Method and system for depositing metal-containing layers

Abstract

The present disclosure relates to methods and apparatus for depositing a metal-containing material on a substrate by a selective deposition process. The method includes providing a substrate in a reaction chamber, providing a metal alkoxide precursor into the reaction chamber in a vapor phase; and providing a second precursor in a vapor phase into the reaction chamber to form a metal-containing material on the substrate. A second precursor according to the present disclosure includes a borane compound, and a substrate includes a first surface and a second surface.

Description

[0001] Parties to the Joint Research Agreement

[0002] The invention claimed herein was made by, on behalf of, or in connection with a joint research agreement between the University of Helsinki and ASM Microchemistry Oy, and / or is related to the agreement. The agreement was in effect on and prior to the date the claimed invention was made and the claimed invention was made as a result of activities undertaken within the scope of the agreement. TECHNICAL FIELD

[0003] The present disclosure relates to methods and apparatuses for manufacturing semiconductor devices. More specifically, the present disclosure relates to methods and apparatuses for depositing metal-containing material on a substrate by a cyclic deposition process, and to layers comprising metal-containing material. BACKGROUND

[0004] Copper is the most commonly used interconnect material in microelectronics and will remain an important metal for interconnects in the near future, despite the trend towards transition to other metals. Modern applications require high quality thin films that are uniformly deposited over large areas and over 3D structures. To achieve these qualities, vapor phase thin film deposition methods are needed, and among these methods, the one that can best meet the needs is atomic layer deposition (ALD).

[0005] There are multiple existing processes for depositing copper with ALD, but many of them require high temperatures. In the case of metals, typically high deposition temperatures lead to increased agglomeration of the film during growth. This means that the critical thickness, the thickness at which metal islands coalesce into a continuous film, is higher than when the deposition temperature is lower. Low-temperature thermal ALD processes can be achieved with smart chemistry.

[0006] On the other hand, other metals, such as bismuth, do not have such an important role in current microelectronics. However, this does not mean that they are not interesting materials, as many of them have unique properties that can be utilized in the future. Possible applications presented in the literature include semiconductor devices, superconductors, and anodes for batteries. For example, bismuth undergoes a semimetal-semiconductor (SMSC) transition, which is a unique and interesting effect. In addition, many other important materials include bismuth as a component, such as bismuth chalcogenides. Bismuth is a heavy element, so Bi films can be applied, for example, to x-ray optics and various novel patterning methods (EUV, multiple patterning).

[0007] Any discussion of the background of the disclosure included herein (including a discussion of problems and solutions) is included in the disclosure solely for the purpose of providing a context for the disclosure. Such discussion is not an admission that any or all of the information is known in the art or is known to be useful in any way. SUMMARY

[0008] This Summary is provided to introduce a selection of concepts in a simplified form. These concepts are further described in detail in the following detailed description of example embodiments of the disclosure. This Summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0009] Various embodiments of the disclosure relate to methods of depositing a metal- containing material on a substrate, metal-containing layers, semiconductor structures and devices containing the layers, and deposition assemblies for depositing a metal-containing material on a substrate.

[0010] In a first aspect, a method of depositing a material on a substrate by a cyclic deposition process is disclosed. The method includes providing a substrate into a reaction chamber, providing a metal alkoxide precursor into the reaction chamber in a gas phase, and providing a second precursor into the reaction chamber in a gas phase to form the material on the substrate. In the method, the second precursor includes a borane compound.

[0011] In some embodiments, the method selectively deposits the material on the substrate by the cyclic deposition process. In some embodiments, the material is formed more on a first surface than on a second surface of the substrate.

[0012] In some embodiments, the metal alkoxide precursor is provided into the reaction chamber at a deposition temperature of 80-130 °C or 200-300 °C or 80-250 °C.

[0013] In some embodiments, the metal alkoxide precursor comprises at least one alkoxide ligand.

[0014] In some embodiments, the metal alkoxide precursor comprises at least two alkoxide ligands.

[0015] In some embodiments, the metal alkoxide precursor comprises three alkoxide ligands.

[0016] In some embodiments, the metal alkoxide precursor is a metal aminoalkoxide precursor.

[0017] In some embodiments, the metal alkoxide precursor includes a ligand selected from the group consisting of dmap, dmamp, emamp, deamp, emamb, deamb, dmamb, and dmaeb.

[0018] In some embodiments, the metal atom of the metal alkoxide precursor is selected from the group consisting of late transition metals and post-transition metals.

[0019] In some embodiments, the metal atom is selected from the group consisting of Ni, Cu, Co, Zn, Fe, Al, Bi, Ga, In, Tl, Sn, and Pb.

[0020] In some embodiments, the metal atom comprises Bi or Cu.

[0021] In some embodiments, the metal alkoxide precursor is selected from Ni(dmap)2, Ni(dmamp)2, Ni(emamp)2, Ni(deamp)2, Ni(emamb)2, Ni(deamb)2, Ni(dmaeb)2, Co(dmap)2, Co(dmamp)2, Co(emamp)2, Co(deamp)2, Co(emamb)2, Co(deamb)2, Co(dmaeb)2, Cu(dmap)2, Cu(dmamp)2, Cu(emamp)2, Cu(deamp)2, Cu(emamb)2, Cu(deamb)2, Cu(dmaeb)2, Fe(dmap)2, Fe(dmamp)2, Fe(emamp)2, Fe(deamp)2, Fe(emamb)2, Fe(deamb)2, Fe(dmaeb)2, Zn(dmap)2, Zn(dmamp)2, Zn(emamp)2, Zn(deamp)2, Zn(emamb)2, Zn(deamb)2, Zn(dmaeb)2, Al(O i Pr)3, Al(OBu)3, Al(OEt)3, AlO i Pr(Me)2, Bi(OCMe2 i Pr)3,Ga(O t Bu)3, GaCl2(OCH2CH2NMe2), Cu(OMe)2, Cu(dmap)2, Pb(dmamp)2, Tl(OEt), Sn(O t Bu)4, Sn(OEt), Zn(O i Pr)2, Mo(thd), Nb(OEt)5and Mo2(O2CCH3)4.

[0022] In some embodiments, the metal alkoxide precursor is selected from Al(O i Pr)3, Al(OBu)3, Al(OEt)3, AlO i Pr(Me)2, Bi(OCMe2 i Pr)3, Ga(O t Bu)3, GaCl2(OCH2CH2NMe2), In(O t Bu)3, Cu(OMe)2, Cu(dmap)2, Pb(dmamp)2, Tl(OEt), Sn(O tBu)4, Sn(OEt)2, and Zn(OiPr)2.

[0023] In some embodiments, the metal alkoxide precursor is selected from Bi(OCMe2iPr)3and Cu(dmap)2.

[0024] In some embodiments, the second precursor is a reducing agent.

[0025] In some embodiments, the second precursor is selected from pinacol borane, bis-pinacol boron, 9-BBN, borane morpholine, catechol borane, 2-methylpyridine borane, borane pyridine adduct, decaborane, 1,4-bis(pinacol boron)-1,4-dihydropyrazine, H3B*NEt3, H3B*NHMe2, H3B*SMe2, BN(Et) i Pr2, and BH3*THF.

[0026] In some embodiments, the second precursor comprises an alkoxy borane compound.

[0027] In some embodiments, the second precursor comprises pinacol borane.

[0028] In some embodiments, the second precursor comprises 1,4-bis(pinacol boron ketone)-1,4-dihydropyrazine.

[0029] In some embodiments, the metal-containing material comprises an elemental metal.

[0030] In a second aspect, a metal-containing layer produced by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form a material on the substrate. In the process, the second precursor comprises a borane compound.

[0031] In a third aspect, a semiconductor structure comprising a metal-containing layer deposited by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form a material on the substrate. In the process, the second precursor comprises a borane compound.

[0032] In a fourth aspect, a semiconductor device comprising a metal-containing layer deposited by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form a material on the substrate. In the process, the second precursor comprises a borane compound.

[0033] In a fifth aspect, a deposition assembly for depositing a metal-containing material on a substrate is disclosed. The deposition assembly includes one or more reaction chambers configured and arranged to hold a substrate; a precursor injector system configured and arranged to provide a metal alkoxide precursor and a second precursor in a gas phase into the reaction chamber. The second precursor includes a borane compound. The deposition assembly further includes a precursor container configured and arranged to contain the metal alkoxide precursor; and the assembly is configured and arranged to provide the metal alkoxide precursor and the second precursor to the reaction chamber through the precursor injector system to deposit the metal-containing material on the substrate.

[0034] In a sixth aspect, a container containing a chemical precursor is disclosed. The container contains a bismuth alkoxide, wherein the container is configured to supply a vapor of the chemical precursor to a semiconductor processing equipment chamber.

[0035] In a seventh aspect, a metal-containing film deposition product is disclosed. The product includes: a metal-containing chemical precursor including a metal alkoxide; a second precursor including an alkoxyborane; a first container containing the chemical precursor; and a second container containing the second precursor, wherein the metal-containing chemical precursor is provided in the first container and the second precursor is provided in the second container, wherein the first container and the second container are configured to be coupled to a semiconductor equipment via a reactant delivery system.

[0036] In an eighth aspect, a selective deposition method is disclosed. The method includes: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form a material on the substrate. In the method, the second precursor includes a borane compound. The substrate includes a first surface and a second surface. The material is formed more on the first surface than the second surface. BRIEF DESCRIPTION OF DRAWINGS

[0037] The accompanying drawings, which are included to provide a further understanding of the disclosure and constitute a part of this specification, illustrate exemplary embodiments and together with the description help to explain the principles of the disclosure. In the drawings:

[0038] Figure 1A and Figure 1B A block diagram illustrating an exemplary embodiment of a method according to the present disclosure is shown.

[0039] Figure 2 is a schematic view of a deposition assembly according to the present disclosure.

[0040] It should be understood that the elements in the figures are shown for the purpose of illustrating exemplary embodiments only and are not necessarily drawn to scale. For example, the dimensions of some of the elements in the figures can be exaggerated relative to other elements to help improve the understanding of the exemplary embodiments of the present disclosure being shown. DETAILED DESCRIPTION

[0041] While certain embodiments and examples are disclosed below, one skilled in the art will understand that the application extends beyond the specifically disclosed embodiments and / or uses of the application and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the application disclosed herein should not be limited by the particular disclosed embodiments described below.

[0042] In one aspect, a method of depositing a material on a substrate by a cyclic deposition process is disclosed. The method includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form the material on the substrate. In the method, the second precursor includes a borane compound.

[0043] In the cyclic deposition process, the stages of providing the metal alkoxide precursor and providing the second precursor into the reaction chamber are repeated until a desired thickness of the material is obtained.

[0044] In the method according to the present disclosure, the material deposited on the substrate includes a metal. In some embodiments, the metal-containing material includes a transition metal. In some embodiments, the metal-containing material includes a late transition metal. Late transition metal is defined as metals from Groups 8 to 12. In some embodiments, the metal-containing material includes a post-transition metal. Post-transition metal is defined as a group of metals consisting of aluminum, gallium, indium, thallium, tin, lead, bismuth, germanium, antimony, and polonium. In some embodiments, the metal-containing material includes copper. In some embodiments, the metal-containing material includes bismuth. In some embodiments, the metal-containing material includes an elemental metal.

[0045] In some embodiments, the metal-containing material includes a metal oxide. In some embodiments, the metal-containing material includes a metal nitride. In some embodiments, the metal-containing material includes a metal carbide. In some embodiments, the metal-containing material includes a metal selenide. In some embodiments, the metal-containing material includes a metal sulfide. In some embodiments, the metal-containing material includes a metal phosphide. In some embodiments, the metal-containing material includes a metal boride. In some embodiments, the metal-containing material includes a metal germanide.

[0046] As used herein, the terms "layer" and / or "film" can refer to any continuous or discontinuous structure and material, such as a material deposited by the methods disclosed herein. For example, a layer and / or film can include a two-dimensional material, a three-dimensional material, a nanoparticle, or even a partial or full molecular layer or a partial or full atomic layer or an atomic and / or molecular cluster. A film or layer can include a material or layer with pinholes, which can be at least partially continuous. A seed layer can be a discontinuous layer used to increase the nucleation rate of another material. However, a seed layer can also be substantially or completely continuous. A layer of a desired thickness can be deposited by repeatedly providing a metal alkoxide precursor and a second precursor in a reaction chamber a sufficient number of times. Layers produced according to the methods disclosed herein can form part of a semiconductor structure and / or a semiconductor device.

[0047] In another aspect, a semiconductor structure is disclosed that includes a metal-containing layer deposited by a cyclic deposition process. The cyclic deposition process is performed as described herein and the process is integrated with additional processing steps to produce the semiconductor structure. The semiconductor structure can be part of a semiconductor device. Such devices are used in the manufacture of integrated circuits.

[0048] In some embodiments, a metal-containing material is deposited as a layer on a substrate. In some embodiments, the metal-containing layer contains an elemental metal. The thickness of the metal-containing material layer can be adjusted by adjusting the number of cycles of the cyclic deposition process. In some embodiments, the cyclic deposition process includes alternating and sequentially providing a metal alkoxide precursor and a second precursor into a reaction chamber. In some embodiments, the reaction chamber is purged between providing the precursors into the reaction chamber. Examples of such cyclic deposition processes are atomic layer deposition and cyclic chemical vapor deposition.

[0049] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which a device, circuit, material, or layer of material can be formed. A substrate can include a bulk material such as silicon (e.g., single crystal silicon), other Group IV materials (e.g., germanium), or other semiconductor materials (e.g., Group II-VI or Group III-V semiconductor materials). A substrate can include one or more layers overlying a bulk material. A substrate can include various topologies such as gaps, recesses, lines, trenches, or spaces between raised portions (such as fins or the like) formed within or on at least a portion of a layer of the substrate. A substrate can include nitrides (e.g., TiN), oxides, insulating materials, dielectric materials, conductive materials, metals (e.g., tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper) or metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single crystalline materials. In some embodiments of the disclosure, a substrate includes silicon. In addition to silicon, a substrate can include other materials as described above. Other materials can form a layer.

[0050] In the present disclosure, the deposition process includes a cyclic deposition process, such as an atomic layer deposition (ALD) process or a cyclic chemical vapor deposition (CVD) process. The term “cyclic deposition process” can refer to the sequential introduction of one or more precursors and / or one or more reactants into a reaction chamber to deposit a material, such as a metal, on a substrate. Cyclic deposition includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD components and cyclic CVD components. The process can include a purge step between providing precursors or between providing precursors and reactants in the reaction chamber.

[0051] In the present disclosure, any two numbers of a variable can constitute a working range of the variable, and any range indicated can include or exclude endpoints.

[0052] Additionally, any value of a variable indicated, whether or not it is indicated with “about,” can refer to an exact value or an approximate value and include equivalents, and can refer to an average value, a median value, a representative value, a plurality of values, etc. Furthermore, in the present disclosure, the terms “comprising,” “consisting of,” and “having” independently refer, in some embodiments, to “generally includes,” “includes,” “is composed essentially of,” or “is composed of.” In the present disclosure, any defined meaning does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0053] “at least one,” “one or more,” and “and / or” are open-ended expressions that are both conjunctive and disjunctive in operation. For example, each of the expressions “at least one of A, B, and C,” “at least one of A, B, or C,” “one or more of A, B, and C,” “one or more of A, B, or C,” and “A, B, and / or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B, and C together. When each of the above expressions is recited with respect to elements such as X, Y, and Z, or categories of elements such as X1-X n , Y1-Y m , and Z1-Z o , the phrase is intended to mean a single element from X, Y, and Z, a combination of elements from the same category (e.g., X1and X2), and a combination of elements from two or more categories (e.g., Y1and Z o ).

[0054] The process can include one or more cyclic phases. For example, the pulses of metal alkoxide precursor and second precursor can be repeated. Repeating the cyclic deposition steps can be used to control the thickness of the deposited material. In some embodiments, the process includes one or more non-cyclic phases. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In some embodiments, the reactants can be continuously provided in the reaction chamber. In such embodiments, the process includes a continuous flow of the precursors or reactants. In some embodiments, one or more of the precursors and / or reactants are continuously provided in the reaction chamber. The cyclic deposition process can generally be initiated with any of the at least two precursors and / or reactants used in the process. Thus, in the present method, the first deposition cycle can be started by providing the metal alkoxide precursor or the second precursor in the reaction chamber.

[0055] The term "atomic layer deposition" (ALD) can refer to a vapor deposition process in which deposition cycles, e.g., a plurality of consecutive deposition cycles, are performed in a reaction chamber. As used herein, the term atomic layer deposition is also intended to include processes designated by related terms, e.g., chemical vapor atomic layer deposition when performed with alternating pulses of precursors / reactants and optional purge gases. Generally, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbs to a deposition surface (e.g., a substrate surface that can include previously deposited material or other material from a previous ALD cycle), forming a monolayer or sub-monolayer of material that is not readily reactive with additional precursors (i.e., self-limiting reaction). Thereafter, in some cases, another precursor or reactant can be subsequently introduced into the processing chamber for converting the chemisorbed precursor into the desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. Purge steps can be utilized during one or more cycles (e.g., during each step of each cycle) to remove any excess precursor from the processing chamber and / or any excess second precursor, reactant, and / or reaction byproducts from the reaction chamber. Thus, in some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a precursor into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the metal alkoxide precursor into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the second precursor into the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing each precursor into the reaction chamber.

[0056] CVD-type processes generally involve a gas phase reaction between two or more precursors and / or reactants. The precursors and reactants can be provided to the reaction space or substrate simultaneously or in partially or fully separated pulses. The substrate and / or reaction space can be heated to promote reaction between the gaseous precursors and / or reactants. In some embodiments, one or more precursors and one or more reactants are provided until a layer having a desired thickness is deposited. In some embodiments, a cyclic CVD process can be used with multiple cycles to deposit a thin film having a desired thickness. In a cyclic CVD process, the precursors and / or reactants can be provided to the reaction chamber in non-overlapping or partially or fully overlapping pulses.

[0057] As used herein, the term "purge" can refer to a process in which gaseous precursors and / or gaseous byproducts are removed from the substrate surface, for example, by evacuating the reaction chamber with a vacuum pump and / or by replacing the gas inside the reaction chamber with an inert or substantially inert gas, such as argon or nitrogen. A purge can be performed between two pulses of gases that react with each other. However, a purge can be performed between two pulses of gases that do not react with each other. For example, a purge can be provided between pulses of two precursors or between a precursor and a reactant. A purge can avoid or at least reduce gas phase interactions between two gases that react with each other. It will be appreciated that a purge can be performed in time or in space or both. For example, in the case of a temporal purge, the purge step can be used, for example, in a time sequence of providing a first precursor to the reactor chamber, providing a purge gas to the reactor chamber, and providing a second precursor to the reactor chamber, with the substrate on which the layer is deposited not moving. For example, in the case of a spatial purge, the purge step can take the form of moving the substrate from a first location where a first precursor is continuously supplied through a curtain of purge gas to a second location where a second precursor is continuously supplied. The purge time can be, for example, from about 0.01 seconds to about 20 seconds, from about 0.05 seconds to about 20 seconds, or from about 1 second to about 20 seconds, or from about 0.5 seconds to about 10 seconds, or from about 1 second to about 7 seconds, for example, 1 second or 2 seconds. However, other purge times can be utilized if desired, for example, where highly conformal step coverage on very high aspect ratio structures or other structures having complex surface topography is desired, or particular reactor types can be used, for example, batch reactors.

[0058] In some embodiments, the cyclic deposition process according to the present disclosure comprises a thermal deposition process. In thermal deposition, the chemical reaction can be promoted by an elevated temperature relative to ambient temperature. Generally, the temperature elevation provides the energy required to form the metal-containing material in the absence of other external energy sources, such as plasma, radicals, or other forms of radiation. In some embodiments, the method according to the present disclosure is a plasma-enhanced deposition method, such as PEALD or PECVD.

[0059] The method according to the present invention comprises providing a substrate in a reaction chamber, providing a metal alkoxide precursor in a gas phase to the reaction chamber, and providing a second precursor in a gas phase to the reaction chamber to form a metal-containing material on the substrate.

[0060] The method of depositing a metal-containing material according to the present disclosure comprises providing a substrate in a reaction chamber. In other words, the substrate is brought into a space where the deposition conditions can be controlled. The reaction chamber can be part of a cluster tool in which different processes are performed to form an integrated circuit. In some embodiments, the reaction chamber can be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber can be a showerhead reactor. In some embodiments, the reaction chamber can be a spatially segregated reactor. In some embodiments, the reaction chamber can be a single wafer ALD reactor. In some embodiments, the reaction chamber can be a single wafer ALD reactor for high volume manufacturing. In some embodiments, the reaction chamber can be a batch reactor for manufacturing multiple substrates simultaneously. The reaction chamber according to the present disclosure can also be a deposition station in a multi-station chamber.

[0061] Furthermore, in the method according to the present disclosure, the metal alkoxide precursor is provided in a gas phase to the reaction chamber, and the second precursor is provided in a gas phase to the reaction chamber to form a metal-containing material on the substrate.

[0062] In the method according to the present disclosure, the metal alkoxide precursor can be in a gas phase when it is in the reaction chamber. The metal alkoxide precursor can be partially gaseous or liquid, or even solid at some point in time before it is provided to the reaction chamber. In other words, the metal alkoxide precursor can be a solid, a liquid, or a gas, for example in a precursor container or other container, and then transported in the reaction chamber. When the transport into the reaction chamber is performed, various means can be applied to bring the precursor into a gas phase. Such means can include, for example, a heater, a vaporizer, a gas flow, or applying a reduced pressure, or any combination thereof. Thus, the method according to the present disclosure can comprise heating the metal alkoxide precursor before providing it to the reaction chamber.

[0063] In view of a conventional cyclic deposition process, the metal alkoxide compound can decompose at a relatively low temperature. For example, the compound can start decomposing at a temperature below 200 °C. Some metal alkoxide compounds can start decomposing at a temperature below 150 °C. However, the present inventors have found that a metal alkoxide compound according to the present disclosure can be suitable or even advantageous for a cyclic deposition process at a temperature below about 140 °C.

[0064] In some embodiments, deposition of the metal-containing material according to the present disclosure is conducted at a temperature below about 200 °C, or below about 185 °C, or below about 150 °C. In some embodiments, deposition is conducted at a temperature of about 80 °C to about 150 °C, such as about 85 °C to about 130 °C, for example at a temperature of about 80 °C, about 90 °C, about 110 °C, or about 130 °C.

[0065] In some embodiments, the metal alkoxide precursor is heated to at least 30 °C, at least 50 °C, or at least 70 °C, or at least 90 °C, or at least 100 °C, or at least 110 °C, prior to being provided to the reaction chamber. In some embodiments, the metal alkoxide precursor is heated to at least 120 °C, or at least 150 °C. The heating can be conducted in the precursor container. In some embodiments, the metal alkoxide precursor is heated to at most 180 °C, or at most 160 °C, or at most 150 °C, or at most 120 °C, or at most 100 °C, or at most 80 °C, or at most 60 °C, prior to being provided to the reaction chamber. The injector system of the vapor deposition assembly can be heated to improve vapor phase transport of the metal alkoxide precursor to the reaction chamber.

[0066] In the present disclosure, “gas” can include materials that are gaseous at normal temperature and pressure (NTP), vaporized solids, and / or vaporized liquids, and can be composed of a single gas or a mixture of gases, depending on the circumstances. The metal alkoxide precursor can be provided to the reaction chamber in the vapor phase. The second precursor can be provided to the reaction chamber in the vapor phase. The term “inert gas” can refer to a gas that does not participate in chemical reactions and / or does not become part of the layer to a significant extent. Exemplary inert gases include He and Ar, and any combination thereof. In some circumstances, molecular nitrogen and / or hydrogen can be inert gases. Gas other than the process gas, i.e., gas that is not introduced through the precursor injector system, other gas distribution devices, etc., can be used, for example, to seal the reaction space, and can include a seal gas.

[0067] In some embodiments, the metal-containing material includes an elemental metal. Thus, the deposited metal can have an oxidation state of at least in part 0. In some embodiments, all or substantially all of the metal is deposited as an elemental metal. In some embodiments, the deposited metal includes, consists of, or consists essentially of elemental copper. In some embodiments, the deposited metal includes, consists of, or consists essentially of elemental bismuth. In some embodiments, a layer is deposited that consists of, or consists essentially of, an elemental metal. In some embodiments, the metal deposition according to the present disclosure is a layer, and the layer includes a substantial amount of another element in addition to the metal. In such embodiments, the metal can be present as an elemental metal. In some embodiments, the metal deposited according to the present disclosure is present as an alloy with another metal.

[0068] In some embodiments, the metal deposited according to the present disclosure is at least partially present in a non-zero oxidation state. In some embodiments, the metal deposited according to the present disclosure forms a compound with another element. In some embodiments, the metal-containing material deposited according to the present disclosure comprises a metal oxide. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal nitride. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal silicide. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal germanide. In some embodiments, the metal-containing material deposited according to the present disclosure comprises a metal sulfide. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal selenide. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal phosphide. In some embodiments, the metal-containing material deposited according to the present disclosure includes a metal boride. In some embodiments, the metal-containing material according to the present disclosure comprises two or more of the above materials. For example, the metal-containing material can include an elemental metal and a metal carbide, or an elemental metal and a metal nitride, or a combination of a metal carbide and a metal nitride.

[0069] The growth rate of the metal-containing material can be, for example, about 0.05 to about 1.5 A / cycle. The growth rate and layer properties can depend on the temperature at which the deposition process is performed. In some embodiments, the growth rate can be about 0.1 A / cycle, or about 0.2 A / cycle, or about 0.5 A / cycle, or about 1 A / cycle. The growth rate can vary during the deposition process.

[0070] The deposition cycle, which includes providing a metal alkoxide precursor into the reaction chamber (e.g., pulsing the metal alkoxide precursor) and providing a second precursor into the reaction chamber (e.g., pulsing the second precursor) and optionally a purge phase, can be repeated, for example, about 100 times, about 125 times, about 200 times, about 250 times, about 350 times, about 500 times, about 750 times, about 1000 times, or about 1500 times. In some embodiments, the deposition cycle can be repeated at least about 100 times, about 250 times, at least about 350 times, at least about 500 times, at least about 750 times, at least about 1000 times, at least about 1500 times, at least about 2000 times, or at least about 2500 times.

[0071] The resistivity of the metal-containing material deposited as a layer depends on the material composition. Further, for a given material, e.g., an elemental metal-containing material, the resistivity can depend on the process conditions, e.g., the temperature of the layer and the growth rate. In embodiments where the metal-containing layer includes primarily or substantially only an elemental metal, the resistivity can be, for example, less than about 10 μΩ cm, e.g., less than about 7 μΩ cm, e.g., less than about 5 μΩ cm, e.g., between 1 and 10 μΩ cm, e.g., between 2 and 7 μΩ cm.

[0072] In some embodiments, the metal-containing material includes elemental metal and less than 20 atomic percent carbon. In some embodiments, the metal-containing layer includes elemental metal and less than 15 atomic percent carbon. In some embodiments, the metal-containing layer includes elemental metal and less than 10 atomic percent carbon. In some embodiments, the metal-containing material includes elemental metal and less than 2 atomic percent oxygen. In some embodiments, the metal-containing material includes elemental metal and less than 1 atomic percent nitrogen.

[0073] The terms "precursor" and "reactant" can refer to a molecule (compound or molecule comprising a single element) that participates in a chemical reaction to produce another compound. A precursor typically includes a moiety that is at least partially incorporated into the compound or element produced by the chemical reaction in question. The resulting compound or element can be deposited on a substrate. A reactant can be an element or compound that is not incorporated into the resulting compound or element to a significant extent. However, in certain embodiments, a reactant can also contribute to the resulting compound or element.

[0074] As used herein, a "metal alkoxide precursor" includes a gas or a material that can be rendered gaseous, and can be represented by a chemical formula that includes a metal alkoxide.

[0075] In some embodiments, the metal atom of the metal alkoxide precursor is a transition metal. In some embodiments, the metal atom of the metal alkoxide precursor is a late transition metal or a post-transition metal. In some embodiments, the metal is selected from nickel (Ni), copper (Cu), cobalt (Co), zinc (Zn), iron (Fe), aluminum (Al), bismuth (Bi), gallium (Ga), indium (In), thallium (Tl), tin (Sn), lead (Pb), molybdenum (Mo), tungsten (W), and niobium (Nb). In some embodiments, the metal includes bismuth or copper.

[0076] In some embodiments, the metal alkoxide precursor includes at least one alkoxide ligand. In some embodiments, the metal alkoxide precursor includes at least two alkoxide ligands. In some embodiments, the metal alkoxide precursor includes three alkoxide ligands.

[0077] In some embodiments, the metal alkoxide precursor is a metal aminoalkoxide precursor. In some embodiments, the metal alkoxide precursor includes a ligand selected from 1- dimethylamino-2-propanolate (dmap), 1-dimethylamino-2-methyl-2-propanolate (dmamp), 1- ethylmethylamino-2-methyl-2-propanolate (emamp), 1-diethylamino-2-methyl-2- propanolate (deamp), 1-ethylmethylamino-2-methyl-2-butanolate (emamb), 1- dimethylamino-2-methyl-2-butanolate (dmamb), 1-dimethylamino-2-ethyl-2- butanolate (dmaeb), and 1-diethylamino-2-methyl-2-butanolate (deamb).

[0078] In some embodiments, the metal alkoxide precursor is selected from Ni(dmap)2, Ni(dmamp)2, Ni(emamp)2, Ni(deamp)2, Ni(emamb)2, Ni(deamb)2, Ni(dmaeb)2, Co(dmap)2, Co(dmamp)2, Co(emamp)2, Co(deamp)2, Co(emamb)2, Co(deamb)2, Co(dmaeb)2, Cu(dmap)2, Cu(dmamp)2, Cu(emamp)2, Cu(deamp)2, Cu(emamb)2, Cu(deamb)2, Cu(dmaeb)2, Fe(dmap)2, Fe(dmamp)2, Fe(emamp)2, Fe(deamp)2, Fe(emamb)2, Fe(deamb)2, Fe(dmaeb)2, Zn(dmap)2, Zn(dmamp)2, Zn(emamp)2, Zn(deamp)2, Zn(emamb)2, Zn(deamb)2, Zn(dmaeb)2, Al(O i Pr)3, Al(OBu) 3, Al(OEt) 3, AlO i Pr(Me) 2, Bi(OCMe2 i Pr) 3, Ga(O t Bu)3, GaCl2(OCH2CH2NMe2), Cu(OMe) 2, Cu(dmap) 2, Pb(dmamp)2, Tl(OEt), Sn(O t Bu)4,Sn(OEt)2and Zn(O i Pr)2. In some embodiments, the metal alkoxide precursor is selected from Al(O i Pr)3, Al(OBu) 3, Al(OEt) 3, AlO i Pr(Me) 2, Bi(OCMe2 i Pr) 3, Ga(O t Bu)3, GaCl2(OCH2CH2NMe2), In(O t Bu)3 Cu(OMe) 2, Cu(dmap) 2,Pb(dmamp)2, (C5H5)2Ni, Tl(OEt), Sn(O t Bu)4, Sn(OEt)2, Zn(O i Pr)2,Mo2(OCMe3)6, W(OEt)6, Nb2(OEt) 10 , Nb(OEt)5, Mo2(O2CMe3)4and Mo(thd)3(thd = 2,2,6,6-tetramethylheptane-3,5-diketone).

[0079] In some embodiments, the metal alkoxide precursor comprises Bi(OCMe2 i Pr)3, consists of, or consists essentially of. In some embodiments, the metal alkoxide precursor comprises Cu(dmap)2, consists of, or consists essentially of.

[0080] In some embodiments, the metal alkoxide precursor is provided in a mixture of two or more compounds. In the mixture, the other compounds besides the metal alkoxide precursor can be inert compounds or elements. In some embodiments, the metal alkoxide precursor is provided in a composition. Compositions suitable for use as a composition can include a metal alkoxide compound and an effective amount of one or more stabilizers. The composition can be a solution or a gas under standard conditions. In some embodiments, a mixture of at least two metals can be deposited. In such embodiments, the metal alkoxide precursor can include two different metal-containing compounds, one or more of which is a metal alkoxide compound according to the present disclosure.

[0081] The metal-containing material is formed by providing the second precursor into the reaction chamber in the gas phase. The conversion of the metal alkoxide precursor to the desired metal- containing material can occur at the surface of the substrate. In some embodiments, the conversion can occur at least partially in the gas phase. In some embodiments, the reaction between the metal alkoxide precursor and the second precursor occurs substantially only at the surface of the substrate.

[0082] In some embodiments, the second precursor is a reducing agent. The reducing agent can reduce the metal of the metal alkoxide precursor to elemental metal. In some embodiments, the reducing agent is selected from synthesis gas (H2+N2), ammonia (NH3), NH3 plasma, hydrazine (e.g., hydrazine (N2H4), t-butylhydrazine (tBuHNNH2), and 1,1’-dimethylhydrazine (Me2NNH2)), molecular hydrogen (H2), hydrogen atom (H), hydrogen plasma, hydrogen radical, hydrogen excimers, alcohols (e.g., MeOH), aldehydes, carboxylic acids (e.g., formic acid), boranes (e.g., borane (BH3), diborane (B2H6), borane dimethylamine (BH3(NHMe2)), amines (e.g., t-butylamine (tBu)NH2, diethylamine (Et2NH)), silanes (e.g., silane (SiH4), disilane (Si2H6), trisilane (Si3H8)), and germane (e.g., germane (GeH4) and digermane (Ge2H6)). Many of the reducing agents listed above can only work with certain metal alkoxide precursors. Thus, the listed compounds can not be used as a general reducing agent.

[0083] In some embodiments, the second precursor is an oxygen precursor, a nitrogen precursor, a carbon precursor, a silicon precursor, a sulfur precursor, a selenium precursor, a phosphorous precursor, or a boron precursor.

[0084] In some embodiments, the second precursor comprises a borane compound. In some embodiments, the second precursor is selected from pinacol borane, bis-pinacol boron, 9-BBN, borane morpholine, catechol borane, 2-methylpyridine borane, borane pyridine adduct, decaborane, 1,4-bis(pinacolato boron)-1,4-dihydropyrazine, H3B*NEt3, H3B*NHMe2, H3B*SMe2, BN(Et) i Pr2, and BH3*THF. In some embodiments, the second precursor comprises an alkoxyborane compound. In some embodiments, the second precursor comprises, consists of, or consists essentially of pinacol borane.

[0085] Similar to the metal alkoxide precursor, the second precursor can be heated prior to being provided to the reaction chamber. The temperature to which the second precursor is heated depends on the nature of the second precursor. As will be appreciated by one of skill in the art, the vaporization temperatures of the metal alkoxide precursor and the second precursor can need to be compatible.

[0086] In some embodiments, the second precursor is heated to at least 20 °C, at least 25 °C, at least 30 °C, at least 50 °C, or at least 70 °C, or at least 90 °C, or at least 100 °C, or at least 110 °C prior to being provided to the reaction chamber. The heating can be performed in the precursor container. In some embodiments, the second precursor is heated to at most 120 °C, or at most 100 °C, or at most 80 °C, or at most 60 °C prior to being provided to the reaction chamber. The syringe system of the vapor deposition assembly can be heated to improve vapor phase delivery of the second precursor to the reaction chamber.

[0087] In one aspect of the application, a metal-containing layer produced by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In the process, the second precursor includes a borane compound.

[0088] In one aspect of the application, a semiconductor structure including a metal-containing layer deposited by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In the process, the second precursor includes a borane compound.

[0089] In one aspect of the application, a semiconductor device including a metal-containing layer deposited by a cyclic deposition process is disclosed. The process includes providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In the process, the second precursor includes a borane compound.

[0090] In one aspect of the application, a deposition assembly for depositing a metal-containing material on a substrate is disclosed. The deposition assembly includes one or more reaction chambers configured and arranged to hold a substrate; a precursor injector system configured and arranged to provide a metal alkoxide precursor and a second precursor into the reaction chamber in a vapor phase. The second precursor includes a borane compound. The deposition assembly further includes a precursor container configured and arranged to contain the metal alkoxide precursor; and the assembly is configured and arranged to provide the metal alkoxide precursor and the second precursor to the reaction chamber through the precursor injector system to deposit the metal-containing material on the substrate.

[0091] In one aspect of the application, a container containing a chemical precursor is disclosed. The container contains a bismuth alkoxide, wherein the container is configured to supply a vapor of the chemical precursor to a semiconductor processing equipment chamber.

[0092] In one aspect of the application, a metal-containing film deposition product is disclosed. The product includes: a metal-containing chemical precursor including a metal alkoxide; a second precursor including an alkoxyborane; a first container containing the chemical precursor; and a second container containing the second precursor, wherein the metal-containing chemical precursor is provided in the first container and the second precursor is provided in the second container, wherein the first and second containers are configured to be coupled to a semiconductor equipment via a reactant delivery system.

[0093] A vapor deposition assembly for depositing a metal-containing material on a substrate 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 metal alkoxide precursor according to the invention in the gas phase into the reaction chambers. The vapor deposition assembly also includes a reactant container configured and arranged to contain a composition according to the present disclosure, and the assembly is configured and arranged to provide the composition according to the present disclosure to the reaction chambers via the precursor injector system to deposit the metal-containing material on the substrate.

[0094] In some embodiments, the vapor deposition assembly may further include a control processor and software configured to operate the reaction chamber to perform an ALD process. In some embodiments, the vapor deposition assembly may further include a control processor and software configured to operate the reaction chamber to perform a CVD process.

[0095] In one embodiment of this disclosure, a selective deposition method is disclosed. The method includes: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into the reaction chamber in a gas phase; and providing a second precursor into the reaction chamber in a gas phase to form a material on the substrate. In this method, the second precursor comprises a borane compound. The substrate includes a first surface and a second surface. The deposited material is formed more extensively on the first surface than on the second surface. In other words, the first surface is the growth surface on which the deposited layer grows, and the second surface is the non-growth surface on which the deposited layer does not grow or grows only minimally.

[0096] In some embodiments, the first surface is selected from silicon, titanium nitride, and aluminum oxide. In some embodiments, the first surface is selected from Si, SiO2, SiN, SiC, SiOC, Ge, SiGe, TiN, TiCx, TaN, TaC, MoN, MoC, WN, WC, NbN, NbC, VN, VC, Al2O3, AlN, Ga2O3, GaN, In2O3, IGZO, TiO2, ZrO2, HfO2, V2O5, VO2, Nb2O5, Ta2O5, MoO3, MoO2, WO3, MoS2, WS2, Sc2O3, Y2O3, La2O3, Ce2O3, and CeO2. In some embodiments, the second surface is selected from cobalt and platinum. In some embodiments, the second surface is selected from Ni, Pd, Pt, Co, Rh, Ir, Ru, Re, Cr, Mo, and W.

[0097] This disclosure is further explained by the following exemplary embodiments depicted in the accompanying drawings. The illustrations presented herein are not intended to be actual views of any particular material, structure, device, or apparatus, but are merely schematic representations for describing embodiments of this 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 drawings may be exaggerated relative to other elements to aid in understanding the illustrated embodiments of this disclosure. The structures and apparatus depicted in the drawings may include additional elements and details, which may be omitted for clarity.

[0098] The specific embodiments shown and described are illustrative of the invention and are not intended to limit the scope of aspects and embodiments in any way. In fact, for the sake of brevity, conventional manufacturing, connection, preparation, and other functional aspects of the system may not be described in detail. Furthermore, the connecting lines shown in the figures are intended to represent exemplary functional relationships and / or physical connections between various elements. Many alternative or additional functional relationships or physical connections may exist in the actual system, and / or may not exist in some embodiments.

[0099] 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, as many variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in a different order, or in some cases omitted.

[0100] The subject matter of this disclosure includes all novel and non-obvious combinations and sub-combinations of the various processes, systems and configurations disclosed herein, as well as any and all equivalents thereof.

[0101] Figure 1A and Figure 1B Each diagram illustrates an exemplary embodiment of a method 100 for depositing a metallic material on a substrate. In a first stage 102, the substrate is provided into a reaction chamber. The substrate according to this disclosure may include, for example, oxides, such as silicon oxide (e.g., thermally heated silicon oxide or natural silicon oxide). The substrate may include nitrides (e.g., silicon nitride or titanium nitride), metals (e.g., copper, cobalt, or tungsten), or chalcogenide materials (e.g., molybdenum sulfide). The metallic material according to this disclosure may be deposited on the surface.

[0102] The reaction chamber may form part of an atomic layer deposition (ALD) assembly. The reaction chamber may form part of a chemical vapor deposition (CVD) assembly. The assembly may be a single-wafer reactor. Alternatively, the reactor may be a batch reactor. The assembly may include one or more multi-station deposition chambers. The various stages of method 100 may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a clustering tool. In some embodiments, method 100 is performed in a single reaction chamber of a clustering tool, but other, prior or subsequent manufacturing steps of the structure or apparatus are performed in another reaction chamber of the same clustering tool. Optionally, the assembly including the reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate and / or reactants and / or precursors. Metallic materials according to this disclosure may be deposited in a crossflow reaction chamber. Metallic materials according to this disclosure may be deposited in a spray head reaction chamber.

[0103] A metal alkoxide precursor 104 is provided in a reaction chamber containing a substrate. Without limiting this disclosure to any particular theory, the metal alkoxide precursor may be chemisorbed onto the substrate during the process of providing the metal alkoxide precursor to the reaction chamber. The duration for which the metal alkoxide precursor is provided to the reaction chamber (metal alkoxide precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0104] In the second deposition stage 106 of method 100, a second precursor is provided in a reaction chamber. In some embodiments, the second precursor comprises a reducing agent for depositing an elemental metal onto a substrate. In some embodiments, the second precursor comprises an oxygen precursor for depositing a metal oxide onto the substrate. In some embodiments, the second precursor comprises a nitrogen precursor for depositing a metal nitride onto the substrate. In some embodiments, the second precursor comprises a carbon precursor for depositing a metal carbide onto the substrate. In some embodiments, the second precursor comprises a silicon precursor for depositing a metal silicide onto the substrate. In some embodiments, the second precursor comprises a chalcogenide precursor (e.g., a sulfur or selenium precursor) for depositing a metal chalcogenide (e.g., a metal sulfide or a metal selenide) onto the substrate. In some embodiments, the second precursor comprises a phosphorus precursor for depositing a metal phosphide onto the substrate.

[0105] The stages 104 (providing the metal alkoxide precursor) and 106 (providing the second precursor) can be performed in any order. The stages 104 and 106 can constitute a deposition cycle, resulting in the deposition of a metal-containing material. In some embodiments, the two stages of metal-containing material deposition, namely the provision of the metal alkoxide precursor and the second precursor (104 and 106) (loop 108), can be repeated in the reaction chamber. Such embodiments include multiple deposition cycles. The thickness of the deposited metal-containing material can be adjusted by varying the number of deposition cycles. The deposition cycle (loop 108) can be repeated until the desired metal-containing material thickness is achieved. For example, approximately 50, 100, 200, 300, 400, 500, 700, 800, 1000, 1200, 1500, 2000, 2400, or 3000 deposition cycles can be performed. Cyclic deposition can result in the formation of a metal-containing layer. This layer can be continuous or substantially continuous.

[0106] In some embodiments, the cyclic deposition process includes alternately and sequentially providing a metal precursor and a second precursor in the reaction chamber. In some embodiments, the reaction chamber is purged between precursors 105 and 107, such as... Figure 1B As shown. In such an embodiment, the deposition cycle can be considered to include stages 104, 105, 106, and 107. As described above, the deposition cycle can be repeated 108 times to achieve the desired thickness of the metallic material.

[0107] The metal alkoxide precursor and the second precursor can be provided to the reaction chamber in separate steps (104 and 106). Figure 1B An embodiment according to this disclosure is shown, wherein steps 104 and 106 are separated by purging steps 105 and 107. In such an embodiment, the deposition cycle includes one or more purging steps 103, 105. During the purging steps, the precursors and / or reactants can be separated from each other in time by an inert gas (e.g., argon (Ar), nitrogen (N2), or helium (He)) and / or vacuum pressure. Alternatively, the separation of the metal alkoxide precursor and the second precursor can be spatial.

[0108] Purging reaction chambers 103 and 105 prevents or mitigates gas-phase reactions between the metal alkoxide precursor and the second precursor, and enables possible self-saturating surface reactions. Excess chemicals and reaction byproducts (if any) can be removed from the substrate surface before the substrate comes into contact with the next reactive chemical, for example, by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate is movable to contact the metal alkoxide precursor and the second precursor separately. Because the reaction can be self-saturating in some embodiments, strict temperature control of the substrate and precise dosage control of the precursor may not be required. However, the substrate temperature is preferably such that the incident gaseous material does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0109] When method 100 is performed, a metallic material is deposited onto a substrate. The deposition process can be a cyclic deposition process and can include cyclic CVD, ALD, or a hybrid cyclic CVD / ALD process. For example, in some embodiments, the growth rate of a particular ALD process may be lower than that of a CVD process. One way to increase the growth rate is to operate at a deposition temperature higher than that typically used in ALD processes, resulting in a portion of the chemical vapor deposition process, but still utilizing the sequential introduction of a metal alkoxide precursor and a second precursor. Such a process may be referred to as cyclic CVD. In some embodiments, a cyclic CVD process may include introducing two or more precursors into a reaction chamber, wherein there may be overlapping time periods between the two or more precursors in the reaction chamber, resulting in both the deposited ALD component and the deposited CVD component. This is referred to as a hybrid process. According to another example, a cyclic deposition process may include a continuous flow of one reactant or precursor and periodic pulses of another chemical component into the reaction chamber. The temperature and / or pressure within the reaction chamber during step 104 may be the same as or similar to any of the pressures and temperatures mentioned above in conjunction with step 102.

[0110] In some embodiments, a metal alkoxide precursor is contacted with a substrate surface 104, excess metal alkoxide precursor is partially or substantially completely removed by an inert gas or vacuum 105, and a second precursor is contacted with the substrate surface containing the metal alkoxide precursor. The metal alkoxide precursor may be contacted with the substrate surface by one or more pulses 104. In other words, the pulses 104 of the metal alkoxide precursor may be repeated. The metal alkoxide precursor on the substrate surface may react with the second precursor to form a metal-containing material on the substrate surface. The pulses 106 of the second precursor may also be repeated. In some embodiments, the second precursor 106 may be provided first in the reaction chamber. Thereafter, the reaction chamber 105 may be purged, and the metal alkoxide precursor 104 may be provided in the reaction chamber with one or more pulses.

[0111] Figure 2 A deposition assembly 200 according to the present disclosure is illustrated schematically. The deposition assembly 200 can be used to perform the methods described herein and / or form structures or devices or portions thereof as described herein.

[0112] In the example shown, the deposition assembly 200 includes one or more reaction chambers 202, a precursor injector system 201, a metal alkoxide precursor container 204, a second precursor container 206, an exhaust source 210, and a controller 212. The deposition assembly 200 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.

[0113] Reaction chamber 202 may include any suitable reaction chamber, such as the ALD or CVD reaction chamber described herein.

[0114] Metal alkoxide precursor container 204 may include a container and one or more metal alkoxide precursors as described herein—either alone or mixed with one or more carrier gases (e.g., inert gases). Second precursor container 206 may include a container and a second precursor as described herein—either alone or mixed with one or more carrier gases. Although two source containers 204, 206 are shown, the deposition assembly 200 may include any suitable number of source containers. Source containers 204, 206 may be coupled to reaction chamber 202 via lines 214, 216, each of which may include a flow controller, valve, heater, etc. In some embodiments, the metal alkoxide precursor in metal alkoxide precursor container 204 and the second precursor in second precursor container 206 may be heated. In some embodiments, the containers are heated such that the precursor or reactant reaches a temperature, for example, between about 20°C and about 200°C, depending on the nature of the chemical in question.

[0115] The emission source 210 may include one or more vacuum pumps.

[0116] Controller 212 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in the deposition assembly 200. Such circuitry and components operate to introduce precursors, reactants, and purge gases from appropriate sources. Controller 212 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 202, the pressure within the reaction chamber 202, and various other operations to provide appropriate operation of the deposition assembly 200. Controller 212 may include control software to electrically or pneumatically control valves to control the inflow and outflow of precursors, reactants, and purge gases from the reaction chamber 202. Controller 212 may include modules, such as software or hardware components, that perform certain tasks. Modules may be configured to reside on addressable storage media of the control system and configured to perform one or more processes.

[0117] Other configurations of the deposition assembly 200 are possible, including different numbers and types of precursor and reactant sources. Furthermore, it should be understood that numerous arrangements of valves, conduits, precursor sources, and auxiliary reactant sources exist to achieve the goal of selectively and in a coordinated manner feeding gas into the reaction chamber 202. Additionally, as a schematic representation of the deposition assembly, many components have been omitted for simplicity, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0118] During operation of the deposition assembly 200, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate transport system to a reaction chamber 202. Once the substrate is transferred to the reaction chamber 202, one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) from a gas source are introduced into the reaction chamber 202.

[0119] In some embodiments, the metal alkoxide precursor is supplied in pulses, the second precursor is supplied in pulses, and the reaction chamber is purged between consecutive pulses of the metal alkoxide precursor and the second precursor.

[0120] The exemplary embodiments of this disclosure described above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, which are defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to fall within the scope of the invention. Various modifications to this disclosure, such as alternative useful combinations of the elements, beyond those shown and described herein, will become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for selectively depositing a material on a substrate by a cyclic deposition process, the method comprising: providing a substrate into a reaction chamber, wherein the substrate comprises a first surface and a second surface; providing a metal alkoxide precursor in a gas phase into the reaction chamber; and providing a second precursor in a gas phase into the reaction chamber to form a material on the substrate; wherein the second precursor comprises a borane compound, and wherein the deposited material forms more on the first surface than on the second surface.

2. The method of claim 1, wherein, the first surface is selected from silicon, titanium nitride, and aluminum oxide.

3. The method of claim 1, wherein, the second surface is selected from cobalt and platinum.

4. The method of claim 1, wherein, the metal alkoxide precursor comprises at least one alkoxide ligand.

5. The method according to any one of the preceding claims, wherein, the metal alkoxide precursor comprises at least two alkoxide ligands.

6. The method according to any one of the preceding claims, wherein, the metal alkoxide precursor comprises three alkoxide ligands.

7. The method of any of the preceding claims, wherein, the metal alkoxide precursor is a metal aminoalkoxide precursor.

8. The method of claim 6, wherein, the metal alkoxide precursor comprises a ligand selected from dmap, dmamp, emamp, deamp, emamb, deamb, dmamb, and dmaeb.

9. The method of any of the preceding claims, wherein, the metal atom of the metal alkoxide precursor is selected from late transition metals and post transition metals.

10. The method of any of the preceding claims, wherein, the metal atom is selected from Ni, Cu, Co, Zn, Fe, Al, Bi, Ga, In, Tl, Sn, Mo, Nb, and Pb.

11. The method of any of the preceding claims, wherein, the metal atom comprises Bi or Cu.

12. The method of any of the preceding claims, wherein, The metal alkoxide precursor is selected from the group consisting of Ni(dmap)2, Ni(dmamp)2, Ni(emamp)2, Ni(deamp)2, Ni(emamb)2, Ni(deamb)2, Ni(dmaeb)2, Co(dmap)2, Co(dmamp)2, Co(emamp)2, Co(deamp)2, Co(emamb)2, Co(deamb)2, Co(dmaeb)2, Cu(dmap)2, Cu(dmamp)2, Cu(emamp)2, Cu(deamp)2, Cu(emamb)2, Cu(deamb)2, Cu(dmaeb)2, Fe(dmap)2, Fe(dmamp)2, Fe(emamp)2, Fe(deamp)2, Fe(emamb)2, Fe(deamb)2, Fe(dmaeb)2, Zn(dmap)2, Zn(dmamp)2, Zn(emamp)2, Zn(deamp)2, Zn(emamb)2, Zn(deamb)2, Zn(dmaeb)2, Al(O i Pr)3, Al(OBu) 3, Al(OEt) 3, AlO i Pr(Me) 2, Bi(OCMe2 i Pr) 3, Ga(O t Bu)3, GaCl2(OCH2CH2NMe2), Cu(OMe) 2, Cu(dmap) 2, Pb(dmamp)2, Tl(OEt), Sn(O t Bu)4, Sn(OEt)2, Zn(O i Pr) 2. Mo2(OCMe3)6, Nb2(OEt) 10 , Nb(OEt)5, Mo2(O2CMe3)4and Mo(thd)3.

13. The method of any of the preceding claims, wherein, said metal alkoxide precursor is selected from the group consisting of Al(O i Pr)3, Al(OBu) 3, Pr)3, Al(OBu) 3, Pr)3, Al(OBu) i Pr)3, Al(OBu) 2, Pr)3, Al(OBu) i Pr)3, Al(OBu) 3, Pr)3, Al(OBu) t Pr)3, Al(OBu) t Pr)3, Al(OBu) 2, Pr)3, Al(OBu) 2, Pr)3, Al(OBu) t Pr)3, Al(OBu) 14. The method of any of the preceding claims, wherein, said metal alkoxide precursor is selected from the group consisting of Bi(OCMe2 i Pr)3 and Cu(dmap)2.

15. The method of any of the preceding claims, wherein, the second precursor is a reducing agent.

16. The method of any of the preceding claims, wherein, said second precursor is selected from the group consisting of pinacolborane, bispinacolboron, 9-BBN, borane morpholine, catecholborane, 2-methylpyridineborane, borane pyridine adduct, 1,4-bis(pinacolato-boron)-1,4-dihydropyrazine, decaborane and BN(Et) i Pr2.

17. The method of any of the preceding claims, wherein, the second precursor comprises an alkoxyborane compound.

18. The method of any of the preceding claims, wherein, the second precursor comprises pinacolborane.

19. The method of any of the preceding claims, wherein, the metal-containing material comprises an elemental metal.

20. The method of any of the preceding claims, wherein, the metal alkoxide precursor is provided into the reaction chamber at a deposition temperature of 80-130 °C.

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