or 1 nm, or 2 nm and / or less than or equal to 40 nm, or 30 nm, or 20 nm.

[0113] In some embodiments, the process of depositing the rare earth-containing layer includes providing a first hydrogen-containing species after the process of providing a rare earth precursor and / or providing a second hydrogen-containing species after the process of providing a metal precursor.

[0114] In some embodiments, the first hydrogen-containing species and / or the second hydrogen-containing species include hydrogen gas.

[0115] In some embodiments, providing a first hydrogen-containing substance after providing a rare earth precursor and / or providing a second hydrogen-containing substance after providing a metal precursor can enable control of the rare earth metal and carbon content of the rare earth-containing layer. The subject matter currently disclosed is not subject to any particular theory or mode of operation, and it is believed that the provision of hydrogen can lead to weakening and / or breaking of chemical bonds between the ligands in the rare earth element and the rare earth precursor or between the ligands in the metal element and the metal precursor. Alternatively, it is believed that the provision of hydrogen can convert the ligands containing carbon and hydrogen into volatile byproducts, such as CH4, which are easily removed from the processing chamber. Therefore, providing hydrogen can advantageously remove residual carbon.

[0116] It should be understood that any continuous process, step and / or pulse may or may not be separated by purging. In some embodiments, the process of providing a rare earth precursor and providing a metal precursor can be separated by purging. In some embodiments, providing a rare earth precursor and providing a first non-metallic element reactant can be separated by purging. In some embodiments, providing a rare earth precursor and providing a second non-metallic element reactant can be separated by purging. In some embodiments, providing a rare earth precursor and providing a non-metallic multi-element reactant can be separated by purging. In some embodiments, providing a metal precursor and providing a first non-metallic element reactant can be separated by purging. In some embodiments, providing a metal precursor and providing a second non-metallic element reactant can be separated by purging. In some embodiments, providing a metal precursor and providing a non-metallic multi-element reactant can be separated by purging. In some embodiments, providing a first non-metallic element reactant and providing a second non-metallic element reactant can be separated by purging. In some embodiments, providing a first non-metallic element reactant and providing a non-metallic multi-element reactant can be separated by purging. In some embodiments, providing a second non-metallic element reactant and providing a non-metallic multi-element reactant can be separated by purging.

[0117] In some embodiments, the rare earth-containing layer is formed at a deposition temperature greater than or equal to 100° C., or 200° C., or 300° C., or 350° C. and / or less than or equal to 550° C., or 500° C., or 450° C., or 400° C. In some embodiments, where the rare earth-containing layer may or may not be formed at such a deposition temperature, the activation energy for driving the chemical reaction required to form the rare earth-containing layer may be provided at least in part by non-thermal means, such as using electromagnetic radiation.

[0118] In some embodiments, the rare earth-containing layer is deposited at a pressure of at least 0.01 Torr to at most 100 Torr, or at least 0.1 Torr to at most 50 Torr, or at least 0.5 Torr to at most 25 Torr, or at least 1 Torr to at most 10 Torr, or at least 2 Torr to at most 5 Torr.

[0119] In some embodiments, the thickness of the rare earth-containing layer is greater than or equal to 0.1 nm, or 0.5 nm, or 1 nm, or 2 nm and / or less than or equal to 10 nm, or 8 nm, or 5 nm.

[0120] The rare earth-containing layer can be formed in any suitable processing chamber. In some embodiments, the rare earth-containing layer is formed in a cross-flow processing chamber, a showerhead processing chamber, or a hot wall processing chamber. In some embodiments, the rare earth-containing layer can be formed in a single substrate processing chamber, while in other embodiments, the rare earth-containing layer can be formed in a multi-substrate (e.g., batch) processing chamber.

[0121] In some embodiments, the process of providing a rare earth precursor includes maintaining the rare earth precursor in a rare earth precursor container and delivering the rare earth precursor to a processing chamber using a rare earth precursor carrier gas, and / or the process of providing a metal precursor includes maintaining the metal precursor in a metal precursor container and delivering the metal precursor to a processing chamber using a metal precursor carrier gas.

[0122] In some embodiments, the rare earth precursor carrier gas and / or the metal precursor carrier gas are independently selected from nitrogen, helium, neon, argon, krypton, xenon, radon and mixtures thereof. In some embodiments, for example, when the rare earth precursor and / or the metal precursor have a sufficiently high vapor pressure at a suitable temperature, the use of one or more such carrier gases may be omitted.

[0123] In some embodiments, the rare earth precursor container is configured to cool the rare earth precursor. In some embodiments, the rare earth precursor container is configured to heat the rare earth precursor. In some embodiments, the metal precursor container is configured to cool the metal precursor. In some embodiments, the metal precursor container is configured to heat the metal precursor.

[0124] In some embodiments, the rare earth precursor and / or the metal precursor is maintained at a container temperature greater than or equal to 20° C., or 50° C., or 70° C., or 350° C. and / or less than or equal to 200° C., or 150° C., or 130° C. In some embodiments, the container temperature is selected to affect evaporation and / or sublimation of the rare earth precursor and / or the metal precursor.

[0125] In some embodiments, the process of depositing the rare earth-containing layer is implemented as a chemical vapor deposition process, such as a cyclic chemical vapor deposition process, such as an atomic layer deposition process, such as a time atomic layer deposition process. In some embodiments, the chemical vapor deposition process includes one or more cycles. Typically, each cycle of the one or more cycles includes two or more pulses. In some embodiments, at least one of the two or more pulses involves a self-limiting surface reaction. In some embodiments, each of the two or more pulses involves a self-limiting surface reaction.

[0126] In some embodiments, the rare earth precursor pulse and / or the metal precursor pulse lasts at least 0.01 second to at most 120 seconds, or at least 0.01 second to at most 0.1 second, or at least 0.01 second to at most 0.02 seconds, or at least 0.02 seconds to at most 0.05 seconds, or at least 0.05 seconds to at most 0.1 second, or at least 0.1 second to at most 20 seconds, or at least 0.1 second to at most 0.2 seconds, or at least 0.2 seconds to at most 0.5 seconds, or at least 0.5 seconds to at most 1.0 second, or at least 1.0 second to at most 2.0 seconds, or at least 2.0 seconds to at most 5.0 seconds, or at least 5.0 seconds to at most 10.0 seconds, or at least 10.0 seconds to at most 20.0 seconds.

[0127] In some embodiments, a non-metal element reactant pulse, such as a first non-metal element reactant pulse, a second non-metal element reactant pulse, and / or a non-metal multi-element reactant pulse, lasts from at least 0.1 second to at most 20 seconds, or from at least 0.1 second to at most 0.2 seconds, or from at least 0.2 seconds to at most 0.5 seconds, or from at least 0.5 seconds to at most 1.0 seconds, or from at least 1.0 seconds to at most 2.0 seconds, or from at least 2.0 seconds to at most 5.0 seconds, or from at least 5.0 seconds to at most 10.0 seconds, or from at least 10.0 seconds to at most 20.0 seconds, or from at least 20.0 seconds to at most 120.0 seconds, or from at least 20.0 seconds to at most 50.0 seconds, or from at least 50.0 seconds to at most 80.0 seconds, or from at least 80.0 seconds to at most 120.0 seconds.

[0128] In some embodiments, the process of depositing the rare earth-containing layer is implemented as a thermal deposition process or an active species enhanced deposition process, such as a free radical enhanced deposition process.

[0129] In the case where the process of depositing the rare earth-containing layer is implemented as a thermal deposition process, the duration of the process of providing a rare earth precursor, providing a metal precursor, providing one or more non-metallic element reactants, providing a first hydrogen-containing substance, and / or providing a second hydrogen-containing substance may be relatively long. For example, one or more of the durations may be greater than or equal to 5 seconds or to 10 seconds or from about 5 seconds to about 10 seconds.

[0130] In some embodiments, after the process of depositing the rare earth-containing layer, the substrate is subjected to an annealing step in an environment including hydrogen and nitrogen, ammonia (NH3) and / or argon. Suitably, the annealing step may be performed at a temperature of at least 300°C to at most 600°C. Alternatively, the annealing step may be performed at a temperature of at least 300°C to at most 1300°C, 1200°C or 1100°C.

[0131] In some embodiments, the presently described methods may be used to form a metal gate electrode of a CMOS (eg, n-MOS or p-MOS) transistor.

[0132] Further described herein is an apparatus comprising a process chamber, a precursor supply unit for supplying a rare earth precursor and a metal precursor in the process chamber, a reactant supply unit for supplying one or more non-metallic element reactants into the process chamber, and a control unit configured to at least control the precursor supply unit and the reactant supply unit to perform any method according to the present description.

[0133] Turning now to the accompanying drawings, Figure 1A A method 100 for forming a rare earth-containing layer according to one embodiment is shown. Unless otherwise expressly stated, Figure 1A The method 100 of an embodiment may or may not include any of the features disclosed in this specification.

[0134] Figure 1A The method 100 of an embodiment of the present invention includes providing a substrate in a processing chamber, optionally forming a first conductive layer 102, depositing a rare earth-containing layer 103 on the substrate after forming the first conductive layer 102, and optionally forming a second conductive layer 116 after depositing the rare earth-containing layer 103. The rare earth-containing layer formed by the method 100 includes a rare earth element, such as cerium; a metal element other than the rare earth element, such as erbium; a first non-metal element, such as carbon; and a second non-metal element different from the first non-metal element, such as sulfur.

[0135] Figure 1A The process of depositing the rare earth-containing layer 103 of the embodiment includes providing a rare earth precursor, such as tri(isopropylcyclopentadienyl)cerium (Ce(iPrCp)3), into a processing chamber 104; optionally, after the process of providing the rare earth precursor 104, providing a first hydrogen-containing substance 107, such as hydrogen (H2); providing a metal precursor, such as tri(isopropylcyclopentadienyl)erbium (Er(iPrCp)3), into the processing chamber 108; optionally, after the process of providing the metal precursor 108, providing a second hydrogen-containing substance 111, such as hydrogen (H2), and providing one or more non-metallic element reactants into the processing chamber 112.

[0136] exist Figure 1A In an embodiment of the present invention, the process of providing a rare earth precursor 104 may include maintaining the rare earth precursor in a rare earth precursor container 105 and transporting the rare earth precursor to a processing chamber 106 using a rare earth precursor carrier gas, and the process of providing a metal precursor 108 may include maintaining the metal precursor in a metal precursor container 109 and transporting the metal precursor to a processing chamber 110 using a metal precursor carrier gas.

[0137] In addition, provide Figure 1A The process of providing one or more non-metallic element reactants 112 of an embodiment may include providing a first non-metallic element reactant 113, such as diiodoethane, and providing a second non-metallic element reactant 114 different from the first non-metallic element reactant, such as hydrogen sulfide (H2S). Additionally or alternatively, the process of providing one or more non-metallic element reactants 112 may include providing a non-metallic multi-element reactant 115, such as dimethyl sulfide (DMS, (CH3)2S), which includes a first non-metallic element and a second first non-metallic element.

[0138] like Figure 1A As shown by the dashed arrows in FIG. 1 , the process of depositing the rare earth-containing layer 103 can be implemented as a cyclic chemical vapor deposition process. Additionally or alternatively, the method 100 can include a purge step between any or all of the above processes. Figure 1AThe process of depositing the rare earth containing layer 103 of the embodiment may be implemented as a time atomic layer deposition process.

[0139] Figure 1B 1 shows at least a portion of a method 100 for forming a rare earth-containing layer according to another embodiment. Figure 1B The method 100 of the embodiment may include or not include the above disclosed Figure 1A Any features of method 100 of an embodiment and / or any features disclosed in this specification.

[0140] Figure 1B The method 100 of the embodiment includes providing a substrate in a processing chamber and depositing a rare earth-containing layer 103 on the substrate. The rare earth-containing layer formed by the method 100 includes a rare earth element, a metal element different from the rare earth element, a first non-metal element, and a second non-metal element different from the first non-metal element.

[0141] Deposition Figure 1B The process of forming the rare earth containing layer 103 of the embodiment includes providing a rare earth precursor into a process chamber 104 , providing a metal precursor into a process chamber 108 , and providing one or more non-metal element reactants into a process chamber 112 .

[0142] exist Figure 1B In an embodiment of the present invention, the process of providing one or more non-metal element reactants 112 may include providing a first non-metal element reactant 113 after the process of providing the rare earth precursor 104, and providing a second non-metal element reactant 114 different from the first non-metal element reactant after the process of providing the metal precursor 108. Additionally or alternatively, the process of providing one or more non-metal element reactants 112 may include providing a non-metal multi-element reactant 115 containing a first non-metal element and a second first non-metal element after the process of providing the rare earth precursor 104 and / or after the process of providing the metal precursor 108.

[0143] Figure 2 An apparatus 200 according to an embodiment is depicted. Figure 2The device 200 of the embodiment of the present invention can be implemented as, for example, an atomic layer deposition device, such as a time atomic layer deposition device, which includes a process chamber 201, a precursor supply unit 202 for supplying a rare earth precursor 204 and a metal precursor 206 into the process chamber 201, a reactant supply unit 207 for supplying one or more non-metallic element reactants 208 into the process chamber 201, and a control unit 213, which is configured to at least control the precursor supply unit 202 and the reactant supply unit 207 to perform the method according to the present disclosure. The device 200 may further include an exhaust unit 214, which is suitable for or configured to remove fluid and / or fluid-like substances, such as precursors, reactants, reaction byproducts, from the process chamber 201, and / or maintain the pressure in the process chamber 201 within a predetermined pressure range, such as reduced pressure or below atmospheric pressure.

[0144] exist Figure 2 In an embodiment of the present invention, the precursor supply unit 202 may include a rare earth precursor container 203 for storing a rare earth precursor 204, a metal precursor container 205 for storing a metal precursor 206, a first non-metal element reactant container 209 for storing a first non-metal element reactant 210, and / or a second non-metal element reactant container 211 for storing a second non-metal element reactant 212.

[0145] Figure 2 The process chamber 201 of the embodiment of the present invention may be implemented as any suitable type of process chamber, such as a cross-flow process chamber, a showerhead process chamber, or a hot wall process chamber.

[0146] Figure 3 A partial cross-sectional view of a structure 300 is shown in accordance with an embodiment. Figure 3 The structure 300 of the embodiment may be formed using the method according to the first aspect.

[0147] Figure 3 The structure 300 of the embodiment includes a substrate 301 and a rare earth-containing layer 305 on the substrate 301. The rare earth-containing layer 305 includes a rare earth element, such as cerium; a metal element different from the rare earth element, such as erbium; a first non-metal element, such as carbon; and a second non-metal element different from the first non-metal element, such as sulfur.

[0148] exist Figure 3 In some embodiments, structure 300 may form at least a portion of a semiconductor device, such as a semiconductor transistor, such as a metal oxide semiconductor field effect transistor.

[0149] Figure 3 The substrate 301 of the embodiment of has an outer surface 302 and includes a dielectric layer 303 extending along the outer surface 302. The dielectric layer 303 may include, for example, hafnium dioxide.

[0150] exist Figure 3 In an embodiment of the present invention, structure 300 further includes a first conductive layer 304 between substrate 301 and rare earth-containing layer 305 and a second conductive layer 306 on rare earth-containing layer 305. Each of first conductive layer 304 and second conductive layer 306 may include titanium nitride. One or more of first conductive layer 304 and second conductive layer 306 may further include titanium carbide.

[0151] The exemplary embodiments disclosed above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention, and the scope of the present invention is defined by the appended claims and their legal equivalents. Any equivalent embodiments are within the scope of the present invention. In fact, various modifications of the present disclosure, such as alternative useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for forming a rare earth-containing layer, the method comprising: - providing a substrate within a processing chamber; and -Depositing a rare earth-containing layer on a substrate, the process of depositing the rare earth-containing layer comprising: i) providing a rare earth precursor into a process chamber, ii) providing a metal precursor into the process chamber, and iii) providing one or more non-metallic element reactants into the process chamber; The rare earth-containing layer includes a rare earth element, a metal element different from the rare earth element, a first non-metal element and a second non-metal element different from the first non-metal element.

2. The method according to claim 1, wherein: The rare earth element is selected from the group consisting of cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium and yttrium.

3. The method according to claim 1 or 2, wherein: The rare earth precursor includes at least one of cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, scandium, terbium, thulium, ytterbium and yttrium.

4. A method according to any one of the preceding claims, wherein: The rare earth precursor comprises a rare earth element in an oxidation state of +3 or an oxidation state of +4.

5. A method according to any one of the preceding claims, wherein: The rare earth precursor includes a cyclopentadienyl ligand, such as an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, for example an isopropylcyclopentadienyl ligand.

6. A method according to any one of the preceding claims, wherein: The metal element is selected from Group 3 metals, such as scandium and yttrium; Group 4 metals, such as titanium and zirconium; Group 5 metals, such as vanadium and niobium; Group 6 metals, such as chromium and molybdenum; Group 7 metals, such as manganese; Group 8 metals, such as iron and ruthenium; Group 9 metals, such as cobalt and rhodium; Group 10 metals, such as nickel and palladium; Group 11 metals, such as copper and silver; Group 12 metals, such as zinc and cadmium; Group 13 metals, such as aluminum, gallium and indium; and lanthanide elements; such as cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium and ytterbium.

7. A method according to any one of the preceding claims, wherein: The metal precursor includes at least one of the following: a Group 3 metal, such as scandium or yttrium; a Group 4 metal, such as titanium or zirconium; a Group 5 metal, such as vanadium or niobium; a Group 6 metal, such as chromium or molybdenum; a Group 7 metal, such as manganese; a Group 8 metal, such as iron or ruthenium; a Group 9 metal, such as cobalt or rhodium; a Group 10 metal, such as nickel or palladium; a Group 11 metal, such as copper or silver; a Group 12 metal, such as zinc or cadmium; a Group 13 metal, such as aluminum, gallium or indium; and a lanthanide element; such as cerium, dysprosium, erbium, europium, gadolinium, holmium, lanthanum, lutetium, neodymium, praseodymium, promethium, samarium, terbium, thulium or ytterbium.

8. A method according to any one of the preceding claims, wherein: The metal precursor comprises a metal element in an oxidation state of +3 or an oxidation state of +4.

9. A method according to any one of the preceding claims, wherein: The metal precursor includes a cyclopentadienyl ligand, such as an unsubstituted cyclopentadienyl ligand or a substituted cyclopentadienyl ligand, such as an alkylsilyl-substituted cyclopentadienyl ligand, for example an isopropylcyclopentadienyl ligand.

10. A method according to any one of the preceding claims, wherein: The first non-metallic element and / or the second non-metallic element are selected from boron, Group 14 non-metallics, such as carbon or silicon; Group 15 non-metallics, such as nitrogen, phosphorus or arsenide; Group 16 non-metallics, such as oxygen, sulfur, selenium or tellurium; and Group 17 non-metallics, such as fluorine, chlorine, bromine or iodine.

11. A method according to any one of the preceding claims, wherein: The process of providing one or more non-metal element reactants includes providing a first non-metal element reactant and providing a second non-metal element reactant different from the first non-metal element reactant.

12. The method according to claim 11, wherein: The first non-metallic element reactant includes boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as at least one of fluorine, chlorine, bromine or iodine; the second non-metallic element reactant includes boron, a Group 14 non-metal, such as carbon or silicon; a Group 15 non-metal, such as nitrogen, phosphorus or arsenide; a Group 16 non-metal, such as oxygen, sulfur, selenium or tellurium; and a Group 17 non-metal, such as at least another one of fluorine, chlorine, bromine or iodine.

13. A method according to any one of the preceding claims, wherein: The process of providing one or more non-metallic element reactants includes providing a non-metallic multi-element reactant comprising a first non-metallic element and a second first non-metallic element.

14. A method according to any one of the preceding claims, wherein: The substrate has an outer surface and includes a dielectric layer extending along the outer surface.

15. The method according to claim 14, wherein: The dielectric layer includes a high-k dielectric material, such as a high-k silicate, such as hafnium silicate; a high-k oxide, such as hafnium dioxide, tantalum oxide or zirconium dioxide; or a mixture thereof, such as a solid solution or a mixed oxide.

16. A method according to any one of the preceding claims, wherein: The method includes forming a first conductive layer before depositing the rare earth-containing layer.

17. The method according to claim 16, wherein: The first conductive layer includes a first transition metal compound.

18. The method according to claim 17, wherein: The first transition metal compound includes a first non-metal constituent element different from the first non-metal element and / or the second first non-metal element.

19. The method according to claim 17 or 18, wherein: The first transition metal compound includes a first transition metal element different from the rare earth element and / or the metal element.

20. The method according to any one of claims 17 to 19, wherein: The first transition metal compound is embodied as a first transition metal carbide and / or a first transition metal nitride.

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