Method, system and apparatus for N-metal film deposition

Abstract

Methods, systems, and apparatus are disclosed for depositing a composite film, including providing a substrate in a reaction chamber, depositing a first material layer comprising a first metal nitride according to a first cyclic deposition process, depositing a second material layer comprising aluminum carbide according to a second cyclic deposition process, and depositing a second metal nitride according to a third cyclic deposition process. And depositing a third material layer comprising the second metal nitride according to a third cyclic deposition process.

Description

Technical Field

[0001] The present disclosure generally relates to methods, systems, and apparatus suitable for forming one or more layers on a surface of a substrate, and to structures including the one or more layers. More specifically, the present disclosure relates to methods and systems for forming layers including a work function layer of a metal oxide semiconductor capacitor (MOSCAP), and to structures formed using the methods, systems, and apparatus. Background Art

[0002] Semiconductor fabrication processes used to form semiconductor device structures, such as transistors, memory elements, and integrated circuits, are extensive and may include deposition processes, etching processes, thermal annealing processes, photolithography processes, and doping processes, among other processes.

[0003] Metal oxide semiconductor capacitor (MOSCAP) devices have become a cornerstone of modern electronics, playing a vital role in the operation of a wide range of electronic devices. Traditionally, titanium carbide (TiC) has been used as the n-type work function (nWF) metal in these devices. This material choice has served well for planar devices and even for more advanced structures such as FinFETs.

[0004] However, as the industry continues to push the boundaries of miniaturization, transitioning from planar structures to FinFETs and now to gate-all-around (GAA) structures, the size of these structures has decreased significantly. This miniaturization trend has necessitated a corresponding reduction in the thickness of the n-metal film, which now needs to be less than 50 angstroms. While still maintaining a low effective work function (eWF).

[0005] This requirement poses a significant challenge to current TiC processes. The process of depositing ultrathin TiC layers while maintaining a low eWF is complex and difficult to control. In addition, the growth rate of TiC is relatively high, which makes achieving the desired thinness challenging.

[0006] Therefore, there is an urgent need for a new n-metal material with not only a lower eWF but also a lower growth rate. Such a material would enable continued miniaturization of MOSCAP devices while continuing to optimize performance. Summary of the Invention

[0007] This summary is provided to introduce a selection of concepts in a simplified form. These concepts are further described in detail in the detailed description of the examples of the present disclosure below. This summary is not 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.

[0008] Disclosed are methods, systems, and apparatus for depositing a composite film, including providing a substrate in a reaction chamber, depositing a first material layer comprising a first metal nitride according to a first cyclic deposition process, depositing a second material layer comprising aluminum carbide according to a second cyclic deposition process, and depositing a third material layer comprising the second metal nitride according to a third cyclic deposition process. In some examples, the first metal nitride comprises titanium nitride (TiN) or vanadium nitride (VN), or a combination thereof.

[0009] In a specific example, the second metal nitride includes titanium nitride (TiN), vanadium nitride (VN), or molybdenum nitride (MoN), or a combination thereof.

[0010] In some examples, the first metal nitride and the second metal nitride are different. In some examples, the first metal nitride and the second metal nitride are the same.

[0011] In some examples, the aluminum carbide comprises 5-65 atomic percent aluminum. In various examples, the aluminum carbide comprises niobium aluminum carbide. In some examples, the aluminum carbide comprises 5 to 50 atomic percent aluminum and 10 to 50 atomic percent niobium. In some examples, the substrate surface comprises a high-k material.

[0012] In various examples, the high-k material is hafnium oxide (HfO x ).

[0013] In some examples, a first cyclic deposition process includes contacting the substrate with a first vapor precursor, contacting the substrate with a second vapor precursor, purging the reaction chamber, and repeating one or more of operations a), b), or c), or any combination thereof, in any order, until a first material layer of a first predetermined thickness is deposited on the surface of the substrate. In some examples, the first vapor precursor includes at least one of titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), or a combination thereof. In some examples, the second vapor precursor includes at least one of ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, an alkyl hydrazine, tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N2 plasma, N2 / H2 plasma, NH3 plasma, excited nitrogen species, nitrogen ions, nitrogen radicals, or any combination thereof. In an example, the first material layer includes TiN or VN. In some examples, the first predetermined thickness is in a range of approximately 1 angstrom to 15 angstroms.

[0014] In some examples, the second cyclic deposition process includes contacting the substrate with a third vapor precursor, contacting the substrate with a co-reactant or a fourth vapor precursor or a combination thereof, purging the reaction chamber and repeating one or more operations d), e) or f) or any combination thereof, in any order, until a second material layer of a second predetermined thickness is deposited on the surface.

[0015] In some examples, the third vapor-phase precursor includes at least one of triethylaluminum (TEA), triisobutylaluminum (TIBA), dimethylaluminum hydride (DMAH), trimethylaluminum (TMA), tri-tert-butylaluminum (TTBA), bis(tert-butylamino)aluminum hydride (BTBAH), methylaluminum trichloride (MTCA), diethylaluminum chloride (DEAC), or combinations thereof. In various examples, the co-reactant includes hydrogen (H2), hydrogen plasma, or other excited species of hydrogen.

[0016] In some examples, the second material layer includes aluminum carbide. In specific examples, the second predetermined thickness is in the range of 5 to 30 angstroms. In some examples, the percentage of Al is in the range of 5% to 65%. In some examples, the fourth vapor phase precursor includes a niobium vapor phase reactant, which includes niobium pentachloride (NbCl5), niobium pentafluoride (NbF5), niobium pentaiodide (NbI5), niobium pentabromide (NbBr5), or a combination thereof. In certain examples, the second cyclic deposition process includes contacting the substrate with a third vapor phase precursor and a co-reactant to deposit a second material layer including aluminum carbide, and then contacting the second material layer with a fourth vapor phase precursor. In some examples, the second material layer includes niobium aluminum carbide. In certain examples, the second predetermined thickness is 5-50 angstroms. In various examples, the ratio of the fourth vapor phase precursor to the third vapor phase precursor is in the range of 1:2 to 1:10.

[0017] In some examples, the reaction chamber is pre-cleaned prior to contacting the substrate with the first vapor-phase precursor, wherein the pre-cleaning includes exposing the reaction chamber to ammonia. In an example, the percentage of Al is in a range of 10% to 60%.

[0018] In some examples, the third cyclic deposition process includes contacting the substrate with a fifth vapor-phase precursor, contacting the substrate with a sixth vapor-phase precursor, or contacting the substrate with a seventh vapor-phase precursor, or a combination thereof, purging the reaction chamber and repeating one or more operations g), h), or i), or any combination thereof, in any order, until a third material layer of a third predetermined thickness is deposited on the surface of the substrate.

[0019] In some examples, the fifth vapor-phase precursor includes at least one of titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), molybdenum (V) oxychloride trichloride (MoOCl3), molybdenum (VI) oxychloride tetrachloride (MoOCl4), or molybdenum (IV) dichloride (MoO2Cl2), or a combination thereof. In some examples, the sixth vapor-phase precursor includes at least one of ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, an alkyl hydrazine, tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N2 plasma, N2 / H2 plasma, NH3 plasma, excited nitrogen species, nitrogen ions, nitrogen radicals, or any combination thereof. In certain examples, the seventh vapor-phase precursor is a silicon-containing precursor. In some examples, the silicon-containing precursor is silane (SiH4), disilane (Si2H6), monomethylsilane (CH3SiH3), or trisilane (H2Si(SiH3)2), or a combination thereof. In certain examples, the third material layer includes TiN, VN, MoN, TiSiN, VSiN, or MoSiN. In some examples, the third predetermined thickness is in a range of 5 to 20 angstroms.

[0020] In another example, the third cyclic deposition process includes contacting the substrate with a fifth vapor precursor and a sixth vapor precursor to deposit a third material layer including a metal nitride, and then contacting the third material layer with a seventh vapor precursor.

[0021] For the purpose of summarizing the present invention and the advantages achieved over the prior art, certain objects and advantages of the present invention have been described above. Of course, it will be understood that not all of these objects or advantages may be achieved according to any particular embodiment of the present invention. Thus, for example, those skilled in the art will recognize that the present invention may be implemented or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages as may be taught or suggested herein.

[0022] All of these examples are intended to fall within the scope of the invention disclosed herein. These and other examples will become readily apparent to those skilled in the art from the following detailed description of certain examples with reference to the accompanying drawings, the invention not being limited to any particular example disclosed. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] While this specification concludes with claims that particularly point out and distinctly claim what are considered to be examples of the present invention, advantages of examples of the present disclosure may be more readily ascertained from the description of certain examples thereof when read in conjunction with the accompanying drawings, in which:

[0024] Figure 1 A schematic diagram of a reactor system according to an example of the present technology is shown.

[0025] Figure 2 A schematic diagram of a reactor system having multiple reaction chambers according to an example of the present technology is shown.

[0026] Figures 3A to 3B An exemplary structure according to an embodiment of the present disclosure is shown.

[0027] Figure 4 An exemplary structure according to an embodiment of the present disclosure is shown.

[0028] Figure 5 An exemplary structure according to an embodiment of the present disclosure is shown.

[0029] Figure 6A An example process for depositing a composite film according to examples of the present disclosure is shown.

[0030] Figure 6B An example cyclic deposition process according to examples of the present disclosure is shown.

[0031] Figure 6C An example cyclic deposition process according to examples of the present disclosure is shown.

[0032] Figure 6D An example cyclic deposition process according to examples of the present disclosure is shown.

[0033] 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 sizes of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0034] The detailed description of various examples herein refers to the accompanying drawings, which illustrate exemplary examples by way of illustration. Although these exemplary examples are described in sufficient detail to enable those skilled in the art to practice the present disclosure, it should be understood that other examples can be implemented and that logical, chemical and / or mechanical changes can be made without departing from the spirit and scope of the present disclosure. Therefore, the detailed description herein is provided for illustrative purposes only and not for limiting purposes. For example, the steps described in any method or process description can be performed in any combination and / or order and are not limited to the combinations and / or orders presented. In addition, one or more steps from one of the disclosed methods or processes can be combined with one or more steps from another of the disclosed methods or processes in any suitable combination and / or order. In addition, any function or step can be outsourced to one or more third parties or performed by one or more third parties. In addition, any reference to the singular includes plural examples, and any reference to more than one component can include a singular example.

[0035] Although certain examples are disclosed below, those skilled in the art will appreciate that the disclosure extends beyond the specific disclosed examples and / or uses of the disclosure and its obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosure should not be limited by the specific examples described herein.

[0036] The illustrations presented herein are not meant to be actual views of any particular material, apparatus, structure, or device, but are merely representations of examples used to describe the present disclosure.

[0037] As used herein, the term "substrate" may refer to any underlying material or materials on which a device, circuit, or film / layer may be used or formed. A substrate may comprise a bulk material, such as silicon (e.g., single crystal silicon), other Group IV materials (e.g., germanium), or other semiconductor materials (e.g., Group II-VI or Group III-V semiconductor materials), and may comprise one or more layers overlying or underlying the bulk material. Additionally, a substrate may include various features, such as recesses, protrusions, etc., formed within or on at least a portion of a layer of the substrate. For example, a substrate may include a bulk semiconductor material and a layer of insulating or dielectric material covering at least a portion of the bulk semiconductor material.

[0038] As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle, preferably a plurality of consecutive deposition cycles, is performed in a processing chamber. Typically, during each cycle, a precursor is chemically adsorbed to a deposition surface (e.g., a substrate surface or a previously deposited underlying surface, such as material from a previous ALD cycle) to form a monolayer or sub-monolayer that is not easily reacted with another precursor (i.e., a self-limiting reaction). Thereafter, if desired, a reactant (e.g., another precursor or a reactive gas) may be subsequently introduced into the processing chamber for converting the chemically adsorbed precursor into the desired material on the deposition surface. Typically, the reactant is capable of further reacting with the precursor. In addition, a purge step may also be utilized during each cycle to remove excess precursor from the processing chamber and / or remove excess reactant and / or reaction byproducts from the processing chamber after the chemically adsorbed precursor is converted. In addition, as used herein, the term "atomic layer deposition" is also intended to include processes 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, and chemical beam epitaxy when performed with alternating pulses of a precursor composition, a reactive gas, and a purge gas (e.g., an inert carrier gas).

[0039] As used herein, the term "chemical vapor deposition" (CVD) may refer to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposit.

[0040] As used herein, the term "cyclic deposition" may refer to the sequential introduction of one or more precursors and / or reactants into a reaction chamber to deposit a film on a substrate, and includes deposition techniques such as atomic layer deposition and cyclic chemical vapor deposition.

[0041] As used herein, the terms "layer," "film," and / or "thin film" may refer to any continuous or non-continuous structure and material deposited by the methods disclosed herein. For example, a "layer," "film," and / or "thin film" may include a 2D material, nanorods, nanotubes, or nanoparticles, or even a partial or complete molecular layer, or a partial or complete atomic layer, or clusters of atoms and / or molecules. A "layer," "film," and / or "thin film" may include a material or layer that has pinholes, but is still at least partially continuous.

[0042] Throughout the examples of this disclosure, numerous example materials are given, and it should be noted that the chemical formula given for each example material should not be construed as limiting, and that the non-limiting example materials given should not be limited by the example stoichiometries given.

[0043] In addition, in the present disclosure, any two numbers of a variable can constitute the working range of the variable, and any range indicated can include or exclude endpoints. In addition, any value of the variable indicated (whether or not they are indicated with "about") can refer to an exact value or an approximate value, and include equivalent values, and can refer to an average value, a median value, a representative value, a majority value, etc. In addition, in the present disclosure, the terms "including", "consisting of" and "having" can independently refer to "generally or widely including", "comprising", "essentially consisting of" or "consisting of" in some examples. In the present disclosure, the meaning of any definition does not necessarily exclude the ordinary and customary meanings in some examples.

[0044] The present disclosure includes methods for depositing low effective work function (eWF) n metal layers. Such films can be used in many applications, such as semiconductor device applications, such as MOSCAP (metal oxide semiconductor capacitor), GAA (gate-all-around) devices and / or CFET (complementary field effect transistor). In MOSCAP devices, the work function of the metal gate is crucial in determining the threshold voltage of the device. Low eWF can help achieve a desired threshold voltage that affects device characteristics. Using low work function metal gate materials can provide greater gate controllability. Work function tuning is an important aspect of transistor device control.

[0045] Figure 1 is an abstract schematic diagram representing an example reactor system 150. Reactor system 150 may include one or more reaction chambers 104, 105, and 107, each housing a susceptor 106 to hold a substrate 130 during processing; and a fluid distribution system 108 (e.g., a showerhead) to distribute one or more reactants to the surface of substrate 130. Reactor system 150 may include a direct plasma source 175 incorporated into any of chambers 104, 105, or 107 and / or a remote plasma source 170 coupled to any of chambers 104, 105, or 107. Multiple deposition and / or etching processes may be performed in a single reaction chamber 104 and / or various processes may be performed in separate reaction chambers 104, 105, and / or 107.

[0046] For simplicity, the reactant sources and carrier / purge gas sources are shown as coupled to a single reaction chamber 104 , however, it should be understood that the reactant sources and carrier / purge gases for separate processes may be coupled to respective reaction chambers for those specific processes.

[0047] In an example, reactant (or co-reactant) source containers 110, 112, 113, 114, 140, 142, 144, 164 and / or carrier gas or purge gas source container 154 can be fluidly connected to reaction chamber 104 via corresponding pipelines 116, 118, 119, 120, 141, 143, 145, 168 and 160 and corresponding valves or controllers 122, 123, 125, 126, 146, 147, 148, 166 and 158.

[0048] In an example, the reactant gases can be contained in the above-described containers and can be applied to the substrate 130 in the reaction chamber during processing. For example, the first vapor-phase precursor 115 can be contained in the container 110, the second vapor-phase precursor 117 can be contained in the container 112, the third vapor-phase precursor 121 can be contained in the container 113, the fourth vapor-phase precursor 124 can be contained in the container 114, the co-reactant 132 can be contained in the container 140, and the fifth vapor-phase precursor 134 can be contained in the container 142 (in some examples, the first vapor-phase precursor 115 and the fifth vapor-phase precursor 134 can be the same precursor and can be contained in the same container (for example, the first vapor-phase precursor 115 and the fifth vapor-phase precursor 134 can both be the same precursor). The sixth vapor-phase precursor 133 may be contained in container 144 (in some examples, the second vapor-phase precursor 117 and the sixth vapor-phase precursor 133 may be the same precursor and may be contained in the same container (e.g., the second vapor-phase precursor 117 and the sixth vapor-phase precursor 133 may both be contained in container 112 or container 144). The seventh vapor-phase precursor 162 may be contained in container 164, a purge gas and / or a carrier gas may be contained in container 156, and / or other materials from corresponding source containers may be applied to the substrate 130 in the reaction chamber 104.

[0049] In an example, a carrier gas or purge gas 156 from a gas source container 154 can be an inert gas and can flow to and through a reaction chamber (e.g., reaction chamber 104) to remove any excess reactants or other undesirable materials from reaction chamber 104. System 150 can also include a vacuum source (e.g., vacuum source 128) fluidly coupled to the reaction chamber that can be configured to evacuate reactants, purge gas, or other materials from the reaction chamber. Carrier gas or purge gas 156 can include argon, helium, neon, krypton, nitrogen, and / or xenon, among others, or combinations thereof.

[0050] In an example, the controller 152 can be configured to perform various functions and / or steps as described herein. The controller 152 can include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although shown as a single unit, the controller 152 can alternatively include multiple devices. For example, the controller 152 can be used to control gas flow (e.g., by monitoring flow and controlling valves 122, 123, 125, 126, 146, 147, 148, 158, and / or 166), motors, showerheads 108, remote plasma sources 170, heaters, cooling devices, and / or vacuum sources 158 to perform various processes (e.g., at corresponding Figure 6A 、 6B , 6C, and / or 6D). In addition, when the system includes two or more reaction chambers, as described in more detail below, the two or more reaction chambers can be coupled to the same / shared controller.

[0051] As used herein, "composite membrane" refers to a membrane composed of layers of different materials that remain substantially distinct. These layers may serve specific purposes and contribute to the overall properties of the membrane. Diffusion can occur between adjacent layers, allowing chemicals or substances to migrate across the interface and be incorporated into adjacent membranes. This diffusion can be intentional or unintentional.

[0052] In some examples, system 150 may perform a thin film deposition or composite film deposition process to deposit one or more material layers on the surface of substrate 130. In some examples, the composite film may be formed from a first material layer comprising a first metal nitride deposited on the high-k surface of substrate 130. The composite film may also include a second material layer comprising aluminum carbide. In some examples, the second material layer comprises niobium aluminum carbide. In some examples, the composite film may also include a third material layer comprising a second metal nitride deposited on the second material layer. In some examples, the first metal nitride may be titanium nitride, titanium silicon nitride, silicon-doped titanium nitride, vanadium nitride, vanadium nitride silicon, and / or silicon-doped vanadium nitride. In certain non-limiting examples, the second metal nitride may include titanium nitride, titanium silicon nitride, silicon-doped titanium nitride, vanadium nitride, vanadium nitride silicon, silicon-doped vanadium nitride, molybdenum nitride, molybdenum silicon nitride, and / or silicon-doped molybdenum nitride. In some examples, the first metal nitride and the second metal nitride may be the same. In other examples, the first metal nitride and the second metal nitride may be different.

[0053] In an example, the process for depositing a composite film may include multiple sub-cycles. In a first sub-cycle, a first cycle deposition process, a first vapor precursor 115 and a second vapor precursor 117 may contact a substrate 130 to deposit a first metal nitride layer on the substrate 130. In a second cycle deposition process, a third vapor precursor 121, a fourth vapor precursor 124, and / or a co-reactant 140 may contact the substrate 130 to deposit an aluminum carbide layer and / or a niobium aluminum carbide layer on the substrate 130. In a third cycle deposition process, a fifth vapor precursor 134, a sixth vapor precursor 133, and an optional seventh vapor precursor 164 may contact the substrate 130 to deposit a second metal nitride layer and / or a second metal nitride layer containing silicon on the substrate 130. In an example, a first metal nitride may be deposited according to the third cycle deposition process.

[0054] In a first cyclic deposition process, depositing a first metal nitride layer on substrate 130 may include pulsing a first vapor precursor 115 from reactant source vessel 110 to reaction chamber 104 via showerhead 108. A second vapor precursor 117 may be pulsed from reactant source vessel 112 to reaction chamber 104 via showerhead 108, either together with or separately from the first vapor precursor 115. When the first vapor precursor 115 and the second vapor precursor 117 contact substrate 130, a first metal nitride may be formed on substrate 130. Reaction chamber 104 may be purged with a purge gas 156 between one or more pulses of the first vapor precursor 115, the second vapor precursor 117, and / or between one or more deposition cycles. The first cyclic deposition process (or portions thereof) may be repeated until a desired thickness of the first material layer is achieved.

[0055] In the second sub-cycle, the second cyclic deposition process for depositing an aluminum carbide layer on the substrate 130 may include pulsing the third vapor-phase precursor 121 from the reactant source container 113 to the reaction chamber 104 via the showerhead 108. The co-reactant 132 and / or the fourth vapor-phase precursor 124 may be pulsed from their respective reactant source containers 140 and 114 to the reaction chamber 104 via the showerhead 108 simultaneously with or separately from the third vapor-phase precursor 121. In an example, the third vapor-phase precursor 121 and the co-reactant 132 may contact the substrate 130 to form an aluminum carbide layer thereon.

[0056] In another example, the third vapor-phase precursor 121 and the fourth vapor-phase precursor 124 may contact the substrate 130 to form a niobium aluminum carbide layer.

[0057] In another example, a third vapor-phase precursor 121 and a co-reactant 132 may contact a substrate 130 to form an aluminum carbide layer thereon. After the aluminum carbide layer is formed, the substrate 130 may be exposed to a fourth vapor-phase precursor 124 to form a niobium aluminum carbide layer or a niobium-doped aluminum carbide layer via an immersion process. A "immersion process" may include a deposition process whereby, after the initial precursors (e.g., the third vapor-phase precursor 121 and the co-reactant 132) have been pulsed onto the substrate and a layer (e.g., an aluminum carbide layer) has been formed, an additional precursor (e.g., the fourth vapor-phase precursor 124) may be introduced into the chamber. The additional precursor may react with the newly formed layer (e.g., the aluminum carbide layer) at the surface, and certain components of the precursor (e.g., niobium) may diffuse into the layer, thereby creating a gradient (e.g., a niobium gradient) within the newly formed layer (e.g., the aluminum carbide layer). The additional precursor may be exposed and in contact with the newly formed layer for an extended period of time (e.g., seconds or minutes, depending on the application). This extended exposure time may be generated by repeated pulsing of the additional precursor or by extending the length of one or more pulses. Diffused species from the precursor can form a stable layer and enable controlled diffusion of added species into the existing layer.

[0058] In various examples, the reaction chamber 104 can be purged with a purge gas 156 between one or more pulses of the third vapor precursor 121, the co-reactant 132, and / or the fourth vapor precursor 124. The purge can be performed before, during, between, and / or after one or more deposition cycles. The second cyclic deposition process (or portions thereof) can be repeated until the desired thickness of the second material layer is reached.

[0059] In the third sub-cycle, the third cyclic deposition process for depositing the second metal nitride layer on the substrate 130 may include pulsing the fifth vapor-phase precursor 134 from the reactant source container 142 to the reaction chamber 104 via the showerhead 108. The sixth vapor-phase precursor 133 may be pulsed from the reactant source container 144 to the reaction chamber 104 via the showerhead 108 together with or separately from the fifth vapor-phase precursor 134. When the fifth vapor-phase precursor 134 and the sixth vapor-phase precursor 133 contact the substrate 130, a second metal nitride layer may be formed on the substrate 130.

[0060] In another example, after forming the second metal nitride layer, the substrate 130 can be exposed to a seventh vapor-phase precursor 162 to form a silicon-metal nitride layer or a silicon-doped metal nitride layer by an immersion process. The seventh vapor-phase precursor 162 can be pulsed from the reactant source container 164 to the reaction chamber 104 via the showerhead 108. The seventh vapor-phase precursor 162 can be pulsed together with or separately from the fifth vapor-phase precursor 134 and / or the sixth vapor-phase precursor 133. The "immersion process" is similar to that described above and can include a deposition process, whereby after the initial precursors (e.g., the fifth vapor-phase precursor 134 and the sixth vapor-phase precursor 133) are pulsed onto the substrate and form a layer (e.g., the second metal nitride layer), an additional precursor (e.g., the seventh vapor-phase precursor 162) can be introduced into the chamber. The additional precursor can react with the newly formed layer (e.g., the second metal nitride layer) at the surface, and certain components of the additional precursor (e.g., silicon) can diffuse into the layer, thereby generating a silicon gradient within the metal nitride layer. The additional precursor (e.g., seventh vapor-phase precursor 162) can be exposed and in contact with the newly formed layer (e.g., second metal nitride layer) for an extended period of time (e.g., seconds or minutes, depending on the application). This extended exposure time can be generated by repeated pulses of the additional precursor and / or by extending the length of one or more pulses. The diffusing species from the additional precursor can form a stable layer and achieve controlled diffusion of the added species into the existing layer.

[0061] The reaction chamber 104 may be purged with a purge gas 156 between one or more pulses of the fifth vapor precursor 134, the sixth vapor precursor 133, and / or the seventh vapor precursor 162. The purge may be performed before, during, between, and / or after one or more deposition cycles. The third cyclic deposition process (or portions thereof) may be repeated until the desired thickness of the third material layer is reached.

[0062] In some examples, the first material layer, the second material layer, and / or the third material layer can be deposited in the same chamber or can be deposited in different chambers. In addition, each layer can be deposited separately or in applications other than the composite film described above, and the claimed subject matter is not limited in this respect. For example, the above layers can be used in device applications other than work function materials, such as in MOSCAPs.

[0063] The first material layer, the second material layer, and / or the third material layer may be formed by any of various methods including various deposition cycles.

[0064] In some examples, a reactor system (e.g., reactor system 150) may include multiple reaction chambers. For example, in reactor system 200, Figure 2 As shown, a plurality of reaction chambers 204 (each of which may be Figure 1104, 105, and / or 107 in the load lock chamber 212) can be disposed around and / or coupled to a transfer chamber 280 that includes a transfer tool 285 for transferring substrates between the reaction chambers 204. The substrates can be transferred from the load lock chamber 212 and between the reaction chambers 204 (e.g., via the transfer chamber 280). For example, the substrates 130 can be disposed in different chambers for different steps of a semiconductor manufacturing process (i.e., a first deposition cycle, a second deposition cycle, and / or a third deposition cycle can each be performed in the same or different chambers).

[0065] Figure 3A Device 316 is shown according to an example of the present disclosure. Device 316 can include a MOSCAP and / or devices incorporated into other specific device architectures, such as gate stacks, planar semiconductor devices, FinFETs, nanosheets, nanowires, gate-all-around (GAA), complementary FETs (CFETs), and / or any of a variety of other devices, and claimed subject matter is not limited in this respect.

[0066] In an example, the device 316 includes a substrate 302 , a dielectric or insulating material 304 , a liner layer 306 , a metal carbide layer 308 , and a capping layer 312 .

[0067] In an example, substrate 302 may be or include any of the substrate materials described above.

[0068] In an example, dielectric or insulating material 304 may be disposed on substrate 302 surface 322 and may be a high-k material, such as a metal oxide having a dielectric constant greater than about 7. In some embodiments, the dielectric constant of the high-k material is higher than that of silicon oxide. Exemplary high-k materials include one or more of hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiOx), aluminum oxide (Al2O3), lanthanum oxide (La2O3), and mixtures / laminates including one or more such layers. In an example, thickness T1 may be less than 100 angstroms (Å), or about 75Å to about 100Å, or about 50Å to about 75Å, or about 25Å to about 50Å, or about 15Å to about 30Å, or any suitable thickness (in this context, "about" means + / - 10Å).

[0069] In an example, the liner layer 306 may be deposited on the surface 324 of the dielectric or insulating material 304 and may include a metal nitride, a metal silicon nitride, or a silicon-doped metal nitride, as described with respect to Figures 6A-6DDiscussed in more detail. In examples, thickness T2 can be less than 25 Angstroms (Å), or about 1 Å to about 25 Å, or about 1 Å to about 15 Å, or about 2 Å to about 25 Å, or about 2 Å to about 15 Å, or about 2 Å to about 10 Å, or any suitable thickness (in this context, "about" means + / - 2 Å).

[0070] In an example, the metal carbide layer 308 may include a work function layer disposed on the surface 326 of the liner layer 306. The metal carbide layer 308 may be formed as follows: Figures 6A-6D The metal carbide layer 308 is deposited in a cyclic deposition process described in more detail. In some examples, the metal carbide layer 308 may include aluminum carbide. Because the metal carbide layer 308 is formed using a cyclic deposition process, the concentration of aluminum, carbon, and / or other components in the metal carbide layer 308 can be controlled by, for example, controlling the temperature, pressure, and / or pulse time during one or more deposition cycles. In some cases, the metal carbide layer 308 may have a stoichiometric composition. In some examples, the metal carbide layer 308 may have a non-stoichiometric composition. The work function and other properties of the metal carbide layer 308 can be changed by varying the amount of metal, carbon, and / or other components in the layer or during the deposition cycle.

[0071] In an example, the metal carbide layer 308 may include impurities, such as hydrogen and / or oxygen, etc., alone or in combination, in an amount less than 10 atomic %, 5 atomic %, less than 1 atomic %, less than 0.2 atomic %, less than 0.1 atomic %, or less than 0.05 atomic %.

[0072] The thickness of the metal carbide layer 308 can vary depending on the application. For example, the desired or predetermined thickness of the metal carbide layer 308 (shown as thickness T3) can be from about 1 Å to about 50 Å, or from about 5 Å to about 50 Å, or from about 2 Å to about 40 Å, or from about 3 Å to about 35 Å, or from about 5 Å to about 30 Å, or from about 5 Å to about 25 Å, or any suitable thickness ("about" in this context means + / - 5°C).

[0073] The thickness and / or composition of the metal carbide layer 308 can be adjusted to obtain a desired work function. In an example, the work function of the metal carbide layer 308 can be ≤4.0 eV, ≤4.1 eV, ≤4.2 eV, ≤4.3 eV, ≤4.4 eV, ≤4.5 eV, ≤4.6 eV, ≤4.7 eV, or any suitable work function (“about” in this context means + / - 0.1 eV).

[0074] In an example, the metal carbide layer 308 can be tuned to obtain a desired percentage of aluminum by adjusting the process window (e.g., temperature, pressure, and / or pulse time and number of pulses). In an example, the metal carbide layer 308 can contain about 65 atomic % aluminum, or less than about 60 atomic % aluminum, or less than about 50 atomic % aluminum, or less than about 40 atomic % aluminum, or less than about 30 atomic % aluminum, or less than about 25 atomic % aluminum, or less than about 20 atomic % aluminum, or less than about 15 atomic % aluminum, or less than about 10 atomic % aluminum, or less than about 5 atomic % aluminum, or any suitable atomic % aluminum (where "about" in this context means + / - 5%).

[0075] In an example, the capping layer 312 may be disposed on the top surface 328 of the aluminum carbide layer 308 and may include a metal nitride, a metal silicon nitride, or a silicon-doped metal nitride, as described with respect to Figures 6A-6D Discussed in more detail. In some examples where the capping layer 312 includes silicon, the silicon can be deposited such that a silicon gradient is formed with a maximum silicon concentration near the top 342 of the capping layer 312. In examples, the capping layer 312 can be adjusted to a predetermined thickness T4. The predetermined thickness T4 can be less than about 100 angstroms (Å), or about 1 Å to about 100 Å, or about 2 Å to about 80 Å, or about 3 Å to about 60 Å, or about 4 Å to about 40 Å, or about 5 Å to about 30 Å, or any suitable thickness (in this context, "about" means + / - 5 Å).

[0076] Figure 3B Device 318 is shown according to an example of the present disclosure. Device 318 can include a MOSCAP and / or devices incorporated into other specific device architectures, such as gate stacks, planar semiconductor devices, FinFETs, nanosheets, nanowires, gate-all-around (GAA), complementary FETs (CFETs), and / or any of a variety of other devices, and claimed subject matter is not limited in this respect.

[0077] In an example, the device 318 includes a substrate 302 , a dielectric or insulating material 304 , a liner layer 306 , a metal carbide layer 340 , and a capping layer 312 .

[0078] In an example, substrate 302 may be or include any of the substrate materials described above.

[0079] In an example, dielectric or insulating material 304 may be disposed on substrate 302 surface 332 and may be a high-k material, such as a metal oxide having a dielectric constant greater than about 7. In some embodiments, the dielectric constant of the high-k material is higher than the dielectric constant of silicon oxide. Exemplary high-k materials include one or more of the following: hafnium oxide (HfO2), tantalum oxide (Ta2O5), zirconium oxide (ZrO2), titanium oxide (TiO2), hafnium silicate (HfSiO x ), aluminum oxide (Al2O3), lanthanum oxide (La2O3), and mixtures / laminates including one or more such layers. In examples, thickness T5 can be less than 100 angstroms (Å), or about 75Å to about 100Å, or about 50Å to about 75Å, or about 25Å to about 50Å, or about 1Å to about 30Å, or any suitable thickness ("about" in this context means + / - 10Å).

[0080] In an example, the liner layer 306 may be deposited on the surface 334 of the dielectric or insulating material 304 and may include a metal nitride, a metal silicon nitride, or a silicon-doped metal nitride, as described with respect to Figures 6A-6D Discussed in more detail. In examples, thickness T6 can be less than 25 angstroms (Å), or about 1 Å to about 25 Å, or about 1 Å to about 15 Å, or about 2 Å to about 25 Å, or about 2 Å to about 15 Å, or about 2 Å to about 10 Å, or any suitable thickness (where "about" in this context means + / - 2 Å).

[0081] In an example, the metal carbide layer 340 may include a work function layer disposed on the surface 326 of the liner layer 306. The metal carbide layer 340 may be formed as follows: 6A to 6D The metal carbide layer 340 is deposited in a cyclic deposition process described in more detail. In some examples, the metal carbide layer 340 may include niobium aluminum carbide or niobium-doped aluminum carbide. The metal carbide layer 340 can be tuned to obtain a desired percentage of aluminum by adjusting the process window (e.g., temperature, pressure, and / or pulse time and number of pulses). In addition, because the metal carbide layer 340 is formed using a cyclic deposition process, the concentration of aluminum, carbon, and / or other components (e.g., niobium) can be adjusted by, for example, controlling the ratio of an aluminum-containing precursor to other precursors (e.g., a niobium-containing precursor) used during deposition.

[0082] In some examples, the precursor ratio can be controlled by adjusting the pulse cycle and / or pulse ratio. For example, in an example where the metal carbide layer 340 comprises niobium aluminum carbide to increase the aluminum content in the metal carbide layer 340, the ratio of niobium-containing precursor pulses to aluminum-containing precursor pulses can be about 1:1 to 1:10, or about 1:1 to 1:8, or about 1:1 to 1:6, or about 1:1 to 1:4, or about 1:2 to 1:10, or about 1:2 to 1:8, or about 1:2 to 1:6, or about 1:2 to 1:4, or any suitable pulse ratio ("about" in this context means + / - 1 pulse).

[0083] Because each layer can be deposited separately or in applications other than the composite films described above, it may be desirable to increase the niobium content and decrease the aluminum content of the metal carbide layer 340 comprising niobium aluminum carbide. In such examples, the ratio of pulses of the niobium-containing precursor to pulses of the aluminum-containing precursor can be about 1:1 to 10:1, or about 1:1 to 8:1, or about 1:1 to 6:1, or about 1:1 to 4:1, or about 2:1 to 10:1, or about 2:1 to 8:1, or about 2:1 to 6:1, or about 2:1 to 4:1, or any suitable pulse ratio (where "about" in this context means + / - 1 pulse).

[0084] In some cases, the metal carbide layer 340 may have a stoichiometric composition. In some examples, the metal carbide layer 340 may have a non-stoichiometric composition. The work function and other properties of the metal carbide layer 340 may be varied by varying the amount of metal, carbon, and / or other components in the layer or during the deposition cycle.

[0085] In an example, the metal carbide layer 340 may include impurities such as halides, hydrogen, and / or oxygen, etc., in amounts less than 10 atomic %, 5 atomic %, less than 1 atomic %, less than 0.2 atomic %, less than 0.1 atomic %, or less than 0.05 atomic %, alone or in combination.

[0086] The thickness of the metal carbide layer 340 can vary depending on the application. For example, the desired or predetermined thickness of the metal carbide layer 340 (shown as thickness T7) can be about 1 Å to about 50 Å, or about 5 Å to about 50 Å, or about 2 Å′ to about 40 Å′, or about 3 Å′ to about 35 Å′, or about 5 Å to about 30 Å, or about 5 Å to about 25 Å, or any suitable thickness (in this context, "about" means + / - 5 Å).

[0087] The thickness and / or composition of the metal carbide layer 340 can be adjusted to obtain a desired work function and / or threshold voltage. In an example, the work function of the metal carbide layer 308 can be ≤4.0 eV, ≤4.1 eV, ≤4.2 eV, ≤4.3 eV, ≤4.4 eV, ≤4.5 eV, ≤4.6 eV, ≤4.7 eV, or any suitable work function ("about" in this context means + / - 0.1 eV).

[0088] In an example, the metal carbide layer 340 can be adjusted to obtain a desired percentage of aluminum as described herein. In an example, the metal carbide layer 340 can contain about 65 atomic % aluminum, or less than about 60 atomic % aluminum, or less than about 50 atomic % aluminum, or less than about 40 atomic % aluminum, or less than about 30 atomic % aluminum, or less than about 25 atomic % aluminum, or less than about 20 atomic % aluminum, or less than about 15 atomic % aluminum, or less than about 10 atomic % aluminum, or less than about 5 atomic % aluminum, or any suitable atomic % aluminum (where "about" in this context means + / - 5%).

[0089] In an example, the capping layer 312 may be disposed on the top surface 338 of the aluminum carbide layer 340 and may include a metal nitride, a metal silicon nitride, or a silicon-doped metal nitride, as described with respect to Figures 6A-6D Discussed in more detail. In an example, the cover layer 312 can be adjusted to a predetermined thickness T8. The predetermined thickness T8 can be less than about 100 angstroms (Å), or about 1 Å to about 100 Å, or about 2 Å to about 80 Å, or about 3 Å to about 60 Å, or about 4 Å to about 40 Å, or about 5 Å to about 30 Å, or any suitable thickness (in this context, "about" means + / - 5 Å).

[0090] Figure 4 References to examples according to the present disclosure are shown Figure 3A and Figure 3B Another exemplary structure 400 is shown. The device or structure 400 includes a substrate 302, a dielectric or insulating material 304, and a work function layer (shown as a dashed line) including an aluminum carbide layer 308 or a metal carbide layer 340. In the example shown, the structure 400 also includes a liner layer 306 and a capping layer 312.

[0091] In the example shown, substrate 302 includes source region 414, drain region 416, and channel region 418. Although shown as horizontal structures, structures and devices according to examples of the present disclosure may include vertical and / or three-dimensional structures and devices, such as FinFET devices.

[0092] Figure 5 References to examples according to the present disclosure are shown Figure 3A and Figure 3BAnother structure 500 is provided. The structure 500 is suitable for use in a gate-all-around field effect transistor (GAA FET) (also known as a lateral nanowire FET) device, among others.

[0093] In the example shown, structure 500 includes substrate 302 , dielectric material 304 , a work function layer including aluminum carbide layer 308 or metal carbide layer 340 (shown as dashed lines), and also includes liner layer 306 and capping layer 312 .

[0094] Figure 6A An example process 600 for depositing a composite film is shown. Although the example process 600 depicts a particular sequence of operations, this sequence may be varied without departing from the scope of the present disclosure.

[0095] According to some examples, process 600 may begin with an optional (as shown in dashed lines) operation 601, in which the reaction chamber (e.g., reaction chamber 104) is pretreated with NH3 before the deposition process is initiated. Without being limited by theory, it is believed that ammonia can be used to nitride the interior surfaces of the chamber, such as the showerhead (i.e., distribution system 108), to promote aluminum metal formation, thereby resulting in the formation of aluminum carbide due to the decomposition of the aluminum-containing precursor. This nitriding can smooth the interior surfaces, thereby promoting more efficient use of the precursor. Such NH3 pretreatment can be performed by flowing NH3 for a predetermined amount of time. For example, NH3 can be flowed into the reaction chamber for between about 1 second and 100 seconds, or between about 2 seconds and 90 seconds, or between about 4 seconds and 80 seconds, or between about 5 seconds and 60 seconds, or between about 6 seconds and 50 seconds, or between about 8 seconds and 40 seconds, or between about 9 seconds and 30 seconds, or between about 10 seconds and 20 seconds, or any suitable amount of time (in this context, "about" means + / - 5 seconds). NH can flow into the reaction chamber at a rate of between about 0.1 and 10.5 slm, or between about 1 and 9 slm, or between about 1.5 and 6.5 slm, or between about 2 and 5 slm, or between about 2 and 4 slm, or any suitable rate (in this context, "about" means + / - 2 slm). The pressure of reaction chamber 104 during pretreatment operation 601 can be between about 0.1 Torr and 100 Torr, or between about 0.1 Torr and 50 Torr, or between about 0.1 Torr and 25 Torr, or between about 0.1 Torr and 15 Torr, or between about 0.2 Torr and 10 Torr, or between about 0.5 Torr and 8 Torr, or between about 0.5 Torr and 6 Torr, or any suitable pressure (in this context, "about" means + / - 5 Torr).

[0096] In an example, process 600 may proceed to operation 602, where a substrate is provided in a reaction chamber. The substrate surface may include a high-k material. In some embodiments, the high-k material may include hafnium oxide (HfO x ).

[0097] In an example, process 600 may proceed to a first cycle deposition process 605 (see FIG. Figure 6B ), wherein a first material layer comprising a first metal nitride may be deposited (see, for example, Figure 3A , liner layer 306). In an example, the first metal nitride may include various metal nitrides, such as titanium nitride (TiN), molybdenum nitride (MoN), or vanadium nitride (VN), or a combination thereof. In some embodiments, the first metal nitride may further include silicon, such that the first material layer may include any of various compounds, including titanium silicon nitride, molybdenum silicon nitride, or vanadium silicon nitride, or a combination thereof. In an example, the first material layer may include a liner layer.

[0098] In an example, the first cyclic deposition process 605 may be repeated until the first material layer reaches a predetermined thickness.

[0099] The process 600 may proceed to a second cycle deposition process 607 at operation 606 (see Figure 6C ), wherein a second material layer comprising aluminum carbide may be deposited (see, for example, Figure 3A , aluminum carbide layer 308 or see Figure 3B The second material layer may include a percentage of aluminum in the range of approximately 10%-60%, or approximately 10%-40%, or approximately 10%-30%. In some embodiments, the second material layer may include niobium aluminum carbide. The second material layer may include a percentage of niobium in the range of approximately 10%-50% niobium.

[0100] In an example, the second cyclic deposition process 607 may be repeated until the second material layer reaches a predetermined thickness.

[0101] In an example, process 600 may proceed to a third cycle deposition process 609 at operation 608 (see Figure 6D ), wherein a third material layer comprising a second metal nitride may be deposited (see, for example, Figure 3A , capping layer 312). In an example, the second metal nitride may include various metal nitrides, such as titanium nitride (TiN), molybdenum nitride (MoN), or vanadium nitride (VN), or a combination thereof. In some embodiments, the second metal nitride may further include silicon, so that the third material layer may include any of a variety of compounds, including titanium silicon nitride, silicon-doped titanium nitride, molybdenum silicon nitride, silicon-doped molybdenum nitride, vanadium silicon nitride, silicon-doped vanadium nitride, or a combination thereof. The first metal nitride and the second metal nitride may include the same material or different materials. For example, the first metal nitride may not include silicon, while the second metal nitride may include silicon. In an example, the second metal nitride may include a capping layer.

[0102] In an example, the third cyclic deposition process 609 may be repeated until the third material layer reaches a predetermined thickness.

[0103] In an example, the first cycle deposition process 605, the second cycle deposition process 607, and / or the third cycle deposition process 609 may be performed in the same reaction chamber (e.g., see Figure 1 In another example, the first cycle deposition process 605 can be performed in the first reaction chamber (e.g., see Figure 1 , reaction chamber 104), the second cycle deposition process 607 can be carried out in a different second reaction chamber (see Figure 1 , reaction chamber 105), and the third cycle deposition process 609 can be carried out in a different third reaction chamber (see, for example, Figure 1 , reaction chamber 107). In another embodiment, any two of the first cyclic deposition process 605, the second cyclic deposition process 607, and / or the third cyclic deposition process 609 may be performed in the same reaction chamber, and the third cyclic deposition process among the first cyclic deposition process 605, the second cyclic deposition process 607, and / or the third cyclic deposition process 609 may be performed in different reaction chambers.

[0104] Figure 6B Operation 604 for depositing a first material layer is shown in more detail (see Figure 6A ) first cycle deposition process 605. Although the example process 604 depicts a specific sequence of operations, this sequence can be changed without departing from the scope of this disclosure. Operations can be performed in multiple sequences and repetitions to suit specific requirements. In some embodiments, one or more operations can be performed in any order or even omitted entirely, depending on the requirements of the process.

[0105] In an example, the first metal nitride layer may include any of various metal nitrides including, but not limited to, titanium nitride, vanadium nitride, silicon-doped titanium nitride, silicon-doped vanadium nitride, titanium silicon nitride, or vanadium silicon nitride, or combinations thereof.

[0106] According to some examples, process 605 may begin at operation 610, where a first gaseous precursor (e.g., first gaseous precursor 115, see Figure 1 ) may contact the substrate. In an example, the first vapor-phase precursor may be a metal-containing precursor and may include titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), or a combination thereof.

[0107] According to some examples, process 605 may proceed to operation 612, which includes exposing the substrate to a second vapor precursor (e.g., second vapor precursor 117, see Figure 1), wherein the second vapor precursor comprises nitrogen. In an example, the second vapor precursor may include ammonia (NH 3 ), hydrazine (N 2 H 4 ), a hydrazine derivative, an alkyl hydrazine, tert-butyl hydrazine (C 4 H 9 N 2 H 3 ), methyl hydrazine (CH 3 NH NH 2 ), dimethyl hydrazine ((CH 3 ) 2 N 2 H 2 ), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N 2 plasma, N 2 / H 2 plasma, NH 3 plasma, excited species of nitrogen, nitrogen ions, nitrogen radicals, or any combination thereof.

[0108] According to some examples, process 605 includes purging the reaction chamber at operation 614 (e.g., by pulsing purge gas 156 into chamber 104, see Figure 1 ), as shown by the dashed line. The purge operation 614 can be performed at any junction in the first cycle deposition process 605 (e.g., before, after, and / or between operations 610, 612, and / or before or after the second cycle deposition process 605). Excess chemicals and reaction byproducts (if any) can be removed from the reaction chamber by purging. The purge gas (e.g., purge gas 156, see Figure 1 ) is preferably any inert gas, such as but not limited to argon (Ar), nitrogen (N2) or helium (He).

[0109] According to some examples, at operation 616, process 605 includes repeating one or more operations 610, 612, or 614, or any combination thereof, in any order, until a first material layer having a first predetermined thickness is deposited on the surface of the substrate. In an example, the first predetermined thickness of the first material layer is in a range of approximately 5 angstroms to 15 angstroms.

[0110] In some examples, during processing, the temperature of the reaction chamber (e.g., chamber 104) during the first deposition cycle 605 for depositing the second metal nitride layer can be less than about 600° C., or less than about 550° C., or less than about 500° C., or less than about 450° C., or less than about 400° C., or less than about 300° C., or between about 300° C. and 550° C., or any suitable temperature. The pressure of the reaction chamber during the first deposition cycle 605 can be between 0.1 Torr and 100 Torr, or between 0.1 Torr and 50 Torr, or between 0.1 Torr and 25 Torr, or between 0.5 Torr and 8 Torr, 1 Torr to 5 Torr, or any suitable pressure.

[0111] In some examples of the present disclosure, contacting the substrate with the first vapor precursor and / or the second vapor precursor may include contacting the substrate with the first vapor precursor and / or the second vapor precursor for a time period of between about 0.01 seconds and about 1000 seconds, or between about 0.05 seconds and about 500 seconds, or between about 0.1 seconds and about 250 seconds, between about 0.01 seconds and about 100 seconds, or between about 0.1 seconds and about 50 seconds, or between about 0.1 seconds and about 25 seconds, between about 0.1 seconds and about 15 seconds, or between about 0.1 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds, or even between 0.2 seconds and 2 seconds, or any suitable time period.

[0112] Figure 6C Operation 606 for depositing the aluminum carbide layer is shown in more detail (see Figure 6A ) of the second cycle deposition process 607. Although the example process 607 depicts a specific sequence of operations, the sequence can be changed without departing from the scope of the present disclosure. Operations can be performed in multiple sequences and repetitions to suit specific requirements. In some embodiments, one or more operations can be performed in any order or even omitted entirely, depending on the requirements of the process.

[0113] According to some examples, process 607 may begin at operation 618, where the substrate may be contacted with a third vapor precursor (e.g., third vapor precursor 121, see Figure 1 ). In an example, the third vapor-phase precursor may include at least one of triethylaluminum (TEA), triisobutylaluminum (TIBA), dimethylaluminum hydride (DMAH), trimethylaluminum (TMA), tri-tert-butylaluminum (TTBA), bis(tert-butylamino)aluminum hydride (BTBAH), methylaluminum trichloride (MTCA), diethylaluminum chloride (DEAC), AlCl 3 , or a combination thereof.

[0114] In some examples, the second material layer may include aluminum carbide. In such examples, process 607 may proceed to optional (indicated by dashed lines) operation 620, where the substrate may be reacted with a co-reactant (e.g., co-reactant 132, see Figure 1 ) contact. The aluminum carbide layer can be deposited using an aluminum-containing precursor that also contains carbon. In such an example, the aluminum component and the carbon component can both be derived from the same precursor. In an example, a co-reactant can be used, and the co-reactant can include hydrogen (H2), hydrogen plasma, and / or excited species of hydrogen. Without being limited by theory, it is believed that hydrogen can act as a reducing agent to promote Al metal formation, thereby leading to the formation of aluminum carbide due to the decomposition of the aluminum-containing precursor.

[0115] In some embodiments, the second material layer may include niobium, for example, the second material layer may include niobium aluminum carbide. Process 607 may include contacting the substrate with a third vapor precursor at operation 618 and contacting the substrate with a fourth vapor precursor (e.g., fourth vapor precursor 124, see FIG. 1 ) at optional operation 621. Figure 1 ). The fourth vapor-phase precursor may be a niobium-containing vapor-phase precursor. In certain examples, the fourth vapor-phase precursor may include niobium pentachloride (NbCl5), niobium pentafluoride (NbF5), niobium pentaiodide (NbI5), niobium pentabromide (NbBr5), or a combination thereof. In certain examples, a co-reactant (e.g., H2) may or may not be used with the third vapor-phase precursor and / or the fourth vapor-phase precursor to produce a second material layer comprising niobium aluminum carbide.

[0116] In another example, the second cyclic deposition process 607 may include contacting the substrate with a co-reactant (e.g., H2) to deposit aluminum carbide at optional operation 620, followed by contacting the aluminum carbide layer with a fourth vapor-phase precursor at optional operation 621. In some examples, contacting the aluminum carbide layer with the fourth vapor-phase precursor may be performed over an extended period of time or multiple repeated pulses of the fourth vapor-phase precursor during the soaking process as described above. In an example, the fourth vapor-phase precursor may react with the newly formed aluminum carbide layer at the surface, and niobium may diffuse into the aluminum carbide layer, creating a niobium gradient within the top surface of the aluminum carbide layer, wherein the maximum concentration of niobium may be near the surface of the aluminum carbide layer. The diffused species from the precursor may form a stable layer and enable controlled diffusion of the added species into the existing layer. In one example, the aluminum concentration in the second material layer can be adjusted by: 1) varying the thickness of the aluminum carbide layer prior to contact with the fourth vapor-phase precursor, wherein a thinner aluminum carbide layer has less aluminum than a thicker aluminum carbide layer, and 2) exposing the aluminum carbide layer to the fourth vapor-phase precursor for multiple pulses of a selected duration or fewer pulses for a longer period. Additionally, the aluminum in the second material layer can be removed by AlCl3 generated during pulsing with the niobium-containing fourth vapor-phase precursor. Thus, the aluminum concentration can be adjusted by varying the number and duration of pulses of the niobium-containing fourth vapor-phase precursor.

[0117] In an example, the second cyclic deposition process 607 may proceed to a reaction chamber purge step at operation 622 (e.g., by pulsing a purge gas into the chamber), as shown by the dashed line. The purge operation 622 may be performed at any junction in the second cyclic deposition process 607 (e.g., before, after, and / or between operations 618, 620, and / or before or after the second cyclic deposition process 607). Excess chemicals and reaction byproducts (if any) may be removed from the reaction chamber by the purge. The purge gas is preferably any inert gas, such as, but not limited to, argon (Ar), nitrogen (N2), or helium (He).

[0118] According to some examples, process 607 may proceed to operation 624 , which includes repeating one or more operations 618 , 620 , or 622 , or any combination thereof, in any order, until a second material layer of a second predetermined thickness is deposited on the surface of the substrate.

[0119] In an example, the second predetermined thickness of the second material layer is about 5 angstroms. to within the range.

[0120] In some examples, during processing, the temperature of the reaction chamber (e.g., chamber 104) during the second deposition cycle 607 for depositing the second metal nitride layer can be less than about 600° C., or less than about 550° C., or less than about 500° C., or less than about 450° C., or less than about 400° C., or less than about 300° C., or between about 300° C. and 550° C., or any suitable temperature. The pressure of the reaction chamber during the second deposition cycle 607 can be between 0.1 Torr and 100 Torr, or between 0.1 Torr and 50 Torr, or between 0.1 Torr and 25 Torr, or between 0.5 Torr and 8 Torr, 1 Torr to 5 Torr, or any suitable pressure.

[0121] In some examples of the present disclosure, contacting the substrate with the third vapor precursor, the fourth vapor precursor and / or the co-reactant may include contacting the substrate with the third vapor precursor, the fourth vapor precursor and / or the co-reactant for a time period of between about 0.01 seconds and about 1000 seconds, or between about 0.05 seconds and about 500 seconds, or between about 0.1 seconds and about 250 seconds, between about 0.01 seconds and about 100 seconds, or between about 0.1 seconds and about 50 seconds, or between about 0.1 seconds and about 25 seconds, between about 0.1 seconds and about 15 seconds, or between about 0.1 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds, or even between 0.2 seconds and 2 seconds, or any suitable time period.

[0122] Figure 6D An example third cycle deposition process 609 is shown for depositing a second metal nitride layer. Although example process 609 depicts a specific sequence of operations, this sequence may be varied without departing from the scope of this disclosure. Operations may be performed in multiple sequences and repetitions to suit specific requirements. In some embodiments, one or more operations may be performed in any order or even omitted entirely, depending on the requirements of the process.

[0123] In an example, the second metal nitride layer may include any of various metal nitrides including, but not limited to, titanium nitride, vanadium nitride, molybdenum nitride, silicon-doped titanium nitride, silicon-doped vanadium nitride, silicon-doped molybdenum nitride, titanium silicon nitride, vanadium silicon nitride, and / or molybdenum silicon nitride, or combinations thereof.

[0124] According to some examples, process 609 may begin at operation 626 and include exposing the substrate to a fifth vapor-phase precursor (e.g., see Figure 1 , a fifth vapor-phase precursor 134). In an example, the fifth vapor-phase precursor can be a metal-containing precursor and can include, but is not limited to, titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), molybdenum (V) oxychloride trichloride (MoOCl3), molybdenum (VI) oxychloride tetrachloride (MoOCl4), or molybdenum (IV) dichloride (MoO2Cl2), or a combination thereof.

[0125] According to some examples, process 609 may move to operation 628, which includes contacting the substrate with a sixth vapor-phase precursor. In some examples, the sixth vapor-phase precursor may include a nitrogen-containing precursor (e.g., see Figure 1 , sixth gaseous precursor 133). Such nitrogen-containing precursors may include, but are not limited to, ammonia (NH3), hydrazine (N2H4), hydrazine derivatives, alkyl hydrazines, tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N2 plasma, N2 / H2 plasma, NH3 plasma, excited species of nitrogen, nitrogen ions, nitrogen radicals, or any combination thereof.

[0126] In an example, the third cyclic deposition process 609 may proceed to an optional (shown in dashed lines) operation 629. Operation 629 may include contacting the substrate with a seventh vapor-phase precursor (e.g., see Figure 1 , the seventh gas-phase precursor 162 is in contact. In an example, the seventh gas-phase precursor can be a silicon-containing precursor.

[0127] At operation 629, in some examples, upon completion of one or more of operations 626 and 628, a metal nitride layer may be provided on the substrate. The metal nitride may be exposed to a seventh vapor phase precursor comprising silicon so as to deposit the silicon into the metal nitride layer. Operation 629 may include soaking the second metal nitride layer with the seventh vapor phase precursor in a soaking process as previously described for an extended period of time and / or multiple pulses (e.g., approximately 1-1000 pulses, or any suitable number of pulses, wherein the pulses have a duration of approximately 1-10 seconds, or any suitable pulse duration). In an example, the seventh vapor phase precursor may interact with the newly formed second metal nitride layer at the surface, allowing silicon to diffuse into the metal nitride layer, thereby creating a silicon gradient. Thus, the third material layer may include a second metal nitride layer comprising a silicon gradient, wherein the maximum concentration of silicon may be near the top surface of the second metal nitride layer. The diffusing species from the precursor may form a stable layer and enable controlled diffusion of the added species into the existing layer.

[0128] The seventh precursor may include any suitable silicon-containing precursor, such as, but not limited to, silane (SiH4), disilane (Si2H6), silicon tetrachloride (SiCl4), hexachlorodisilane (Si2Cl6), dichlorosilane (SiH2Cl2), monomethylsilane (CH3SiH3) and / or trisilane (H2Si(SiH3)2).

[0129] In an example, the third cyclic deposition process 609 may proceed to a reaction chamber purge step at operation 630 (e.g., by pulsing a purge gas into the chamber), as shown by the dashed line. Purge operation 630 may be performed at any junction in the third cyclic deposition process 609 (e.g., before, after, and / or between operations 626, 628, 629, and / or before or after the third cyclic deposition process 609). Excess chemicals and reaction byproducts (if any) may be removed from the reaction chamber by purging. The purge gas is preferably any inert gas, such as, but not limited to, argon (Ar), nitrogen (N2), or helium (He).

[0130] According to some examples, process 609 includes repeating one or more operations 626 , 628 , 629 , or 630 , in any order, or any combination thereof, until a third material layer of a third predetermined thickness is deposited on the surface of the substrate at operation 632 .

[0131] In some examples, process 609 may be applied mutatis mutandis to deposit a first material layer comprising a metal nitride.

[0132] In an example, the third predetermined thickness of the first material layer may be in a range of approximately 5 Angstroms (Å) to 30 Å.

[0133] In some examples, during processing, the temperature of the reaction chamber (e.g., chamber 104) during the third deposition cycle 609 for depositing the second metal nitride layer can be less than about 600° C., or less than about 550° C., or less than about 500° C., or less than about 450° C., or less than about 400° C., or less than about 300° C., or between about 300° C. and 550° C., or any suitable temperature. The pressure of the reaction chamber during the third deposition cycle 609 can be between 0.1 Torr and 100 Torr, or between 0.1 Torr and 50 Torr, or between 0.1 Torr and 25 Torr, or between 0.5 Torr and 8 Torr, 1 Torr to 5 Torr, or any suitable pressure.

[0134] In some examples of the present disclosure, contacting the substrate with the fifth vapor precursor, the sixth vapor precursor, and / or the seventh vapor precursor may include contacting the substrate with the fifth vapor precursor, the sixth vapor precursor, and / or the seventh vapor precursor for a time period of between about 0.01 seconds and about 1000 seconds, or between about 0.05 seconds and about 500 seconds, or between about 0.1 seconds and about 250 seconds, between about 0.01 seconds and about 100 seconds, or between about 0.1 seconds and about 50 seconds, or between about 0.1 seconds and about 25 seconds, between about 0.1 seconds and about 15 seconds, or between about 0.1 seconds and about 10 seconds, or between about 0.1 seconds and about 5 seconds, or even between 0.2 seconds and 2 seconds, or any suitable time period.

[0135] It should be understood that any conceivable order of deposition, etching processes, purge cycles, and repetitions thereof is contemplated as part of the present disclosure, including combinations of deposition, etching processes, purge cycles, and repetitions thereof disclosed with respect to the different figures, and that the claimed subject matter is not limited in this respect.

[0136] Although exemplary embodiments of the present disclosure have been described herein, it should be understood that the present disclosure is not limited thereto. Various modifications, variations, and enhancements can be made to the systems and methods described herein without departing from the spirit and scope of the present disclosure.

[0137] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various systems, components and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for depositing a composite film, comprising: providing a substrate in a reaction chamber; depositing a first material layer including a first metal nitride according to a first cyclic deposition process; depositing a second material layer including aluminum carbide according to a second cyclic deposition process; as well as A third material layer including a second metal nitride is deposited according to a third cyclic deposition process.

2. The method according to claim 1, wherein The first metal nitride includes titanium nitride (TiN) or vanadium nitride (VN) or a combination thereof.

3. The method according to claim 1, wherein The second metal nitride includes titanium nitride (TiN), vanadium nitride (VN), molybdenum nitride (MoN), or a combination thereof.

4. The method according to claim 1, wherein The first metal nitride and the second metal nitride are different.

5. The method according to claim 1, wherein The first metal nitride and the second metal nitride are the same.

6. The method according to claim 1, wherein The aluminum carbide contains 5-65 atomic % aluminum.

7. The method according to claim 1, wherein The aluminum carbide includes niobium aluminum carbide.

8. The method according to claim 7, wherein: The aluminum carbide contains 5 to 50 atomic % of aluminum and 10 to 50 atomic % of niobium.

9. The method according to claim 1, wherein The substrate surface includes a high-k material.

10. The method according to claim 9, wherein: The high-k material is hafnium oxide (HfO x ).

11. The method according to claim 1, wherein The first cycle deposition process includes: a) contacting a substrate with a first vapor precursor; b) contacting the substrate with a second vapor-phase precursor; c) purging the reaction chamber; and One or more of operations a), b), or c), or any combination thereof, are repeated in any order until a layer of the first material of a first predetermined thickness is deposited on the surface of the substrate.

12. The method according to claim 11, wherein The first gas-phase precursor includes at least one of titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), or a combination thereof.

13. The method according to claim 12, wherein: The second gaseous precursor includes at least one of the following: ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, an alkyl hydrazine, tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N2 plasma, N2 / H2 plasma, NH3 plasma, excited species of nitrogen, nitrogen ions, nitrogen radicals or any combination thereof.

14. The method according to claim 11, wherein The first material layer includes TiN or VN.

15. The method according to claim 14, wherein The first predetermined thickness is in a range of approximately 1 angstrom to 15 angstroms.

16. The method according to claim 1, wherein The second cycle deposition process includes: d) contacting the substrate with a third vapor-phase precursor; e) contacting the substrate with a co-reactant or a fourth vapor-phase precursor, or a combination thereof: f) purging the reaction chamber; and One or more of operations d), e) or f) or any combination thereof are repeated in any order until a layer of a second material of a second predetermined thickness is deposited on the surface.

17. The method according to claim 16, wherein: The third gaseous precursor comprises at least one of triethylaluminum (TEA), triisobutylaluminum (TIBA), dimethylaluminum hydride (DMAH), trimethylaluminum (TMA), tri-tert-butylaluminum (TTBA), bis(tert-butylamino)aluminum hydride (BTBAH), methylaluminum trichloride (MTCA), diethylaluminum chloride (DEAC), or a combination thereof.

18. The method according to claim 17, wherein The co-reactant comprises hydrogen (H2), hydrogen plasma, or other excited species of hydrogen.

19. The method according to claim 18, wherein The second material layer includes aluminum carbide.

20. The method according to claim 19, wherein The second predetermined thickness is in the range of 5 to 30 angstroms.

21. The method according to claim 19, wherein The percentage of Al ranges from 5% to 65%.

22. The method according to claim 16, wherein The fourth vapor-phase precursor includes a niobium vapor-phase reactant, and the niobium vapor-phase reactant includes niobium pentachloride (NbCl5), niobium pentafluoride (NbF5), niobium pentaiodide (NbI5), niobium pentabromide (NbBr5), or a combination thereof.

23. The method according to claim 22, wherein The second cyclic deposition process includes contacting the substrate with the third vapor-phase precursor and a co-reactant to deposit a second material layer comprising aluminum carbide, and subsequently contacting the second material layer with the fourth vapor-phase precursor.

24. The method according to claim 22, wherein The second material layer includes niobium aluminum carbide.

25. The method according to claim 24, wherein The second predetermined thickness is 5-50 angstroms.

26. The method according to claim 24, wherein The ratio of the fourth gas-phase precursor to the third gas-phase precursor is in the range of 1:2 to 1:

10.

27. The method of claim 1, further comprising pre-cleaning the reaction chamber prior to contacting the substrate with the first vapor-phase precursor.

28. The method according to claim 27, wherein Pre-cleaning includes exposing the reaction chamber to ammonia.

29. The method according to claim 26, wherein The percentage of Al ranges from 10% to 60%.

30. The method of claim 1, wherein The third cycle deposition process includes: g) contacting the substrate with a fifth vapor-phase precursor; h) contacting the substrate with a sixth vapor-phase precursor, or contacting the substrate with a seventh vapor-phase precursor, or a combination thereof; i) purging the reaction chamber; and One or more of operations g), h), or i), or any combination thereof, are repeated in any order until a third material layer of a third predetermined thickness is deposited on the surface of the substrate.

31. The method according to claim 30, wherein The fifth gaseous precursor includes at least one of the following: titanium tetrachloride (TiCl4), titanium tetraiodide (TiI4), titanium tetrabromide (TiBr3), vanadium fluoride (VF3), vanadium chloride (VCl3), vanadium oxychloride (VOCl3), molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), molybdenum (V) oxychloride trichloride (MoOCl3), molybdenum (VI) oxychloride tetrachloride (MoOCl4) or molybdenum (IV) dichloride (MoO2Cl2) or a combination thereof.

32. The method according to claim 31, wherein The sixth gas-phase precursor includes at least one of the following: ammonia (NH3), hydrazine (N2H4), a hydrazine derivative, an alkyl hydrazine, tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), dimethylhydrazine ((CH3)2N2H2), phenylhydrazine, tert-butylamine, isobutylamine, tert-amylamine, N2 plasma, N2 / H2 plasma, NH3 plasma, excited nitrogen species, nitrogen ions, nitrogen radicals or any combination thereof.

33. The method according to claim 32, wherein The seventh gas-phase precursor is a silicon-containing precursor.

34. The method according to claim 33, wherein The silicon-containing precursor is silane (SiH4), disilane (Si2H6), monomethylsilane (CH3SiH3) or trisilane (H2Si(SiH3)2) or a combination thereof.

35. The method of claim 30, wherein: The third material layer includes TiN, VN, MoN, TiSiN, VSiN or MoSiN.

36. The method of claim 30, wherein: The third predetermined thickness is in the range of 5 to 20 angstroms.

37. The method of claim 30, wherein: The third cyclic deposition process includes contacting the substrate with the fifth vapor precursor and the sixth vapor precursor to deposit a third material layer including a metal nitride, and then contacting the third material layer with the seventh vapor precursor.

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