Methods and assemblies for selective deposition of metal-containing materials

Abstract

The present disclosure relates to methods and assemblies for selectively depositing a metal-containing material, such as a metal oxide, on different surfaces of a semiconductor substrate by a cyclic vapor deposition technique including atomic layer deposition. A metal-containing material is deposited using a metal precursor having a metal atom bound to an acetamidinyl ligand, such as a dialkyl acetamidinyl ligand. In accordance with the process flow, a metal-containing material may be deposited on a metal surface opposite the dielectric surface, or on a dielectric surface opposite the metal surface. The present disclosure also relates to layers, structures and semiconductor devices deposited according to the methods disclosed herein, as well as semiconductor processing assemblies configured and arranged to perform the methods.

Description

Technical Field

[0001] The present disclosure generally relates to methods and components for selectively depositing metal-containing materials by cyclic vapor deposition techniques. Such methods can be used, for example, to process semiconductor substrates. More specifically, the present disclosure relates to methods and components for selectively depositing metal-containing materials. Background Art

[0002] Semiconductor device manufacturing processes typically use advanced vapor deposition methods. Patterning is commonly used to deposit different materials on semiconductor substrates. Semiconductor manufacturers are increasingly interested in selective deposition, which can reduce the steps required for conventional patterning, such as reducing the processing cost by reducing the number of patterning and etching steps. Selective deposition can also enhance scaling in narrow structures. The ability to selectively deposit on surfaces between dielectric materials and conductive materials such as metals can particularly simplify the device manufacturing process flow. Due to better compatibility with sensitive materials, thermal deposition methods may be superior to plasma-enhanced methods. However, the quality of metal-containing materials deposited thermally, such as their electrical properties or etch resistance, may be lower than those deposited using plasma.

[0003] Metal-containing materials such as metal oxides and metal nitrides can be used for various purposes, such as dielectric layers, etch stop layers, and diffusion barrier layers in semiconductor devices. Various alternatives have been proposed for achieving selective deposition of metal-containing materials, and additional improvements are needed to expand the use of selective deposition in industrial-scale device manufacturing, particularly for producing high-quality materials using thermal deposition methods.

[0004] Any discussion set forth in this section, including discussions of problems and solutions, has been included in the present disclosure solely to provide a background for the present disclosure. Such discussion should not be construed as an admission that any of the information was known at the time of the invention or constitutes prior art. Summary of the Invention

[0005] This summary of the invention may introduce some concepts in a simplified form that will be further described in detail below. This summary is not necessarily intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. Various embodiments of the present disclosure relate to methods of depositing metal-containing materials, particularly methods for selectively depositing metal oxides, metal nitrides, and metal fluorides. Embodiments of the present disclosure also relate to methods of manufacturing semiconductor devices, as well as semiconductor processing components.

[0006] Various embodiments of the present disclosure relate to the selective deposition of metal-containing materials, such as dielectric layers, including metal oxides, metal nitrides, and metal fluorides. Specifically, the present disclosure relates to the deposition of materials containing aluminum, gallium, and indium by a cyclic chemical vapor deposition process. The metal-containing materials may include doped metal-containing materials, such as yttrium-doped aluminum oxide (AlYOx), aluminum gallium nitride (AlGaN), or aluminum indium nitride (InAlN). Embodiments of the present disclosure also relate to structures formed using the method and processing components.

[0007] In one aspect, a method of selectively depositing a metal-containing material on a first surface of a semiconductor substrate relative to a second surface of the substrate is disclosed. The method includes providing the substrate in a reaction chamber and depositing the metal-containing material on the first surface of the substrate by a cyclic chemical vapor deposition process. The chemical vapor deposition process includes providing a first metal precursor in the gas phase to the reaction chamber and providing a reactant in the gas phase to the reaction chamber, wherein the first metal precursor includes a heteroleptic precursor that includes a Group 13 metal atom, an amidino ligand, and an alkyl ligand attached to the metal atom.

[0008] In some embodiments, the metal of the metal-containing material is selected from aluminum (Al), gallium (Ga), and indium (In). In some embodiments, the first metal precursor is selected from an aluminum precursor, a gallium precursor, and an indium precursor.

[0009] In some embodiments, the metal-containing material is aluminum oxide (e.g., Al2O3), and the first metal precursor is an aluminum precursor. In some embodiments, the metal-containing material is gallium oxide (e.g., Ga2O3), and the first metal precursor is a gallium precursor. In some embodiments, the metal-containing material is indium oxide (e.g., In2O3), and the first metal precursor is an indium precursor.

[0010] In some embodiments, the metal-containing material is aluminum nitride, and the first metal precursor is an aluminum precursor. In some embodiments, the metal-containing material is gallium nitride, and the first metal precursor is a gallium precursor. In some embodiments, the metal-containing material is indium nitride, and the first metal precursor is an indium precursor.

[0011] In some embodiments, the alkyl ligand attached to the metal atom is selected from methyl, ethyl, and straight-chain or branched-chain alkyls containing three, four, or five carbon atoms. In some embodiments, the first metal precursor includes two alkyl ligands bonded to the metal atom.

[0012] In some embodiments, the amidino ligand includes an acetamidinyl ligand. In some embodiments, the acetamido ligand is an alkylacetamido ligand. In some embodiments, the alkylacetamido ligand is a dialkylacetamido ligand. In some embodiments, one or two alkyls of the alkylacetamido ligand are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and sec-butyl.

[0013] In some embodiments, the first metal precursor is selected from N,N'-di-(isopropylformamido)dimethylaluminum, N,N'-di-(isopropylformamido)diethylaluminum, N,N'-di-(isopropylformamido)-di-n-propylaluminum, N,N'-di-(isopropylformamido)-di-tert-butylaluminum, and N,N'-di-(isopropylformamido)ethylmethylaluminum.

[0014] In some embodiments, the reactant is selected from an oxygen precursor, a nitrogen precursor, and a fluorine precursor. In some embodiments, the reactant is selected from molecular oxygen, ozone, hydrogen peroxide, and water. In some embodiments, the reactant is selected from NH3 and N2H4. In such embodiments, the metal-containing material is a metal nitride. In some embodiments, the reactant is selected from HF, NH4F, TiF4, and WF6. In such embodiments, the metal-containing material is a metal fluoride.

[0015] In some embodiments, a second metal precursor is provided into the reaction chamber to deposit a metal-containing material comprising two different metals. In some embodiments, the deposited metal-containing material has a thickness of from about 0.03 nm to about 10 nm.

[0016] In some embodiments, the first surface is a dielectric surface.

[0017] In some embodiments, the dielectric surface comprises silicon. In some embodiments, the dielectric surface comprises a material selected from the group consisting of SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, and combinations thereof.

[0018] In some embodiments, the dielectric surface comprises a metal oxide. In some embodiments, the metal oxide of the second surface is selected from aluminum oxide, hafnium oxide, and zirconium oxide.

[0019] In some embodiments, the second surface is a conductive surface. In some embodiments, the second surface comprises a material selected from metals, amorphous carbon, metal oxides, and metal nitrides. In some embodiments, the second surface comprises an elemental metal. In some embodiments, the metal of the second surface is selected from Cu, Co, Ru, W, Ti, Al, Ta, Nb, and Mo.

[0020] In some embodiments, the second surface comprises passivation. In some embodiments, the passivation comprises a passivation layer on the second surface. In some embodiments, the passivation layer comprises an organic polymer. In some embodiments, the organic polymer comprises polyimide.

[0021] In some embodiments, the method includes treating a first surface with an inhibitor reactant before providing a first metal precursor into a reaction chamber, and then depositing an organic polymer on a second surface. The organic polymer is deposited on the second surface to passivate the second surface. In some embodiments, the method includes treating a first surface with a silylating agent before providing a first metal precursor into a reaction chamber, and then depositing an organic polymer on a second surface.

[0022] In some embodiments, the first surface is an elemental metal surface. In some embodiments, the metal of the elemental metal surface is selected from Cu, Co, Ru, W, Ti, Al, Ta, Nb, and Mo. In some embodiments, the second surface is a dielectric surface. In some embodiments, the second surface is a metal oxide surface or a silicon-containing surface. In some embodiments, the second surface includes a passivation layer formed by silylating the second surface. In some embodiments, the second surface includes a passivation layer formed by treating the second surface with a metal halide such as NbF5. In some embodiments, the second surface includes an inhibition formed by treating the second surface with an inhibitor reactant.

[0023] In another aspect, a semiconductor processing assembly for selectively depositing a metal-containing material on a first surface of a substrate relative to a second surface of the substrate is disclosed. The semiconductor processing assembly includes one or more reaction chambers and a precursor injector system. The reaction chambers are configured and arranged to hold the substrate, and the precursor injector system is configured and arranged to provide a first metal precursor and a reactant in a gas phase into the reaction chambers. The first metal precursor includes a metal atom bound to an amidino ligand. The semiconductor processing assembly further includes a first metal precursor source container configured and arranged to hold the first metal precursor and a reactant source container configured and arranged to hold the reactant. The semiconductor processing assembly is configured and arranged to provide the first metal precursor and the reactant into the reaction chambers through the precursor injector system to selectively deposit the metal-containing material on the first surface of the substrate.

[0024] In some embodiments, the semiconductor processing assembly further includes one or more passivation source containers, and wherein the precursor injector system is configured and arranged to provide one or more passivating agents in a gas phase into the reaction chambers before providing the first metal precursor into the reaction chambers.

[0025] In one aspect, a semiconductor processing assembly is disclosed that is configured and arranged to perform the method according to the present disclosure.

[0026] The term dielectric is used in the description herein to simplify the distinction from metallic or metalloid surfaces. Those skilled in the art will understand that not all non-conductive surfaces are dielectric surfaces. For example, a metallic or metalloid surface can include an oxidized metal surface that is non-conductive or has a very high resistivity. The selective deposition process taught herein can deposit on a dielectric surface with minimal deposition on such adjacent non-conductive metallic or metalloid surfaces.

[0027] For embodiments in which one surface of the substrate comprises metal, that surface is referred to as a metal surface. In some embodiments, the metal surface consists of or consists essentially of one or more metals. The metal surface can be a metallic surface or a metalloid surface. In some embodiments, the metallic or metalloid surface can include metals, metal-containing materials, and / or mixtures thereof. In some embodiments, the metallic or metalloid surface can include surface oxidation. In some embodiments, the metal or metalloid material of the metallic or metalloid surface is conductive with or without surface oxidation. In some embodiments, the metallic or metalloid surface comprises one or more transition metals. In some embodiments, the metallic or metalloid surface comprises one or more transition metals in row 4 of the periodic table. In some embodiments, the metallic or metalloid surface comprises one or more transition metals in groups 4 to 11 of the periodic table. In some embodiments, the metallic or metalloid surface includes aluminum (Al). In some embodiments, the metallic or metalloid surface includes copper (Cu). In some embodiments, the metallic or metalloid surface includes tungsten (W). In some embodiments, the metallic or metalloid surface comprises cobalt (Co). In some embodiments, the metallic or metalloid surface comprises nickel (Ni). In some embodiments, the metallic or metalloid surface comprises niobium (Nb). In some embodiments, the metallic or metalloid surface comprises iron (Fe). In some embodiments, the metallic or metalloid surface includes molybdenum (Mo). In some embodiments, the metallic or metalloid surface comprises a metal selected from Al, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, and W. In some embodiments, the metallic or metalloid surface comprises a transition metal selected from Zn, Fe, Mn, and Mo.

[0028] In some embodiments, the metallic surface comprises titanium nitride. In some embodiments, the metal or metallic surface comprises one or more noble metals, such as Ru. In some embodiments, the metal or metallic surface comprises a conductive metal-containing material. In some embodiments, the metal or metallic surface comprises a conductive metal nitride. In some embodiments, the metal or metallic surface comprises a conductive metal carbide. In some embodiments, the metal or metallic surface comprises a conductive metal boride. In some embodiments, the metal or metallic surface comprises a combined conductive material. For example, the metal or metallic surface may comprise one or more of ruthenium oxide (RuOx), niobium carbide (NbCx), niobium boride (NbBx), nickel oxide (NiOx), cobalt oxide (CoOx), niobium oxide (NbOx), tungsten carbonitride (WNCx), tantalum nitride (TaN), or titanium nitride (TiN).

[0029] As used herein, the term "comprising" means including certain features, but does not exclude the presence of other features, provided they do not render the claim infeasible. In some embodiments, the term "comprising" includes "consisting of".

[0030] As used herein, the term "consisting of" means that no other features are present in the device / method / product except for the features following the said wording. When the term "consisting of" is used to refer to a compound, substance, or composition of substances, it means that the compound, substance, or composition of substances contains only the listed components. Similarly, when the term "consisting essentially of" is used to refer to a chemical compound, substance, or composition of substances, it means that the chemical compound, substance, or composition of substances contains the listed components, but may also contain trace elements and / or impurities that do not significantly affect the characteristics of the said chemical compound, substrate, or composition of substances. Nevertheless, in some embodiments, the chemical compound, substance, or composition of substances may include other components as trace elements or impurities in addition to the listed components.

[0031] The term "substantially" as applied to a composition, method, or system generally refers to a proportion of a value, property, characteristic, etc., or conversely to its lack, i.e., at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9%, or higher, or any proportion between about 70% and about 100%. In some embodiments, the term "substantially" refers to a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0032] The term "substantially" as applied to a composition, method, or system generally means that additional components do not substantially change the properties and / or functions of the composition, method, or system.

[0033] In the specification, it should be understood that the terms "on" or "above" can be used to describe relative positional relationships. Another element, film, or layer can be directly on the layer, or another layer (intermediate layer) or element can be inserted therebetween, or a layer can be disposed on the layer but not completely cover the surface of the layer. Thus, unless the term "directly" is used alone, the terms "on" or "above" will be interpreted as relative concepts. Similarly, it should be understood that the terms "under", "beneath", or "below" will be interpreted as relative concepts. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings, which are included to provide a further understanding of the disclosure and form a part of this specification, illustrate exemplary embodiments and, together with the description, help to explain the principles of the disclosure.

[0035] In the drawings:

[0036] Figure 1 is a block diagram of an exemplary embodiment of a method according to the present disclosure.

[0037] Figure 2 is a block diagram of another exemplary embodiment of a method according to the present disclosure.

[0038] Figure 3 is a schematic diagram of an embodiment of a semiconductor processing component according to the present disclosure.

[0039] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. The illustrations presented herein are not meant to be actual views of any particular material, structure, or device, but are merely idealized representations for describing embodiments of the present disclosure. For example, the dimensions of some elements in the figures may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0040] The following description of exemplary embodiments of the methods and semiconductor processing components provided is merely exemplary and for illustrative purposes only. The following description is not intended to limit the scope of the present disclosure or the claims. Additionally, the recitation of multiple embodiments with the indicated features is not intended to exclude other embodiments having additional features or other embodiments combining different combinations of the recited features. For example, various embodiments are set forth as exemplary embodiments and may be recited in the dependent claims. Unless otherwise stated, the exemplary embodiments or their components may be combined or may be applied separately from each other.

[0041] The headings (if any) provided herein are for convenience only and do not necessarily affect the scope or meaning of the claimed subject matter.

[0042] In one aspect, a method for selectively depositing a metal-containing material on a first surface of a semiconductor substrate relative to a second surface of the substrate is disclosed. The metal-containing material can be deposited as a layer. As used herein, the terms "layer" and / or "membrane" can refer to any continuous or discontinuous material, such as a material deposited by the methods disclosed herein. For example, a layer and / or membrane can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or atomic and / or molecular clusters. A membrane or layer can include a material or layer having pinholes, which can be at least partially continuous. In some embodiments, the layer according to the present disclosure is substantially continuous. In some embodiments, the layer according to the present disclosure is continuous.

[0043] The deposition method according to the present invention includes providing a substrate in a reaction chamber. The substrate can be any one or more underlying materials that can be used to form or on which structures, devices, circuits, or layers can be formed. The substrate can include bulk materials, such as silicon (e.g., single-crystalline silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials, and can include one or more layers covering or underlying the bulk material. In addition, the substrate can include various features, such as depressions, protrusions, etc., formed in or on at least a portion of the substrate layer. For example, the substrate can include a bulk semiconductor material and a layer of insulating or dielectric material covering at least a portion of the bulk semiconductor material. The substrate can include nitrides, such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single-crystalline materials. In some embodiments of the present disclosure, the substrate includes silicon. As described above, in addition to silicon, the substrate can include other materials. The other materials can form layers. Specifically, the substrate can include a partially fabricated semiconductor device. The substrate according to the present disclosure includes a first surface and a second surface. The first surface and the second surface have different material properties, allowing for the selective deposition of a metal-containing material, such as a metal oxide, metal nitride, or metal fluoride, on the first surface.

[0044] In some embodiments, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition process. In some embodiments, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition process. In some embodiments, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some embodiments, before or at the beginning of the selective deposition process, the substrate surface may be exposed to plasma, radicals, excited species, and / or atomic species. In some embodiments, before or at the beginning of the selective deposition process, the substrate surface may be exposed to hydrogen plasma, radicals, or atomic species. In some embodiments, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition process. However, in some embodiments, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0045] The method includes providing a substrate in a reaction chamber and depositing a metal-containing material on a first surface of the substrate by a cyclic vapor deposition process. Thus, the method of depositing a metal-containing material according to the present invention includes providing a substrate in a reaction chamber. In other words, the substrate is in a space where deposition conditions can be controlled. The reaction chamber may be a single-wafer reactor. Alternatively, the reaction chamber may be a batch reactor. The reaction chamber may form part of a gas-phase processing assembly for manufacturing semiconductor devices. The processing assembly may include one or more multi-station processing chambers. In some embodiments, the substrate moves between processing stations of the multi-station processing chamber. The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. The various stages of the method may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chambers of a cluster tool, or the deposition stations of a multi-station processing chamber.

[0046] In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a showerhead reactor. In some embodiments, the reaction chamber may be a hot-wall reactor. In some embodiments, the reaction chamber may be a spatially separated reactor. In some embodiments, the reaction chamber may be a single-wafer atomic layer deposition (ALD) reactor. In some embodiments, the reaction chamber may be a high-volume manufacturing single-wafer ALD reactor. In some embodiments, the reaction chamber may be a batch reactor for simultaneously manufacturing multiple substrates.

[0047] The reaction chamber can form part of an ALD assembly. The reaction chamber can form part of a chemical vapor deposition (CVD) assembly. The deposition assembly can be an ALD or CVD deposition assembly, but in some processing steps, molecular layer deposition (MLD) can also be used for certain parts of the deposition process flow. In some embodiments, the method is performed in a single reaction chamber of a combination tool, but other, previous, or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same combination tool. Optionally, the assembly including the reaction chamber can be provided with a heater to activate the reaction by raising the temperature of one or more substrates and / or reactants and / or precursors.

[0048] The vapor deposition process according to the present disclosure is a cyclic deposition process. Generally, in a cyclic deposition process according to the present disclosure, such as ALD and MLD, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the substrate surface (e.g., the substrate surface that can include previously deposited material or other materials from a previous deposition cycle). In some embodiments, the precursor on the substrate surface does not readily react with additional precursor (i.e., the deposition of the precursor can be a partial or fully self-limiting reaction). Thereafter, another precursor or reactant can be introduced into the reaction chamber for converting the chemisorbed precursor into the desired material on the deposition surface. The second precursor such as a reactant can react further with the precursor. During one or more cycles, e.g., during each step of each cycle, a purge step can be utilized to remove any excess precursor and / or any excess reactant and / or reaction by-products from the processing chamber. Thus, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the precursor into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the first precursor into the reaction chamber and after providing the second precursor into the reaction chamber. Without limiting the present disclosure to any specific theory, ALD and MLD can be similar processes in terms of self-limiting reactions and slower and more controllable layer growth rates compared to CVD. Generally, ALD is used for depositing inorganic materials, while in MLD, the precursors can be fully organic molecules.

[0049] The process can include one or more cyclic stages. In some embodiments, the process includes one or more non-cyclic (i.e., continuous) stages. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In such embodiments, the process includes a continuous flow of a first metal precursor or reactant. In some embodiments, one or more of the precursor and the reactant are continuously provided in the reaction chamber.

[0050] The vapor deposition process according to the present disclosure includes providing a first metal precursor in a gaseous phase to a reaction chamber and providing a reactant in a gaseous phase to the reaction chamber. In some embodiments, at least one of the first metal precursor and the reactant is provided to the reaction chamber in pulses. In some embodiments, the first metal precursor is supplied in pulses, the reactant is supplied in pulses, and the reaction chamber is purged between consecutive pulses of the first metal precursor and the reactant. The duration of providing the first metal precursor and / or the reactant to the reaction chamber (i.e., the first precursor pulse time and the reactant pulse time, respectively) can be, for example, from about 0.01 second to about 60 seconds, such as from about 0.1 second to about 10 seconds, or from about 0.5 second to about 20 seconds, or from about 0.5 second to about 10 seconds, or from about 2 seconds to about 15 seconds, or from about 10 seconds to about 30 seconds, or from about 10 seconds to about 60 seconds, or from about 20 seconds to about 60 seconds. The duration of the first metal precursor or reactant pulse can be, for example, 0.03 second, 0.1 second, 0.5 second, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 4 seconds, 5 seconds, 8 seconds, 10 seconds, 12 seconds, 15 seconds, 25 seconds, 30 seconds, 40 seconds, 50 seconds, or 60 seconds. In some embodiments, the first metal precursor pulse time can be at least 5 seconds or at least 10 seconds. In some embodiments, the first metal precursor pulse time can be at most 5 seconds, or at most 10 seconds, or at most 20 seconds, or at most 30 seconds. In some embodiments, the reactant pulse time can be at least 5 seconds, or at least 10 seconds, or at least 20 seconds. In some embodiments, the reactant pulse time can be at most 5 seconds, or at most 10 seconds, or at most 20 seconds, or at most 30 seconds.

[0051] The pulse times of the first metal precursor and the reactant can vary independently according to the process under discussion. The selection of suitable pulse times can depend on the substrate topology. For higher aspect ratio structures, longer pulse times may be required to achieve sufficient surface saturation in different regions of the high aspect ratio structure. Additionally, the selected first metal precursor and reactant chemistries can affect the suitable pulse times. For process optimization purposes, shorter pulse times may be preferred as long as appropriate layer characteristics can be achieved. In some embodiments, the first metal precursor pulse time is longer than the reactant pulse time. In some embodiments, the reactant pulse time is longer than the first metal precursor pulse time. In some embodiments, the first metal precursor pulse time is the same as the reactant pulse time.

[0052] In some embodiments, providing the first metal precursor and / or reactant to the reaction chamber includes pulsing the first metal precursor and the reactant onto the substrate. In certain embodiments, a pulse time in the range of several minutes can be used for the first metal precursor and / or the reactant. In some embodiments, the first metal precursor can be pulsed more than once, such as two, three, or four times, before the reactant is pulsed into the reaction chamber. Similarly, the reactant can have more than one pulse, such as two, three, or four pulses, before the first metal precursor is pulsed (i.e., provided) into the reaction chamber.

[0053] The pulses of the first metal precursor and the reactant can together form a deposition cycle. As described above, the process is a cyclic deposition process. Thus, the precursor is repeatedly provided (i.e., pulsed) to the reaction chamber. Depending on, for example, the growth rate of the metal-containing material and the desired thickness of the metal-containing material, the pulsing can be repeated as needed. In some embodiments, the growth rate of the metal-containing material is from about / cycle to about / cycle. In some embodiments, the growth rate of the metal-containing material is from about / cycle to about / cycle, such as about / cycle or about / cycle. In some embodiments, the growth rate of the metal-containing material is from about / cycle to about / cycle, such as about / cycle or about / cycle. In some embodiments, the growth rate of the metal-containing material is from about / cycle to about / cycle, such as about / cycle or about / cycle or about / cycle. In some embodiments, the growth rate of the metal-containing material is from about / cycle to about cycles, such as about / cycle.

[0054] The thickness of the metal-containing material can be selected according to the application in question. In some embodiments, the deposited metal-containing material has a thickness of about 0.03 nm to about 10 nm. Thus, depending on the growth rate of the metal-containing material, the deposition cycle can be performed about 2 to about 800 times. For example, the deposition cycle can be performed about 2, 3, 5, 7, 10, 13, 15, 20, 40, 50, 100, 200, 300, 500, or 600 times.

[0055] In some embodiments, the metal-containing material according to the present disclosure is deposited at a pressure of at least 0.01 Torr to at most 100 Torr, or at a pressure of at least 0.1 Torr to at most 50 Torr, or at a pressure of at least 0.5 Torr to at most 25 Torr, or at a pressure of at least 1 Torr to at most 10 Torr, or at a pressure of at least 2 Torr to at most 5 Torr. For example, the metal-containing material can be deposited at a pressure of about 1 Torr, about 3 Torr, about 6 Torr, about 8 Torr, about 9 Torr, about 12 Torr, or about 18 Torr.

[0056] In some embodiments, the cyclic deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, a temperature elevated relative to the ambient temperature promotes chemical reactions. Generally, in the absence of other external energy sources (such as plasma, radicals, or other forms of radiation), the elevated temperature provides the energy required to form the target material. In some embodiments, the method according to the present disclosure includes a plasma-enhanced deposition method, such as PEALD or PECVD. For example, in some embodiments, the deposition of the metal-containing material can be carried out by PEALD or PECVD.

[0057] In some embodiments, a second metal precursor is provided into the reaction chamber. The second metal precursor can contain the same metal as or a different metal from the first metal precursor. In embodiments where the second metal precursor includes a metal different from the first metal precursor, the metal-containing material includes two metals. In some embodiments, the metal-containing material mainly includes the first metal, and the second metal is used as a dopant. Thus, in some embodiments, a second metal precursor is provided into the reaction chamber to deposit a metal-containing material containing two different metals. In some embodiments, the deposition cycle includes providing a second metal precursor into the reaction chamber. The second metal precursor can be used to dope the metal-containing material to modify its properties according to a specific application. The second metal precursor can be, for example, yttrium (Y), or a second metal selected from Al, In, and Ga.

[0058] In the method according to the present disclosure, the first metal precursor includes a heteroleptic precursor, which includes a Group 13 metal atom, an amidino ligand, and an alkyl ligand attached to the metal atom. In some embodiments, the metal of the metal-containing material is selected from aluminum (Al), gallium (Ga), and indium (In). In some embodiments, the first metal precursor is selected from aluminum precursors, gallium precursors, and indium precursors.

[0059] In some embodiments, the metal-containing material is alumina and the first metal precursor is an aluminum precursor. In some embodiments, the metal-containing material is gallium oxide and the first metal precursor is a gallium precursor. In some embodiments, the metal-containing material is indium oxide and the first metal precursor is an indium precursor. In some embodiments, the metal-containing material is aluminum nitride and the first metal precursor is an aluminum precursor. In some embodiments, the metal-containing material is gallium nitride and the first metal precursor is a gallium precursor. In some embodiments, the metal-containing material is indium nitride and the first metal precursor is an indium precursor. In some embodiments, the metal-containing material is aluminum fluoride and the first metal precursor is an aluminum precursor. In some embodiments, the metal-containing material is gallium fluoride and the first metal precursor is a gallium precursor. In some embodiments, the metal-containing material is indium fluoride and the first metal precursor is an indium precursor.

[0060] In some embodiments, the first metal precursor consists of a metal atom bonded to an amidine ligand and two alkyl ligands. In some embodiments, the first metal precursor does not contain a cyclopentadienyl ligand.

[0061] In some embodiments, the alkyl ligands attached to the metal atom are selected from methyl, ethyl, and straight-chain or branched-chain alkyls having three, four, or five carbon atoms. In some embodiments, the first metal precursor includes two alkyl ligands bonded to the metal atom. In some embodiments, one alkyl ligand is methyl. In some embodiments, one alkyl ligand is ethyl. In some embodiments, one alkyl ligand is n-propyl. In some embodiments, one alkyl ligand is isopropyl. In some embodiments, one alkyl ligand is n-butyl. In some embodiments, one alkyl ligand is isobutyl. In some embodiments, one alkyl ligand is tert-butyl. In some embodiments, one alkyl ligand is sec-butyl. In some embodiments, one alkyl ligand is n-pentyl. In some embodiments, one alkyl ligand is tert-pentyl. In some embodiments, one alkyl ligand is neopentyl. In some embodiments, one alkyl ligand is isopentyl. In some embodiments, one alkyl ligand is sec-pentyl. In some embodiments, the two alkyl ligands are the same. In some embodiments, both alkyl ligands are methyl. In some embodiments, both alkyl ligands are ethyl. In some embodiments, both alkyl ligands are n-propyl. In some embodiments, both alkyl ligands are isopropyl.

[0062] In some embodiments, the amidine ligand includes an acetamidine ligand. In some embodiments, the acetamido ligand is an alkylacetamido ligand. In some embodiments, the alkylacetamido ligand is a dialkylacetamido ligand. In some embodiments, one or both alkyls of the alkylacetamido ligand are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and sec-butyl.

[0063] In some embodiments, the first metal precursor is selected from N,N'-bis-(isopropylformamido)dimethylaluminum, N,N'-bis-(isopropylformamido)diethylaluminum, N,N'-bis-(isopropylformamido)-dipropylaluminum, N,N'-bis-(isopropylformamido)-di-tert-butylaluminum, and N,N'-bis-(isopropylformamido)ethylmethylaluminum. In some embodiments, the metal precursor is selected from N,N'-bis-(isopropylformamido)dimethylindium, N,N'-bis-(isopropylformamido)diethylindium, N,N'-bis-(isopropylformamido)-dipropylindium, N,N'-bis-(isopropylformamido)-di-tert-butylindium, and N,N'-bis-(isopropylformamido)ethylmethylindium. In some embodiments, the metal precursor is selected from N,N'-bis-(isopropylformamido)dimethylgallium, N,N'-bis-(isopropylformamido)diethylgallium, N,N'-bis-(isopropylformamido)-dipropylgallium, N,N'-bis-(isopropylformamido)-di-tert-butylgallium, and N,N'-bis-(isopropylformamido)ethylmethylgallium.

[0064] In some embodiments, the reactant is selected from an oxygen precursor, a nitrogen precursor, and a fluorine precursor. In some embodiments, the reactant is selected from ozone (O3), molecular oxygen (O2), oxygen atoms (O), oxygen plasma, oxygen ions, oxygen radicals, oxygen excited species, water (H2O), and hydrogen peroxide (H2O2). In some embodiments, the metal-containing material is a metal oxide, and the reactant is selected from molecular oxygen, ozone, hydrogen peroxide, and water. In some embodiments, the metal-containing material is a metal oxide, and the reactant is molecular oxygen. In some embodiments, the metal-containing material is a metal oxide, and the reactant is ozone. In some embodiments, the metal-containing material is a metal oxide, and the reactant is hydrogen peroxide. In some embodiments, the metal-containing material is a metal oxide, and the reactant is water.

[0065] In some embodiments, the reactant is selected from NH3 and N2H4. In some embodiments, the nitrogen precursor includes hydrazine. In some embodiments, the nitrogen precursor consists of or consists essentially of hydrazine. In some embodiments, the nitrogen precursor includes hydrazine substituted with one or more alkyl or aryl substituents. In some embodiments, the nitrogen precursor consists of or consists essentially of hydrazine substituted with one or more alkyl or aryl substituents. In some embodiments, the hydrazine derivatives include alkyl hydrazines, which include at least one of the following: tert-butylhydrazine (C4H9N2H3), methylhydrazine (CH3NHNH2), 1,1-dimethylhydrazine ((CH3)2NNH2), 1,2-dimethylhydrazine (CH3)NHNH(CH3), ethylhydrazine, 1,1-diethylhydrazine, 1-ethyl-1-methylhydrazine, isopropylhydrazine, tert-butylhydrazine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine, N-aminopiperidine, N-aminopyrrole, N-aminopyrrolidine, N-methyl-N-phenylhydrazine, 1-amino-1,2,3,4-tetrahydroquinoline, N-aminopiperazine, 1,1-dibenzylhydrazine, 1,2-dibenzylhydrazine, 1-ethyl-1-phenylhydrazine, 1-aminoazacyclohexane, 1-methyl-1-(m-tolyl)hydrazine, 1-ethyl-1-(p-tolyl)hydrazine, 1-aminoimidazole, 1-amino-2,6-dimethylpiperidine, N-aminoaziridine or azo-tert-butane. In such embodiments, the metal-containing material is a metal nitride.

[0066] In some embodiments, the reactant is selected from HF, NH4F, TiF4 and WF6. In such embodiments, the metal-containing material is a metal fluoride.

[0067] Without limiting the present disclosure to any particular theory, the reactant provided to the reaction chamber can react with the first and / or second metal precursor or its derivative chemisorbed on the first surface of the substrate to form a metal-containing material on the first surface.

[0068] The present disclosure relates to a selective deposition process. The selectivity can be given as a percentage calculated by [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). The deposition can be measured by any of a variety of methods. In some embodiments, the deposition can be given as the measured thickness of the deposited material. In some embodiments, the deposition can be given as the measured amount of the deposited material.

[0069] In some embodiments, the selectivity is greater than about 30%. In some embodiments, the selectivity is greater than about 50%. In some embodiments, the selectivity is greater than about 75% or greater than about 85%. In some embodiments, the selectivity is greater than about 90% or greater than about 93%. In some embodiments, the selectivity is greater than about 95% or greater than about 98%. In some embodiments, the selectivity is greater than about 99% or even greater than about 99.5%. In embodiments, the selectivity may vary with the duration or thickness of the deposition.

[0070] In some embodiments, deposition occurs only on the first surface and not on the second surface. In some embodiments, the deposition on the first surface of the substrate has at least about 80% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some embodiments, the deposition on the first surface of the substrate has at least about 50% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some embodiments, the deposition on the first surface of the substrate has at least about 10% selectivity relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications.

[0071] In some embodiments, the selective deposition is inherent and does not require additional processing steps beyond those conveniently performed on the substrate. However, in some embodiments, the second surface may be passivated prior to depositing the metal-containing material on the first surface. The selectivity may be inherent to a particular thickness of the deposited material and is lost if the deposition continues beyond a specific process threshold. Thus, prior to the loss of selectivity, a metal-containing material, such as about 0.1 nm, about 0.5 nm, about 1 nm, about 2 nm, about 3 nm, about 5 nm, or about 6 nm, may be deposited. By passivating the second surface, the contrast between the first and second surfaces can be enhanced. Alternatively or additionally, an intermittent etch stage using, for example, a plasma (such as a hydrogen plasma) can be used to maintain sufficient selectivity of the process.

[0072] In some embodiments, the second surface is passivated. Thus, in some embodiments, the second surface includes passivation. Passivation can be performed using an inhibitor reactant such as a metal halide or a silylating agent. In some embodiments, the metal halide or the silylating agent can be used as the inhibitor reactant. The selected inhibitor reactant, which can be used for the final passivation of the second surface or can be used on the first surface to direct the passivation layer on the second surface of the substrate, may have an impact on the selectivity of subsequent deposition steps. In some embodiments, the selection of the inhibitor reactant can affect, for example, the roughness of the subsequently deposited layer. In some embodiments, passivation includes a passivation layer. In some embodiments, the passivation layer includes an organic polymer. In some embodiments, the organic polymer includes polyimide. In some embodiments, passivation includes the silylation of the second surface.

[0073] In some embodiments, the first surface is a dielectric surface. In some embodiments, the first surface is a low-k surface. Here, a low-k surface refers to a surface with a k value at most similar to that of silicon oxide. In some embodiments, the first surface includes an oxide. In some embodiments, the first surface includes a nitride. In some embodiments, the first surface includes silicon. In some embodiments, the first surface includes a silicon-based dielectric material. Examples of silicon-containing dielectric materials include silicon oxide-based materials, including grown or deposited silicon dioxide, doped and / or porous oxides, and native oxide on silicon. In some embodiments, the first surface includes silicon oxide. In some embodiments, the first surface is a silicon oxide surface, such as a native oxide surface, a thermal oxide surface, or a chemical oxide surface. In some embodiments, the first surface includes carbon. In some embodiments, the first surface includes SiN. In some embodiments, the first surface includes SiOC. In some embodiments, the first surface is an etch stop layer. The etch stop layer can include, for example, a nitride. In some embodiments, the first dielectric surface includes a material selected from the group consisting of SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, and combinations thereof.

[0074] In some embodiments, the substrate includes a first dielectric surface and a second metal or metallic surface. In some embodiments, the substrate includes a first metal-containing material surface. In some embodiments, the first surface can include -OH groups. In some embodiments, the first surface can be a SiO2-based surface. In some embodiments, the first surface can include Si-O bonds. In some embodiments, the first surface can include a SiO2-based low-k material. In some embodiments, the first surface can contain more than about 30% or more than about 50% of SiO2. In certain embodiments, the first surface can include a silicon dioxide surface.

[0075] In some embodiments, the first surface is a SiO2 surface, and the second surface is a metal surface or an amorphous carbon surface or a metal oxide surface or a metal nitride surface. In some embodiments, the first surface is a SiN surface, and the second surface is a metal surface, such as an elemental metal surface. In some embodiments, the first surface is a SiOC surface, and the second surface is a metal surface. In some embodiments, the first surface is a SiON surface, and the second surface is a metal surface. In some embodiments, the first surface is a SiOCN surface, and the second surface is a metal surface. The second metal surface can be, for example, a copper surface, a ruthenium surface, a tungsten surface, or a cobalt surface.

[0076] In some embodiments, the dielectric material of the first surface includes a metal oxide. Thus, in some embodiments, a metal-containing material is selectively deposited on the first metal oxide surface relative to the second surface. In some embodiments, the first surface includes alumina. In some embodiments, the first surface is a high-k surface, such as a hafnium oxide-containing surface, a lanthanum oxide-containing surface, or a zirconium oxide-containing surface.

[0077] In some embodiments, a metal-containing material is selectively deposited on a first surface including the metal-containing material relative to another surface. The metal-containing material surface can be, for example, a tungsten oxide (WOx) surface, a hafnium oxide (HfOx) surface, a titanium oxide (TiOx) surface, an alumina (AlOx) surface, or a zirconium oxide (ZrOx) surface. In some embodiments, the metal-containing material surface is an oxidized surface of a metallic material. In some embodiments, the metal-containing material surface is produced by oxidizing at least the surface of the metallic material using an oxygen-containing compound, such as a compound containing O3, H2O, H2O2, O2, oxygen atoms, plasma, or radicals, or a mixture thereof. In some embodiments, the metal-containing material surface is a native oxide formed on the metallic material.

[0078] In some embodiments, a metal-containing material is selectively deposited on a first dielectric surface of a substrate relative to a second conductive (e.g., metal or metallic) surface of the substrate. In some embodiments, the first surface contains hydroxyl groups (-OH). In some embodiments, the first surface can additionally include hydrogen (-H) terminations, such as an HF-etched Si or HF-etched Ge surface. In such embodiments, the surface of interest will be considered to include the -H terminations and the material underlying the -H terminations. In some embodiments, the first surface and the second surface are adjacent to each other.

[0079] In some embodiments, the first surface is a dielectric surface and the second surface is a conductive surface. In some embodiments, the second surface comprises a material selected from metals, amorphous carbon, metal oxides, and metal nitrides. In some embodiments, the second surface comprises elemental metal. In some embodiments, the second surface consists of or consists essentially of elemental metal. In some embodiments, the metal of the second surface is selected from Cu, Co, Ru, W, Ti, Al, Ta, Nb, and Mo. In some embodiments, the second surface is an amorphous carbon surface. In some embodiments, the second surface is a metal oxide surface. In some embodiments, the second surface is a metal nitride surface. In other words, in some embodiments, the first surface consists of or consists essentially of metal nitride.

[0080] In embodiments where the first surface is a dielectric surface, the second surface can be selectively passivated before depositing the metal-containing material on the first surface. Thus, in some embodiments, the second surface comprises passivation. In some embodiments, the passivation comprises a passivation layer on the second surface. In some embodiments, the passivation layer comprises an organic polymer. In some embodiments, the organic polymer comprises polyimide.

[0081] In some embodiments, the passivation is formed by silylation or metal halide treatment and is used to enhance the contrast between two dielectric surfaces before depositing the metal-containing material on the first dielectric surface. In some embodiments, the first surface is a metal oxide surface, such as a high-k surface, and the second surface is a passivated low-k surface, such as a silicon-containing surface. In some embodiments, the first surface is a hafnium oxide surface and the second surface is a silylated silicon-containing surface. In some embodiments, the first surface is a zirconium oxide surface and the second surface is a silylated silicon-containing surface. In some embodiments, the first surface is a hafnium zirconium oxide surface and the second surface is a silylated silicon-containing surface. The silicon-containing second surface, such as a SiO2, SiN, SiC, SiON, or SiOC surface, can be selectively silylated relative to the first surface by a silylating agent. The silylating agent according to the present disclosure is provided in the gas phase. In some embodiments, the silicon-containing second surface is silylated by exposure to a silylating agent, which is such as an alkylsilane, e.g., allyltrimethylsilane (TMS-A), a halosilane, e.g., trimethylchlorosilane (TMS-Cl) or octadecyltrichlorosilane (ODTCS), an imidazole, e.g., N-(trimethylsilyl)imidazole (TMS-Im), a silazane, e.g., hexamethyldisilazane (HMDS), or a silylamine, e.g., N-(trimethylsilyl)dimethylamine or 1,1,1-trimethoxy-N-silylation can passivate the second dielectric surface and prevent the deposition of the metal-containing material on the first surface.

[0082] In some embodiments, the method includes treating a second surface with a silylating agent to passivate the second surface before providing a first metal precursor into a reaction chamber, and then depositing a metal-containing material on a first surface.

[0083] In some embodiments, the method includes treating a first surface with a silylating agent before providing a first metal precursor into a reaction chamber, and then depositing an organic polymer on a second surface to passivate the second surface.

[0084] The first surface is a metal surface.

[0085] In some embodiments, the first surface is selected from a metal surface, an amorphous carbon surface, a metal oxide surface, and a metal nitride surface. In some embodiments, the first surface comprises a metal.

[0086] In some embodiments, the first surface is an elemental metal surface. For the purposes of the present disclosure, an elemental metal surface is a surface that consists of or consists essentially of an elemental metal. Thus, the oxidation state of most of the metal atoms in such a surface can be 0. In other words, in some embodiments, the first surface consists of or consists essentially of an elemental metal.

[0087] In some embodiments, the metal of the elemental metal surface is selected from Cu, Co, Ru, W, Ti, Al, Ta, Nb, and Mo. In some embodiments, the second surface is a dielectric surface. In some embodiments, the second surface is a metal oxide surface or a silicon-containing surface. In some embodiments, the second surface comprises a passivation formed by silylating the second surface.

[0088] In some embodiments, the first surface is an elemental tungsten (W) surface. In some embodiments, the first surface is a titanium nitride (TiN) surface. In some embodiments, the first surface is an elemental tungsten (W) surface and the second surface is a silicon oxide surface. In some embodiments, the first surface is a titanium nitride (TiN) surface and the second surface is a silicon oxide surface.

[0089] In some embodiments, the first surface comprises a metal oxide, such as a high-k oxide. In some such embodiments, the metal on the first surface is selected from aluminum oxide, hafnium oxide, and zirconium oxide. In some embodiments, the first surface comprises a high-k material. In some embodiments, the high-k material is selected from hafnium oxide, zirconium oxide, and combinations thereof. In some embodiments, the first surface is a hafnium oxide surface. In some embodiments, the first surface is a zirconium oxide surface. In some embodiments, the first surface is a hafnium zirconium oxide surface. In some embodiments, the first surface is a hafnium oxide surface and the second surface is a silicon-containing surface. In some embodiments, the first surface is a zirconium oxide surface and the second surface is a silicon-containing surface. In some embodiments, the first surface is a hafnium zirconium oxide surface and the second surface is a silicon-containing surface.

[0090] In embodiments where the first surface is a metal surface, passivation can be carried out by silylating the second dielectric surface with a silylating agent. The silylating agent can comprise a silicon atom bonded to a dialkylamine. Thus, the silylating agent has the formula according to Formula I:

[0091] Formula I: R2N-SiR’3.

[0092] In some embodiments of Formula I, each R and R’ is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1,1-dimethylpropyl, 3-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,2-dimethylpropyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, and 2-ethylbutyl. In some embodiments, each R and R’ is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. In some embodiments, the two Rs are the same alkyl group. In some embodiments, both Rs are methyl. In some embodiments, both Rs are ethyl. In some embodiments, both Rs are n-propyl. In some embodiments, both Rs are isopropyl. In some embodiments, all R’s are the same alkyl group. In some embodiments, all R’s are methyl. In some embodiments, all R’s are ethyl. In some embodiments, both R’s are n-propyl. In some embodiments, both R’s are isopropyl. In some embodiments, all Rs and R’s are the same alkyl group. In some embodiments, all Rs and R’s are methyl. In some embodiments, all Rs and R’s are ethyl. In some embodiments, all Rs and R’s are n-propyl. In some embodiments, all Rs and R’s are isopropyl.

[0093] In some embodiments of Formula I, at least one R’ is selected from a hydroxyl group and C1 to C5 alkoxide groups. In such embodiments, the alkoxide group is attached to silicon through an oxygen atom. In some embodiments, each alkoxide group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy. In some embodiments, one R’ is selected from a hydroxyl group and C1 to C5 alkoxide groups. In some embodiments, two R’s are selected from a hydroxyl group and C1 to C5 alkoxide groups. In some embodiments, three R’s are selected from a hydroxyl group and C1 to C5 alkoxide groups. In some embodiments, none of the R’s is a hydroxyl group. In some embodiments, one R’ is a hydroxyl group. In some embodiments, two R’s are hydroxyl groups. In some embodiments, three R’s are hydroxyl groups. In some embodiments, one R’ is a hydroxyl group and two R’s are methoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are ethoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are n-propoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are isopropoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are n-butoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are isobutoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are sec-butoxy groups. In some embodiments, one R’ is a hydroxyl group and two R’s are tert-butoxy groups. In some embodiments, two R’s are hydroxyl groups and one of the R’s is a methoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is an ethoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is an n-propoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is an isopropoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is an n-butoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is an isobutoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is a sec-butoxy group. In some embodiments, two R’s are hydroxyl groups and one of the R’s is a tert-butoxy group. In some embodiments, all three R’s are methoxy groups. In some embodiments, all three R’s are ethoxy groups. In some embodiments, all three R’s are n-propoxy groups. In some embodiments, all three R’s are isopropoxy groups. In some embodiments, all three R’s are n-butoxy groups. In some embodiments, all three R’s are isobutoxy groups. In some embodiments, all three R’s are sec-butoxy groups. In some embodiments, all three R’s are tert-butoxy groups.

[0094] In embodiments where the first surface comprises a metal, amorphous carbon, metal oxide, or metal nitride, according to the present disclosure, the second silicon-containing surface is silylated with a silylating agent to passivate the second surface from deposition of the metal-containing material. However, in embodiments where the first surface comprises a silicon-containing material, the silylating agent can be used to prevent deposition of a passivation layer, such as an organic polymer layer, on the first silicon-containing surface. An organic passivation layer, such as a passivation layer containing polyimide, can be deposited on the second surface, which can comprise a metal, metal nitride, metal oxide, or amorphous carbon. Thus, a material containing a target metal, such as an oxide, nitride, or fluoride of aluminum, indium, or gallium, is deposited on the first surface. In some embodiments, the silylation can be removed prior to deposition of the metal-containing material.

[0095] In some embodiments, alternative passivating agents can be used. For example, niobium pentafluoride (NbF5) can be used to passivate a dielectric surface. By way of example, according to the present disclosure, silicon-containing surfaces, including thermally oxidized silicon and native oxidized silicon, can be passivated against deposition of metal-containing materials.

[0096] The second surface can be covered with a passivation layer. In some embodiments, the passivation layer comprises an organic polymer. In some embodiments, the organic polymer comprises polyimide. In some embodiments, silylation and deposition of the organic polymer are performed in the same reaction chamber.

[0097] Deposition of the organic polymer according to the present disclosure is performed by a cyclic vapor deposition process. For example, deposition of the organic polymer can be an MLD process. Deposition of the organic polymer includes providing a first gaseous organic precursor to the reaction chamber and providing a second gaseous organic precursor to the reaction chamber. Providing the first gaseous organic precursor and providing the second gaseous organic precursor can define a deposition cycle. The deposition cycle can be repeated until an organic polymer of a suitable thickness has been deposited on the second surface of the substrate. The first and second gaseous organic precursors selectively form an organic polymer on the second surface. In some embodiments, the organic polymer comprises polyimide. In some embodiments, the organic polymer comprises polyamide. In some embodiments, the organic polymer forms a passivation layer on the second surface.

[0098] According to the processes described herein, various reactants can be used to deposit the organic polymer. For example, in some embodiments, the first organic precursor is a diamine. In some embodiments, the first reactant can be, for example, 1,6-diaminohexane, 1,3-diaminopentane, a triamine, such as tris(2-aminoethyl)amine, or a cyclic compound containing at least two primary amine groups, such as 1,4-diaminocyclohexane or p-phenylenediamine. In some embodiments, the substrate is contacted with the first organic precursor before being contacted with the second organic precursor. Thus, in some embodiments, the substrate can be contacted with a diamine before being contacted with the second organic precursor.

[0099] In some embodiments, the second organic precursor is capable of reacting with the adsorbed species of the first reactant under deposition conditions. For example, in some embodiments, the second organic precursor is an acid anhydride, such as furan-2,5-dione (maleic anhydride). The acid anhydride can be a dianhydride, such as pyromellitic dianhydride (PMDA). In some embodiments, the second reactant can be any other monomer having two reactive groups that will react with the first reactant.

[0100] In some embodiments, the organic precursor does not contain metal atoms. In some embodiments, the organic precursor does not contain metalloid atoms. In some embodiments, one of the organic precursors includes a metal or metalloid atom. In some embodiments, the organic precursor contains carbon and hydrogen and one or more of the following elements: N, O, S, P, or a halide, such as Cl or F.

[0101] In some embodiments, the organic precursor for the selective deposition of an organic polymer can be an aliphatic compound containing 1-6 carbon atoms, 2-5 carbon atoms, 2-4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms. In some embodiments, the bonds between carbon atoms in the reactant or precursor can be single bonds, double bonds, triple bonds, or some combination thereof. Thus, in some embodiments, the first organic precursor can contain two amino groups. In some embodiments, the amino groups of the first organic precursor can occupy one or two terminal positions on the aliphatic carbon chain. However, in some embodiments, the amino groups of the first organic precursor may not occupy any terminal position on the aliphatic carbon chain. In some embodiments, the first organic precursor can include a diamine. In some embodiments, the first organic precursor can include an organic precursor selected from 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopropane, 2,3-butanediamine, 2,2-dimethyl-1,3-propanediamine.

[0102] In some embodiments, at a temperature of about 20 °C or room temperature, the first and / or second organic precursor has a vapor pressure greater than about 0.5 Torr, 0.1 Torr, 0.2 Torr, 0.5 Torr, 1 Torr, 2 Torr, or greater. In some embodiments, the boiling point of the first and / or second organic precursor is less than about 400 °C, less than 300 °C, less than about 250 °C, less than about 200 °C, less than about 175 °C, less than about 150 °C, or less than about 100 °C.

[0103] In some embodiments, the first organic precursor provided to the reaction chamber at 210a is a liquid precursor under standard conditions. In some embodiments, the first organic precursor to be evaporated includes diamines such as 1,6-diaminohexane, 1,3-diaminopentane, triamines such as tris(2-aminoethyl)amine, or cyclic compounds including at least two primary amine groups such as 1,4-diaminocyclohexane or p-phenylenediamine. The substrate is then exposed to the first organic precursor vapor 210a. The substrate is also exposed to a second gas-phase precursor 210b, such as an organic precursor like a dianhydride. The dianhydride can be, for example, pyromellitic dianhydride (PMDA). The cyclic exposure of the substrate to the first and second organic precursors results in the deposition of an organic polymer. The method can include additional steps and can be repeated, but need not be performed in the illustrated order, nor in the same order in each repetition, and can be readily extended to more complex vapor deposition techniques.

[0104] The first organic precursor according to the present disclosure can include at least two carbon atoms, such as 1,2-diaminoethane. In some embodiments, the first organic precursor includes three carbon atoms. In some embodiments, the first organic precursor includes four carbon atoms. For example, the first organic precursor can be selected from 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, and 2,4-diaminobutane. Thus, in some embodiments, at least one amino group is attached to a carbon atom bonded to two other carbon atoms. In other words, at least one amino group can be located at the end of the carbon chain. In some embodiments, the diamine according to the present disclosure includes five carbon atoms. In some embodiments, the diamine according to the present disclosure includes six carbon atoms.

[0105] In some embodiments, the carbon chain of the first organic precursor is branched. Thus, there is at least one carbon atom bonded to three or four other carbon atoms. In some embodiments, there is one such branching position in the first organic precursor. In some embodiments, there are two such branching positions in the first organic precursor. In some embodiments, there are three or more branching points. In some embodiments, the side chain of the longer carbon chain is a methyl group. In some embodiments, the side chain of the longer carbon chain is an ethyl group. In some embodiments, the side chain of the longer carbon chain is a propyl group. In some embodiments, the side chain of the longer carbon chain is an isopropyl group. In some embodiments, the side chain of the longer carbon chain is a butyl group. In some embodiments, the side chain of the longer carbon chain is a tert-butyl group. In some embodiments, the side chain of the first organic precursor is a straight-chain alkyl chain. In some embodiments, the side chain of the first organic precursor is a branched-chain alkyl chain. In some embodiments, the side chain of the first organic precursor is a cyclic alkyl chain.

[0106] In some embodiments, the first organic precursor is a C2 to C11 compound. The number of carbon atoms in the first organic precursor generally affects the volatility of the compound, such that higher weight compounds may not be as volatile as smaller compounds. However, it has been found that medium-sized first organic precursors containing, for example, four, five, or six carbon atoms may have suitable properties for use as the first organic precursor in the selective deposition process according to the present disclosure. For example, 1,3-diaminopentane is a liquid at room temperature, has a boiling point of 164 °C at atmospheric pressure, has a vapor pressure of about 2.22 Torr at 25 °C, and reaches a vapor pressure of 1 Torr at a temperature below 20 °C. Thus, when 1,3-diaminopentane is used as a precursor for the deposition of an organic polymer according to the present invention, the precursor container does not need to be heated. This is advantageous for the tool life of the precursor because it does not readily degrade during continuous use. Additionally, the liquid precursor has the advantage of being less expensive to load into the precursor container than a solid precursor. In some embodiments, the first organic precursor comprises 1,3-diaminopentane.

[0107] In some embodiments of the present disclosure, the amine groups are attached to non-adjacent carbon atoms. This may be advantageous for the availability of the amine groups to react with the second precursor. In some embodiments, there is one carbon atom between the carbon atoms to which the amino groups are attached. In some embodiments, there is at least one carbon atom between the carbon atoms to which the amino groups are attached. In some embodiments, there are two carbon atoms between the carbon atoms to which the amino groups are attached. In some embodiments, there are at least two carbon atoms between the carbon atoms to which the amino groups are attached. In some embodiments, there are three carbon atoms between the carbon atoms to which the amino groups are attached. In some embodiments, there are at least three carbon atoms between the carbon atoms to which the amino groups are attached. In some embodiments, there are four carbon atoms between the carbon atoms to which the amino groups are attached. In some embodiments, there are at least four carbon atoms between the carbon atoms to which the amino groups are attached.

[0108] In some embodiments, the first organic precursor comprises 1,5-diamino-2-methylpentane.

[0109] In some embodiments, the carbon atom bonded to the amine nitrogen in the first organic precursor is bonded to at least two carbon atoms. Thus, in some embodiments in which the first organic precursor contains five or more carbons, at least one amino group can be located away from the end of the carbon chain. The structure of the first organic precursor affects its properties during the vapor deposition process. The branching of the first organic precursor, including the number of branches and the relative position of the amino groups to the branches, can result in the deposited organic polymer having different properties. Without limiting the present disclosure to any specific theory, for example, steric factors can cause certain reactions to be preferred because this can provide the possibility of designing a deposition process for a given purpose by using different first organic precursors, taking into account, for example, the thermal budget, the organic polymer growth rate requirements, and the necessary degree of selectivity.

[0110] In some embodiments, the first organic precursor is a cyclic diamine. In some embodiments, the first organic precursor includes cyclopentane dialkylamine, cyclohexane dialkylamine, cyclopentadiene dialkylamine, benzene dialkylamine, cyclopentane trialkylamine, cyclohexane trialkylamine, cyclopentadiene trialkylamine, and benzene trialkylamine.

[0111] In some embodiments, the first organic precursor is an aromatic diamine. In some embodiments, the aromatic diamine is diaminobenzene, such as 1,2-diaminobenzene, 1,3-diaminobenzene, or 1,4-diaminobenzene. In some embodiments, the aromatic diamine contains an alkylamino group at at least one position. For example, the alkylamino group can be a C1-C3 alkylamino group, such as -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2, or -CH2CH(CH3)NH2.

[0112] In some embodiments, the first organic precursor is selected from 1,3-diaminopentane, 1,4-diaminopentane, 2,4-diaminopentane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diaminobutane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,4-diamino-4-methylpentane, 1,3-diaminobutane, 1,5-diaminohexane, 1,3-diaminohexane, 2,5-diaminohexane, 1,3-diamino-5-methylhexane, 4,4,4-trifluoro-1,3-diamino-3-methylbutane, 2,4-diamino-2-methylpentane, 4-(1-methylethyl)-1,5-diaminohexane, 3-aminobutanamide, 1,3-diamino-2-ethylhexane, 2,7-diamino-2,7-dimethyloctane, 1,3-diaminobenzene, and 1,4-diaminobenzene. In some embodiments, the first organic precursor includes a halogen.

[0113] In some embodiments, according to the present invention, triamines can be used for the deposition of organic polymers. Providing such molecules can advantageously affect the availability of polymerization sites of a second vapor-phase organic precursor. The availability of three amino groups in a single molecule can result in a denser polymer network, which in turn can reduce the migration of metal through the organic polymer. This property can be advantageous in embodiments where an organic polymer according to the present disclosure is used as a passivation layer. Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (with amines on carbons 1, 2, and 3 or on carbons 1, 2, and 4), triaminopentane (especially with amines on carbons 1 and 5, plus an amine on any one of carbons 2, 3, or 4). Similarly, triaminohexane can have amines on carbons 1 and 6, and on any one of the 2, 3, 4, or 5 positions; triaminoheptane can have amines on carbons 1 and 7 and on any one of the 2, 3, 4, 5, or 6 positions; and triaminooctane can have amines on carbons 1 and 8 and on any one of the 2, 3, 4, 5, 6, or 7 positions. In addition, branched carbon chains, especially 2-aminomethyl-1,3-diaminopropane, 2-aminomethyl-1,4-diaminobutane (or alternatives with two amino groups elsewhere on the butane chain), 2-aminomethyl-1,5-diaminopentane (or alternatives with two amino groups elsewhere on the pentane chain), 3-aminomethyl-1,5-diaminopentane (or alternatives with two amino groups elsewhere on the pentane chain), 2-aminomethyl-1,6-diaminohexane (or alternatives with two amino groups elsewhere on the hexane chain), 3-aminomethyl-1,6-diaminohexane (or alternatives with two amino groups elsewhere on the hexane chain), 3-aminoethyl-1,6-diaminohexane (or alternatives with two amino groups elsewhere on the hexane chain). In addition, aromatic triamines such as 1,3,5-triaminobenzene can be alternatives in some embodiments.

[0114] In some embodiments, the deposited polymer includes polyimide. In some embodiments, the organic polymer consists essentially only of polyimide. In some embodiments, the organic polymer includes polyamic acid. In some embodiments, the organic polymer consists essentially only of polyamic acid and polyimide. In some embodiments, the organic polymer is deposited at a temperature below 190 °C and then heat-treated (annealed) at a temperature of about 190 °C or higher (e.g., from about 200 °C to about 500 °C) to increase the proportion of the organic polymer from polyamic acid to polyimide. Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimides, other polymeric forms, or mixtures of the above materials.

[0115] In some embodiments, the substrate is thermally annealed for about 1 to about 15 minutes. In some embodiments, the substrate is thermally annealed at a temperature of about 200 °C to about 500 °C. In some embodiments, the thermal annealing step comprises two or more steps, wherein the substrate is thermally annealed at a first temperature for a first period of time and then at a second temperature for a second period of time.

[0116] In some embodiments, the deposited organic polymer is exposed to plasma-generated active species. In embodiments where the organic polymer is used as a passivation material, this can improve the passivation performance of the organic polymer. For example, active species generated by a plasma containing hydrogen and argon can be used. The organic polymer can be exposed to the plasma for about 1 second to about 1 minute, such as about 1 second to about 30 seconds, or about 5 seconds to about 30 seconds, or about 1 second to about 15 seconds, or about 3 seconds to about 20 seconds, such as about 5 seconds, about 10 seconds, about 20 seconds or about 30 seconds. A plasma power of at least about 20 W, or at least about 50 W, such as about 20 W to about 100 W, such as 30 W, 50 W or 70 W can be used. Suitable plasma power and duration of plasma exposure can be determined experimentally.

[0117] The present disclosure is further explained by the following exemplary embodiments depicted in the drawings. The illustrations given herein are not meant to be actual views of any particular material, structure, or component, but merely schematic representations describing embodiments of the present disclosure. 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 dimensions of some elements in the figures may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. Specifically, the relative deposition rates of the different materials shown in the figures may deviate from experimental results, and the details may vary according to process conditions. The structures, devices, and components depicted in the drawings may contain additional elements and details, which may be omitted for clarity.

[0118] For the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the methods and components described herein may not be described in detail. Additionally, the connecting lines shown in the various figures are intended to represent example functional relationships and / or physical couplings between the various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0119] Figure 1It is a block diagram of an exemplary embodiment of method 100 according to the present disclosure. First, at block 102, a substrate is provided in a reaction chamber. As described in the present disclosure, the substrate includes a first surface and a second surface. For example, the first surface may be a dielectric surface, and the second surface may be a metal or metallic surface. In some embodiments, the first surface is a high-k surface, and the second surface is a silicon-containing dielectric surface, such as a low-k surface. In some embodiments, the first surface is a metal surface, metallic surface, amorphous carbon surface, metal oxide surface, or metal nitride surface (such as a metallic surface), and the second surface is a dielectric surface, such as a silicon-containing surface. The substrate may be heated at block 102 before providing the first metal precursor into the reaction chamber.

[0120] At block 104, a first metal precursor is provided into the reaction chamber in a gaseous phase. In an exemplary embodiment, the first metal precursor is an aluminum precursor disclosed herein. For example, the aluminum precursor may include, consist of, or consist essentially of N,N'-bis(isopropylformamido)dimethylaluminum. The first metal precursor selectively chemisorbs on the first surface with respect to the second surface of the substrate. The first metal precursor may be provided into the reaction chamber (i.e., pulsed) for about 0.2 to 10 seconds, for example, about 0.5 second, about 1 second, about 3 seconds, about 5 seconds, or about 6 seconds. After the first metal precursor pulse, the reaction chamber may be purged. Figure 1 Purging is not shown, but it may optionally be included at block 104.

[0121] At block 106, reactants are provided into the reaction chamber in a gaseous phase. The reactants react with the chemisorbed first metal precursor or its derivatives to form a metal-containing material on the first surface of the substrate. In an exemplary embodiment, the reactant is water, and aluminum oxide is deposited on the first surface. In another exemplary embodiment, the reactant is ammonia, and aluminum nitride is deposited on the first surface. After the reactant pulse, the reaction chamber may be purged. Figure 1 Purging is not shown, but it may optionally be included at block 106.

[0122] The deposition process according to the present disclosure is a cyclic deposition process. Thus, stages 104 and 106 form a deposition cycle. At loop 108, the deposition cycle starts again. The deposition cycle may be repeated as many times as needed to deposit a desired thickness of the metal-containing material on the first surface of the substrate. For example, the deposition cycle may be performed 2 to about 600 times, or 2 to about 500 times, or about 5 to about 200 times, or about 10 to 300 times. For example, the deposition cycle may be executed about 30 times, about 50 times, about 100 times, about 150 times, about 200 times, about 300 times, or about 400 times.

[0123] The deposition temperature, such as the temperature of the reaction chamber or the substrate support, can be from about 150 °C to about 450 °C or from about 200 °C to about 400 °C, or from about 300 °C to about 400 °C. For example, the deposition temperature can be about 250 °C or about 300 °C or about 350 °C or about 375 °C. In some embodiments using passivation, the second surface of the substrate is passivated at a lower temperature that is the same as the deposition temperature of the metal-containing material.

[0124] Although not described in detail in this disclosure, the process can include additional steps, such as refreshing any barriers or passivation that may be necessary for sequential selective deposition, heat treatment, intermediate etchback, or post-deposition etch. In some embodiments, the selective deposition of the metal-containing material on the first surface does not damage the passivation layer present on the second surface, such as an organic passivation layer, such as a layer comprising polyimide. Additionally, in some embodiments, the metal-containing material does not substantially deposit on the passivation. Although Figures 1 to 3 not shown, it is possible for the stages of the deposition process to overlap. For example, stages 104 and 106 can be performed at least partially simultaneously. In some embodiments, stages 104 and 106 are performed at least partially simultaneously.

[0125] Figure 2 is a block diagram of another exemplary embodiment of a method according to the present disclosure, showing the selection of a deposition surface (i.e., the first surface) between metal and metal material on the one hand and dielectric material on the other hand. Block 202 corresponds to Figure 1 block 102 of Figure 1 and blocks 206 and 212 represent the subject matter of blocks 104, 106, and 108 of

[0126] In Figure 2 the process flow, after block 202, the substrate is contacted with an inhibitor reactant in block 204. The inhibitor reactant can be, for example, a silylating agent or a metal halide as described herein. When the substrate is contacted with the inhibitor reactant, the inhibitor reactant reacts with the first surface or the second surface, depending on their composition. The inhibitor reactant forms passivation on the surface. Generally, a silylating agent reacts with a silicon-containing surface or other non-conductive surface. If the surface passivated by the inhibitor reactant is the surface on which deposition is not desired (i.e., the second surface), the process can continue to block 206. If desired, the contact with the inhibitor reactant can be repeated by returning to block 204 through loop 214a. Blocks 204 and 206 can be performed in one reaction chamber, in two deposition stations of a multi-station reaction chamber, in different reaction chambers of one deposition assembly, or in different deposition assemblies. In some embodiments, there is no air break between blocks 204 and 206. In some embodiments, there is an air break between blocks 204 and 206. In some embodiments, the metal-containing material is selectively deposited on the first dielectric surface of the substrate relative to different second dielectric surfaces.

[0127] In embodiments where the metal-containing material is targeted to be passivated by an inhibitor-reactant on the same surface, the initial passivation of the inhibitor-reactant can be used to deposit a passivation layer on another (i.e., second) surface of the substrate. In such embodiments, Figure 2 the process continues to block 208. Block 208 can include a cyclic deposition process, such as an MLD process, to deposit an organic polymer, such as polyimide, as described herein. Similar to block 206, the initial passivation can be restarted by returning from block 208 to the previous block 204, as shown by the dashed arrow 210. This can occur at a predetermined time interval developed for each application. After the passivation layer has been deposited, at optional block 212, the initial passivation can be removed from the first surface, and thereafter at block 214, the metal-containing material can be deposited on the first surface. As shown by the optional loop 216, the passivation can be performed again by returning to block 204. Although not shown in Figure 2 it, the passivation can be performed again by returning to block 208.

[0128] The second surface can be passivated. For example, the second metallic surface can include a passivation layer containing polyimide thereon. Alternatively, as a second dielectric, such as silicon oxide, the surface can include silylation. In an exemplary embodiment, the substrate can include a silicon oxide surface and a tungsten surface, or a silicon oxide surface and a titanium nitride surface, or a silicon oxide surface, a tungsten surface, and a silicon oxide surface. The silicon oxide surface can be passivated with a silylating agent, such as N-(trimethylsilyl)dimethylamine or 1,1,1-trimethoxy-N,N-dimethylsilanamine. Thereafter, aluminum oxide can be deposited on the tungsten surface and / or the titanium nitride surface, depending on their presence on the substrate. The deposition of aluminum oxide can be carried out by alternately and sequentially supplying a first metal precursor (such as N,N'-bis(isopropylformamido)dimethylaluminum) and a reactant (such as water) to the reaction chamber at a temperature of, for example, 300 °C. The growth of the target material (such as aluminum oxide) can be delayed on the second surface. For example, the deposition can be carried out for up to about 100 or more cycles before the growth on the second surface begins. The number of such cycles (sometimes referred to as the selectivity window) can be increased by, for example, intermittent etching.

[0129] In an alternative process flow, silylation can be performed as described above, but then an organic polymer, such as a polyimide-containing polymer, will be deposited as described herein. In such an embodiment, the tungsten and / or metal nitride surface present on the substrate will be the second surface, while the silica surface is the first surface on which alumina is deposited. The first metal (tungsten and / or titanium nitride) surface can be activated by removing the silylation rather than the organic polymer prior to depositing alumina or another metal oxide or metal nitride. After a sufficient amount of the target material has been deposited on the first surface, the organic polymer passivation can be removed from the second surface, for example, by plasma. In some embodiments, at least 3 nm of a metal oxide, such as alumina, is grown on the first metal-containing surface before growth begins on the second silica surface.

[0130] A metal nitride, such as an aluminum nitride film, can be deposited using a similar process as described above. The selectivity of the process has also been tested on a hafnium oxide (HfO2) surface, on which the growth of a metal-containing material (such as aluminum nitride) is inhibited by silylation. In some embodiments, the deposition of the metal-containing material can be accomplished at a temperature of about 350 °C or at a temperature of about 375 °C using ammonia (NH3) as a reactant with the aluminum precursor as described above. The pulse time of the first metal precursor can range from about 1 second (s) to about 8 s, such as about 3 s, 5 s, or 7 s. In some embodiments, the reactant, i.e., the ammonia pulse time, is the same as or longer than the first metal precursor pulse time. For example, the reactant pulse time can range from about 5 seconds to about 30 seconds, such as 10 seconds or 15 seconds. Without limiting the present disclosure to any particular theory, the selectivity of the metal nitride process (such as the aluminum nitride process) can be better than the selectivity of the metal oxide process.

[0131] Figure 3 is a schematic diagram of an embodiment of a semiconductor processing assembly according to the present disclosure.

[0132] In yet another aspect, a semiconductor processing assembly 300 is disclosed for selectively depositing a metal-containing material on a first surface of a substrate relative to a second surface of the substrate. The semiconductor processing assembly 300 includes one or more reaction chambers 320 and a precursor injector system 301. The reaction chambers 320 are configured and arranged to hold the substrate, and the precursor injector system 301 is configured and arranged to provide a first metal precursor and a reactant in a gas phase into the reaction chambers 320. The first metal precursor includes a group 13 metal atom, an amidine ligand, and an alkyl ligand attached to the metal atom. The semiconductor processing assembly 300 further includes a first metal precursor source container 302 and a reactant source container 303. The precursor injector system 301 is configured and arranged to provide the first metal precursor and the reactant in a gas phase into the reaction chambers 320. The first metal precursor and the reactant can be provided into the reaction chamber alternately and sequentially to form a metal-containing material on the first surface.

[0133] The semiconductor processing assembly 300 further includes an optional inhibitor reactant source container 304 that is configured and arranged to contain an inhibitor reactant according to the present disclosure. The semiconductor processing assembly 300 is configured and arranged to provide the inhibitor reactant into the reaction chamber 320 via the precursor injector system 301 for selectively forming an inhibitor material on the first or second surface of the substrate.

[0134] The processing assembly 300 may include an optional additional source container that is configured and arranged to contain additional reactants used in substrate processing. For example, another source container may be configured and arranged to contain a second inhibitor reactant, a precursor for forming a passivation layer, or an etchant. The precursor may be an organic precursor for depositing a passivation layer on the second surface of the substrate.

[0135] The processing assembly 300 is configured and arranged to perform the methods described herein. In the illustrated example, the semiconductor processing assembly 300 includes one or more reaction chambers 320, a precursor injector system 301, source containers 302, 303, 304, optional and additional source containers, an exhaust source 322, and a controller 330. The processing assembly 300 may include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source. The reaction chamber 320 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber described herein.

[0136] The first metal precursor source container 302 may include a container and the first metal precursor described herein—alone or mixed with one or more carrier gases (such as an inert gas). The reactant source container 303 may include a container and a reactant as described herein—alone or mixed with one or more carrier gases (such as an inert gas). Thus, although three source containers 302 - 304 are shown, the processing assembly 300 may include any suitable number of source containers. The source containers 302 - 304 may be coupled to the reaction chamber 320 via lines 312 - 314, which may each include a flow controller, a valve, a heater, etc. In some embodiments, each of the source containers 302 - 304 may be independently heated or maintained at ambient temperature. In some embodiments, the source containers are heated such that the precursor or reactant reaches a temperature suitable for evaporation.

[0137] The exhaust source 322 may include one or more vacuum pumps.

[0138] The controller 330 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the processing assembly 300. The controller is programmed to execute the methods disclosed herein. Such circuitry and components are used to introduce precursors, reactants, and other gases from corresponding sources. The controller 330 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 320, the pressure within the reaction chamber 320, and various other operations to provide proper operation of the processing assembly 300. The controller 330 can include control software to control valves, either electrically or pneumatically, to control the flow of precursors, reactants, and other gases into and out of the reaction chamber 320. The controller 330 can include modules that perform specific tasks, such as software or hardware components.

[0139] Other configurations of the processing assembly 300 are possible, including different numbers and types of precursors and source containers. For example, the reaction chamber 320 can include more than one, such as two or four, deposition stations. Such a multi-station configuration can be advantageous if, for example, inhibition, passivation, deposition, and / or etching are performed in the same reaction chamber. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and reactant sources that can be used to achieve the goal of selectively and in a coordinated manner supplying gases to the reaction chamber 320. In addition, for the sake of simplicity of illustration, many components have been omitted from the schematic representation of the processing assembly 300, and these components can include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0140] During operation of the processing assembly 300, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to the reaction chamber 320. Once the substrate is transferred to the reaction chamber 320 (i.e., they are provided in the reaction chamber 320), one or more gases from a gas source, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into the reaction chamber 320.

[0141] It should be understood that the configurations and / or methods described herein are exemplary in nature and these specific embodiments or examples should not be considered limiting since many variations are possible. The particular routines or methods described herein can represent one or more of any number of processing strategies. Accordingly, the various acts shown can be performed in the order shown, in other orders, or in some cases, omitted.

[0142] The subject matter of the present disclosure includes all novel and non-obvious combinations and sub-combinations of various methods and components, as well as other features, functions, acts, and / or properties disclosed herein, and any and all equivalents thereof.

Claims

1. A method for selectively depositing a metal-containing material on a first surface of a semiconductor substrate relative to a second surface of the substrate, the method comprising: providing a substrate in a reaction chamber; and Depositing a metal-containing material on the first surface of the substrate by a cyclic vapor deposition process, wherein the vapor deposition process comprises: providing a first metal precursor in a vapor phase into the reaction chamber; and providing reactants in a gas phase into a reaction chamber; Wherein, the first metal precursor comprises a heteroleptic precursor comprising a Group 13 metal atom, an amidine ligand, and an alkyl ligand attached to the metal atom.

2. The method according to claim 1, wherein: The metal of the metal-containing material is selected from aluminum (Al), gallium (Ga) and indium (In).

3. The method according to claim 2, wherein: The metal-containing material is aluminum oxide, and the first metal precursor is an aluminum precursor.

4. The method according to claim 2, wherein: The metal-containing material is aluminum nitride, and the first metal precursor is an aluminum precursor.

5. The method according to claim 1, wherein: The alkyl ligand attached to the metal atom is selected from methyl, ethyl and straight or branched chain alkyl groups containing three, four or five carbon atoms.

6. The method according to claim 5, wherein: The first metal precursor comprises two alkyl ligands bonded to the metal atom.

7. The method according to claim 6, wherein: The amidino ligand is an alkylacetamido ligand.

8. The method according to claim 7, wherein: The alkylacetamido ligand is a dialkylacetamido ligand.

9. The method according to claim 7, wherein: One or two alkyl groups of the alkylacetamido ligand are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl and sec-butyl.

10. The method according to claim 9, wherein: The first metal precursor is selected from N,N'-di-(isopropylformamido)dimethylaluminum, N,N'-di-(isopropylformamido)diethylaluminum, N,N'-di-(isopropylformamido)-di-n-propylaluminum, N,N'-di-(isopropylformamido)-di-tert-butylaluminum and N,N'-di-(isopropylformamido)ethylmethylaluminum.

11. The method according to claim 1, wherein: The reactant is selected from an oxygen precursor, a nitrogen precursor, and a fluorine precursor.

12. The method according to claim 1, wherein: The reactants shown are selected from molecular oxygen, ozone, hydrogen peroxide and water.

13. The method according to claim 1, wherein: The first surface is a silicon-containing dielectric surface.

14. The method according to claim 13, wherein: The dielectric surface includes a material selected from the group consisting of SiO2, SiN, SiC, SiOC, SiON, SiOCN, SiGe, and combinations thereof.

15. The method according to claim 1, wherein: The first surface is a dielectric surface comprising a metal oxide.

16. The method according to claim 15, wherein: The metal oxide of the second surface is selected from aluminum oxide, hafnium oxide and zirconium oxide.

17. The method according to claim 1, wherein: The second surface is a conductive surface.

18. The method according to claim 1, wherein: The second surface includes a material selected from the group consisting of: metal, amorphous carbon, metal oxide, and metal nitride.

19. The method according to claim 1, wherein: The second surface includes elemental metal.

20. The method according to claim 1, wherein: The method includes treating the first surface with an inhibitor reactant before providing the first metal precursor into a reaction chamber, and then depositing an organic polymer on the second surface to passivate the second surface.

21. The method according to claim 1, wherein: The first surface is an elemental metal surface or a metal nitride surface.

22. The method according to claim 21, wherein: The second surface is a dielectric surface.

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