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 as a result of, on behalf of, and / or in connection with a joint research agreement between the University of Helsinki and ASM Microchemistry Oy. That agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities carried out within the scope of that agreement. Technical Field

[0003] The present disclosure relates to methods and apparatus for fabricating semiconductor devices. More particularly, the present disclosure relates to methods and apparatus for depositing metal-containing materials on substrates through a cyclic deposition process, and layers including metal-containing materials. Background Art

[0004] Copper is the most commonly used interconnect material in microelectronics, and despite a shift toward other metals, copper will remain the primary metal for interconnects for the foreseeable future. Modern applications require high-quality thin films that are deposited uniformly over large areas and on 3D structures. To achieve these qualities, vapor-phase thin film deposition methods are required, and among these methods, atomic layer deposition (ALD) is the method that best meets these requirements.

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

[0006] On the other hand, other metals such as metallic bismuth do not play such an important role in current microelectronics. However, this does not mean that they are not interesting materials, because many of them have unique properties that can be utilized in the future. Possible applications proposed 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 sulfide. Bismuth is a heavy element, so Bi films can be applied to, for example, x-ray optical devices and various novel patterning methods (EUV, multiple patterning).

[0007] Any discussion set forth in this section (including discussion of problems and solutions) is included in this disclosure solely for the purpose of providing context for this disclosure. Such discussion should not be construed as an admission that any or all of the information was known or otherwise constituted prior art at the time the present invention was made. Summary of the Invention

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

[0009] Various embodiments of the present disclosure relate to methods of depositing metal-containing materials on substrates, metal-containing layers, semiconductor structures and devices including the layers, and deposition assemblies for depositing metal-containing materials on substrates.

[0010] In a first aspect, a method for depositing a material on a substrate using a cyclic deposition process is disclosed. The method includes: providing the 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 the material on the substrate. In the method, the second precursor includes a borane compound.

[0011] In some embodiments, the metal alkoxide precursor is provided to the reaction chamber at a deposition temperature of 80-130°C, or 200-300°C, or 80-250°C.

[0012] In some embodiments, the metal alkoxide precursor comprises at least one alkoxide ligand.

[0013] In some embodiments, the metal alkoxide precursor comprises at least two alkoxide ligands.

[0014] In some embodiments, the metal alkoxide precursor comprises three alkoxide ligands.

[0015] In some embodiments, the metal alkoxide precursor is a metal aminoalkoxide precursor.

[0016] In some embodiments, the metal alkoxide precursor includes a ligand selected from the group consisting of: dmap, dmamp, emamp, deamp, emamb, deamb, and dmaeb.

[0017] In some embodiments, the metal atom of the metal alkoxide precursor is selected from late transition metals and late transition metals.

[0018] In some embodiments, the metal atom is selected from Ni, Cu, Co, Zn, Fe, Al, Bi, Ga, In, Tl, Sn, and Pb.

[0019] In some embodiments, the metal atom comprises Bi or Cu.

[0020] 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)5 and Mo2(O2CCH3)4.

[0021] 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 t Bu)4, Sn(OEt)2 and Zn(O i Pr)2.

[0022] In some embodiments, the metal alkoxide precursor is selected from Bi(OCMe2 iPr)3 and Cu(dmap)2.

[0023] In some embodiments, the second precursor is a reducing agent.

[0024] 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.

[0025] In some embodiments, the second precursor comprises an alkoxyborane compound.

[0026] In some embodiments, the second precursor includes pinacol borane.

[0027] In some embodiments, the second precursor comprises 1,4-bis(pinacolatoborone)-1,4-dihydropyrazine.

[0028] In some embodiments, the metal-containing material includes elemental metal.

[0029] In a second aspect, a metal-containing layer produced 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 vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In the method, the second precursor includes a borane compound.

[0030] In a third aspect, a semiconductor structure is disclosed that includes a metal-containing layer deposited via a cyclic deposition process. The method 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 method, the second precursor includes a borane compound.

[0031] In a fourth aspect, a semiconductor device is disclosed that includes a metal-containing layer deposited via a cyclic deposition process. The method 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 method, the second precursor includes a borane compound.

[0032] 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 constructed and arranged to hold a substrate; and a precursor injector system constructed and arranged to provide a metal alkoxide precursor and a second precursor to the reaction chambers in a vapor phase. The second precursor includes a borane compound. The deposition assembly also includes a precursor container constructed and arranged to hold the metal alkoxide precursor; and the deposition assembly is constructed and arranged to provide the metal alkoxide precursor and the second precursor to the reaction chambers via the precursor injector system to deposit the metal-containing material on the substrate.

[0033] 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 vapor of the chemical precursor to a semiconductor processing equipment chamber.

[0034] In a seventh aspect, a metal-containing film deposition product is disclosed. The product includes: a metal-containing chemical precursor comprising a metal alkoxide; a second precursor comprising an alkoxyborane; a first container comprising the chemical precursor; and a second container comprising 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 device via a reactant delivery system.

[0035] 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 vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In this method, the second precursor includes a borane compound. The substrate includes a first surface and a second surface. The deposited material is formed more on the first surface than on the second surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] 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:

[0037] Figure 1A and Figure 1B A block diagram of an exemplary embodiment of a method according to the present disclosure is shown.

[0038] Figure 2 is a schematic diagram of a deposition assembly 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. For example, the sizes of some elements in the drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION

[0040] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and obvious modifications and equivalents thereof. Accordingly, it is intended that the scope of the disclosed invention should not be limited by the specific disclosed embodiments described below.

[0041] In one aspect, a method for depositing a material on a substrate using a cyclic deposition process is disclosed. The method includes providing the 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 the material on the substrate. In the method, the second precursor includes a borane compound.

[0042] In a cyclic deposition process, the stages of providing a metal alkoxide precursor and providing a second precursor into the reaction chamber are repeated until a desired material thickness is achieved.

[0043] In methods according to the present disclosure, the material deposited on the substrate comprises a metal. In some embodiments, the metal-containing material comprises a transition metal. In some embodiments, the metal-containing material comprises a late transition metal. Late transition metals are defined as Groups 8 to 12 metals. In some embodiments, the metal-containing material comprises a late transition metal. Late transition metals are defined as the group of metals consisting of aluminum, gallium, indium, thallium, tin, lead, bismuth, germanium, antimony, and polonium. In some embodiments, the metal-containing material comprises copper. In some embodiments, the metal-containing material comprises bismuth. In some embodiments, the metal-containing material comprises an elemental metal.

[0044] In some embodiments, the metal-containing material comprises a metal oxide. In some embodiments, the metal-containing material comprises a metal nitride. In some embodiments, the metal-containing material comprises a metal carbide. In some embodiments, the metal-containing material comprises a metal selenide. In some embodiments, the metal-containing material comprises a metal sulfide. In some embodiments, the metal-containing material comprises a metal phosphide. In some embodiments, the metal-containing material comprises a metal boride. In some embodiments, the metal-containing material comprises a metal germanide.

[0045] 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, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or a cluster of atoms and / or molecules. A film or layer can include a material or layer having 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 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. The layer produced according to the methods disclosed herein can form a portion of a semiconductor structure and / or semiconductor device.

[0046] 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 integrated with additional processing steps to produce the semiconductor structure. The semiconductor structure can be part of a semiconductor device. Such a device is used in the manufacture of integrated circuits.

[0047] In some embodiments, the metal-containing material is deposited as a layer on the substrate. In some embodiments, the metal-containing layer comprises 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 comprises alternately and sequentially providing a metal alkoxide precursor and a second precursor to a reaction chamber. In some embodiments, the reaction chamber is purged between providing the precursors to the reaction chamber. Examples of such cyclic deposition processes are atomic layer deposition and cyclic chemical vapor deposition.

[0048] As used herein, the term "substrate" may refer to any one or more underlying materials that can be used to form or on which a device, circuit, material, or material layer can be formed. The substrate may comprise bulk materials 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). The substrate may include one or more layers covering the bulk material. The substrate may include various topological structures, such as gaps, including grooves, lines, trenches, or spaces between elevated portions (e.g., fins, etc.) formed within or on at least a portion of a layer of the substrate. The substrate may 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 materials, heteroepitaxial materials, and / or single crystal materials. In some embodiments of the present disclosure, the substrate comprises silicon. In addition to silicon, the substrate may include other materials as described above. Other materials may form layers.

[0049] In the present disclosure, a 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" may 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 a mixed cyclic deposition process including an ALD component and a cyclic CVD component. The method may include a purge step between providing a precursor or between providing a precursor and a reactant in the reaction chamber.

[0050] In this disclosure, any two numbers of a variable may constitute a working range for the variable, and any range indicated may include or exclude the endpoints.

[0051] In addition, any values of the indicated variables (whether or not they are indicated with "about") may refer to exact values or approximate values and include equivalent values, and may refer to average values, median values, representative values, multiple values, etc. Moreover, in this disclosure, the terms "comprising," "consisting of," and "having" independently refer, in some embodiments, to "generally or broadly comprising," "comprising," "consisting essentially of," or "consisting of." In this disclosure, any defined meaning does not necessarily exclude, in some embodiments, the ordinary and customary meaning.

[0052] The method may include one or more cyclic stages. For example, pulses of the metal alkoxide precursor and the second precursor may be repeated. Repeating the cyclic deposition step can be used to control the thickness of the deposited material. In some embodiments, the method includes one or more non-cyclic stages. In some embodiments, the deposition process includes a continuous flow of at least one precursor. In some embodiments, the reactant can be continuously provided in the reaction chamber. In such embodiments, the method includes a continuous flow of 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 typically be initiated with any one of at least two precursors and / or reactants used in the process. Therefore, in the current method, the first deposition cycle can be started by providing a metal alkoxide precursor or a second precursor in the reaction chamber.

[0053] The term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle, such as a plurality of continuous deposition cycles, is performed in a reaction chamber. As used herein, the term atomic layer deposition is also intended to include processes designated by related terms, such as chemical vapor atomic layer deposition when performed with alternating pulses of precursors / reactants and optional purge gases. Typically, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemically adsorbed onto a deposition surface (e.g., a substrate surface that may include a previously deposited material or other material from a previous ALD cycle) to form a monolayer or sub-monolayer of a material that is not easily reacted with another precursor (i.e., a self-limiting reaction). Thereafter, in some cases, another precursor or reactant may be subsequently introduced into the processing chamber for converting the chemically adsorbed precursor into the desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. A purge step may 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 to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a metal alkoxide precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing a second precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing each precursor to the reaction chamber.

[0054] The CVD type process generally relates to the gas phase reaction between two or more precursors and / or reactants.(one or more) precursors and (one or more) reactants can be provided to reaction space or substrate simultaneously, or are provided with partially or completely separated pulses. Substrate and / or reaction space can be heated to promote the reaction between gaseous precursors and / or reactants. In certain embodiments, one or more precursors and one or more reactants are provided until the layer with desired thickness is deposited. In certain embodiments, the cyclic CVD process can be used together with multiple cycles to deposit a film with desired thickness. In the cyclic CVD process, precursors and / or reactants can be provided to the reaction chamber with non-overlapping or partially or completely overlapping pulses.

[0055] As used herein, the term "purge" may 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). Purge can be performed between two gas pulses that react with each other. However, purge can be performed between two pulses of gases that do not react with each other. For example, purge can be provided between pulses of two precursors or between a precursor and a reactant. Purge can avoid or at least reduce the gaseous phase interaction between the two gases that react with each other. It should be understood that purge can be achieved in time or in space or both. For example, in the case of time purge, a purge step can be used, for example, in the 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, wherein the substrate on which the layer is deposited does not move. For example, in the case of space purge, the purge step can take the following form: the substrate is moved from a first position where the first precursor is continuously supplied through a purge gas curtain to a second position where the 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, such as 1 second or 2 seconds. However, other purge times can be utilized if desired, such as where highly conformal step coverage is desired on very high aspect ratio structures or other structures with complex surface morphology, or where use is required in certain reactor types, such as batch reactors.

[0056] In some embodiments, the cyclic deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, chemical reactions can be promoted by elevated temperatures relative to the ambient temperature. Typically, the elevated temperature provides the energy required to form the metal-containing material in the absence of other external energy sources (e.g., plasma, free 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.

[0057] The method according to the present invention includes providing a substrate in a reaction chamber, providing a metal alkoxide precursor in a vapor phase into the reaction chamber, and providing a second precursor in a vapor phase into the reaction chamber to form a metal-containing material on the substrate.

[0058] The method of depositing a metal-containing material according to the present disclosure includes 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 separated 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 large-scale manufacturing. In some embodiments, the reaction chamber can be a batch reactor for simultaneously manufacturing multiple substrates. The reaction chamber according to the present disclosure can also be a deposition station in a multi-station chamber.

[0059] Furthermore, in the method according to the present disclosure, the metal alkoxide precursor is provided into the reaction chamber in a vapor phase, and the second precursor is provided into the reaction chamber in a vapor phase to form the metal-containing material on the substrate.

[0060] In the method according to the present disclosure, when the metal alkoxide precursor is in the reaction chamber, the metal alkoxide precursor can be in the gas phase. The metal alkoxide precursor can be partially gaseous or liquid, or even solid at some point in time before being provided to the reaction chamber. In other words, the metal alkoxide precursor can be a solid, liquid or gas, for example, in a precursor container or other container, and then transported in the reaction chamber. When transporting to the reaction chamber, various means of causing the precursor to enter the gas phase can be applied. Such means can include, for example, a heater, an evaporator, an air flow or applying a reduced pressure or any combination thereof. Therefore, the method according to the present invention can include heating the metal alkoxide precursor before providing the metal alkoxide precursor to the reaction chamber.

[0061] Considering conventional cyclic deposition processes, metal alkoxide compounds may decompose at relatively low temperatures. For example, the compounds may begin to decompose at temperatures below 200°C. Some metal alkoxide compounds may begin to decompose at temperatures below 150°C. However, the inventors have discovered that metal alkoxide compounds according to the present disclosure may be suitable or even advantageous for cyclic deposition processes at temperatures below about 140°C.

[0062] In some embodiments, deposition of metal-containing materials according to the present disclosure is performed at a temperature below about 200° C., or below about 185° C., or below about 150° C. In some embodiments, deposition is performed 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.

[0063] 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 before 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. Heating can be performed in a 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 before being provided to the reaction chamber. The injector system of the vapor deposition assembly can be heated to improve the vapor delivery of the metal alkoxide precursor to the reaction chamber.

[0064] In the present disclosure, "gas" can include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and can be composed of a single gas or a mixture of gases, depending on the context. The metal alkoxide precursor can be provided to the reaction chamber in a gas phase. The second precursor can be provided to the reaction chamber in a gas phase. The term "inert gas" can refer to a gas that does not participate in the chemical reaction 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 cases, molecular nitrogen and / or hydrogen can be inert gases. Gases other than process gases, i.e., gases that are not introduced through a precursor injector system, other gas distribution devices, etc., can be used, for example, to seal the reaction space and can include sealing gases.

[0065] In some embodiments, the metal-containing material comprises an elemental metal. Thus, the deposited metal may at least partially have an oxidation state of 0. In some embodiments, substantially all or all of the metal is deposited as an elemental metal. In some embodiments, the deposited metal comprises, consists of, or consists essentially of elemental copper. In some embodiments, the deposited metal comprises, consists of, or consists essentially of elemental bismuth. In some embodiments, a layer consisting of, or consisting essentially of, an elemental metal is deposited. In some embodiments, the metal according to the present disclosure is deposited as a layer, and in addition to the metal, the layer also comprises a large amount of other elements. In such embodiments, the metal may exist as an elemental metal. In some embodiments, the metal deposited according to the present disclosure exists as an alloy with another metal.

[0066] 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 comprises a metal nitride. In some embodiments, the metal-containing material deposited according to the present disclosure comprises a metal silicide. In some embodiments, the metal-containing material deposited according to the present disclosure comprises 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 comprises a metal selenide. In some embodiments, the metal-containing material deposited according to the present disclosure comprises a metal phosphide. In some embodiments, the metal-containing material deposited according to the present disclosure comprises 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 may comprise 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.

[0067] The growth rate of the metal-containing material may be, for example, from about 0.05 to about The growth rate and layer properties may depend on the temperature at which the deposition process is performed. In some embodiments, the growth rate may be about or about or about or about The growth rate may vary during the deposition process.

[0068] The deposition cycle, including providing the metal alkoxide precursor to the reaction chamber (i.e., pulsing the metal alkoxide precursor) and providing the second precursor to the reaction chamber (i.e., pulsing the second precursor), and the optional 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.

[0069] The resistivity of a metal-containing material deposited as a layer depends on the material composition. Furthermore, for a given material, such as an elemental metal-containing material, the resistivity may depend on process conditions, such as the temperature and growth rate of the layer. In embodiments where the metal-containing layer comprises primarily or substantially only elemental metal, the resistivity may be, for example, less than about 10 μΩcm, such as less than about 7 μΩcm, such as less than about 5 μΩcm, for example, between 1 μΩcm and 10 μΩcm, such as between 2 μΩcm and 7 μΩcm.

[0070] In some embodiments, the metal-containing material comprises elemental metal and less than 20 atomic percent carbon. In some embodiments, the metal-containing layer comprises elemental metal and less than 15 atomic percent carbon. In some embodiments, the metal-containing layer comprises elemental metal and less than 10 atomic percent carbon. In some embodiments, the metal-containing material comprises elemental metal and less than 2 atomic percent oxygen. In some embodiments, the metal-containing material comprises elemental metal and less than 1 atomic percent nitrogen.

[0071] The terms "precursor" and "reactant" may refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction that produces another compound. A precursor typically comprises 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 may be deposited on a substrate. A reactant may 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 may also contribute to the resulting compound or element.

[0072] As used herein, a "metal alkoxide precursor" includes a gas or a material that can be changed into a gaseous state, and may be represented by a chemical formula including a metal alkoxide.

[0073] 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 comprises bismuth or copper.

[0074] In some embodiments, the metal alkoxide precursor comprises at least one alkoxide ligand. In some embodiments, the metal alkoxide precursor comprises at least two alkoxide ligands. In some embodiments, the metal alkoxide precursor comprises three alkoxide ligands.

[0075] In some embodiments, the metal alkoxide precursor is a metal aminoalkoxide precursor. In some embodiments, the metal alkoxide precursor comprises a ligand selected from the group consisting of 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).

[0076] 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)2 and Zn(O i In some embodiments, the metal alkoxide precursor is selected from Al(O iPr)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)4 and Mo(thd)3 (thd=2,2,6,6-tetramethylheptane-3,5-dione).

[0077] In some embodiments, the metal alkoxide precursor comprises Bi(OCMe2 i Pr)3, consisting essentially of Bi(OCMe2 i In some embodiments, the metal alkoxide precursor comprises, consists of, or consists essentially of Cu(dmap)2.

[0078] In some embodiments, the metal alkoxide precursor is provided as a mixture of two or more compounds. In the mixture, other compounds except the metal alkoxide precursor can be an inert compound or an element. In some embodiments, the metal alkoxide precursor is provided as a composition. A composition suitable for use as a composition may include a metal alkoxide compound and an effective amount of one or more stabilizers. The composition may 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 may include two different metal-containing compounds, one or more of which are metal alkoxide compounds according to the present disclosure.

[0079] The metal-containing material is formed by providing a second precursor to the reaction chamber in a vapor phase. The conversion of the metal alkoxide precursor to the desired metal-containing material can occur on the surface of the substrate. In some embodiments, the conversion can be at least partially performed in the vapor phase. In some embodiments, the reaction between the metal alkoxide precursor and the second precursor occurs substantially only on the surface of the substrate.

[0080] In some embodiments, the second precursor is a reducing agent that can reduce the metal of the metal alkoxide precursor to elemental metal. In some embodiments, the reducing agent is selected from the group consisting of forming gases (H2+N2), ammonia (NH3), NH3 plasma, hydrazine (e.g., hydrazine (N2H4), tert-butylhydrazine (tBuHNNH2), and 1,1'-dimethylhydrazine (Me2NNH2)), molecular hydrogen (H2), hydrogen atoms (H), hydrogen plasma, hydrogen radicals, hydrogen excited species, alcohols (e.g., MeOH), aldehydes, carboxylic acids (e.g., formic acid), boranes (e.g., borane (BH3), diborane (B2H6), boranedimethylamine (BH3(NHMe2)), amines (e.g., tert-butylamine (tBu)NH2, diethylamine (Et2NH)), silanes (e.g., silane (SiH4), disilane (Si2H6), trisilane (Si3H8)), and germanes (e.g., germane (GeH4) and digermane (Ge2H6)). Many of the reducing agents listed above may only work with certain metal alkoxide precursors. Therefore, the listed compounds may not be used as general reducing agents.

[0081] 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 phosphorus precursor, or a boron precursor.

[0082] 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(pinacol boron)-1,4-dihydropyrazine, H3B*NEt3, H3B*NHMe2, H3B*SMe2, BN(Et) i 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.

[0083] Similar to the metal alkoxide precursor, the second precursor may be heated before being provided to the reaction chamber. The temperature to which the second precursor is heated depends on the properties of the second precursor. As will be appreciated by those skilled in the art, the evaporation temperatures of the metal alkoxide precursor and the second precursor may need to be compatible.

[0084] 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. before 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. before being provided to the reaction chamber. The injector system of the vapor deposition assembly can be heated to improve vapor delivery of the second precursor to the reaction chamber.

[0085] In one aspect of the present invention, a metal-containing layer produced 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 vapor phase; and providing a second precursor into the reaction chamber in a vapor phase to form a material on the substrate. In the method, the second precursor includes a borane compound.

[0086] In one aspect of the present invention, a semiconductor structure is disclosed that includes a metal-containing layer deposited via a cyclic deposition process. The method 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 method, the second precursor includes a borane compound.

[0087] In one aspect of the present invention, a semiconductor device is disclosed that includes a metal-containing layer deposited via a cyclic deposition process. The method 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 method, the second precursor includes a borane compound.

[0088] In one aspect of the present invention, a deposition assembly for depositing a metal-containing material on a substrate is disclosed. The deposition assembly includes one or more reaction chambers constructed and arranged to hold a substrate; a precursor injector system constructed and arranged to provide a metal alkoxide precursor and a second precursor to the reaction chambers in a vapor phase. The second precursor includes a borane compound. The deposition assembly also includes a precursor container constructed and arranged to hold the metal alkoxide precursor; and the deposition assembly is constructed and arranged to provide the metal alkoxide precursor and the second precursor to the reaction chambers via the precursor injector system to deposit the metal-containing material on the substrate.

[0089] In one aspect of the present invention, a container comprising a chemical precursor is disclosed. The container contains a bismuth alkoxide, wherein the container is configured to supply vapor of the chemical precursor to a semiconductor processing equipment chamber.

[0090] In one aspect of the present invention, a metal-containing film deposition product is disclosed. The product includes: a metal-containing chemical precursor comprising a metal alkoxide; a second precursor comprising an alkoxyborane; a first container comprising the chemical precursor; and a second container comprising 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 device via a reactant delivery system.

[0091] The vapor deposition assembly for depositing a metal-containing material on a substrate includes one or more reaction chambers constructed and arranged to hold a substrate; and a precursor injector system constructed and arranged to provide an alkoxide metal salt precursor according to the present invention into the reaction chamber in a vapor phase. The vapor deposition assembly also includes a reactant container constructed and arranged to hold a composition according to the present disclosure, and the deposition assembly is constructed and arranged to provide the composition according to the present disclosure to the reaction chamber via the precursor injector system to deposit the metal-containing material on the substrate.

[0092] 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.

[0093] In one embodiment of the present 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 vapor phase; and providing a second precursor into the reaction chamber in a vapor 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 deposited material is formed more on the first surface than on the second surface. In other words, the first surface is a growth surface on which a deposited layer grows, and the second surface is a non-growth surface on which a deposited layer does not grow or only grows minimally.

[0094] 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, TiC xIn some embodiments, the second surface is selected from the group consisting of cobalt and platinum. In some embodiments, the second surface is selected from the group consisting of Ni, Pd, Pt, Co, Rh, Ir, Ru, Re, Cr, Mo, and W.

[0095] In some embodiments, selective deposition can be achieved by selectively forming an inhibitor layer on the first surface. The inhibitor layer is formed on the substrate and inhibits the growth of the deposited material on the surface. In some embodiments, a second precursor can serve as the inhibitor layer. In some embodiments, the second precursor comprises pinacol borane. In some embodiments, the deposited material is selected from Ni, Cu, Co, Zn, Fe, Al, Bi, Ga, In, Tl, Sn, Mo, Nb, and Pb. In some embodiments, the deposited material is selected from Cu and Bi.

[0096] The present 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 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 drawings may be exaggerated relative to other elements to help improve understanding of the illustrated embodiments of the present disclosure. The structures and apparatus depicted in the drawings may contain additional elements and details, which may be omitted for clarity.

[0097] The specific embodiments shown and described are illustrative of the present invention and are not intended to otherwise limit the scope of the various aspects and embodiments in any way. In fact, for the sake of brevity, the conventional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between the various elements. Many alternative or additional functional relationships or physical connections may exist in actual systems, and / or may not exist in some embodiments.

[0098] 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 restrictive, as many variations are possible. The specific 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 other orders, or in some cases omitted.

[0099] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

[0100] Figure 1A and Figure 1B A block diagram of an exemplary embodiment of a method 100 for depositing a metal-containing material on a substrate is shown. In a first stage 102, a substrate is provided to a reaction chamber. The substrate according to the present disclosure may include, for example, an oxide, such as silicon oxide (e.g., thermal silicon oxide or native silicon oxide). The substrate may include a nitride (e.g., silicon nitride or titanium nitride), a metal (e.g., copper, cobalt, or tungsten), or a chalcogenide material (e.g., molybdenum sulfide). The metal-containing material according to the present disclosure may be deposited on the surface.

[0101] 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 reaction chambers of a cluster tool. In some embodiments, method 100 is performed in a single reaction chamber of a cluster tool, but other, previous or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same cluster 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. The metal-containing material according to the present disclosure may be deposited in a cross-flow reaction chamber. The metal-containing material according to the present disclosure may be deposited in a showerhead reaction chamber.

[0102] A metal alkoxide precursor 104 is provided in a reaction chamber containing a substrate. Without limiting the present disclosure to any particular theory, the metal alkoxide precursor may be chemically adsorbed on the substrate during the time the metal alkoxide precursor is provided to the reaction chamber. The duration of providing the metal alkoxide precursor 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.

[0103] In the second deposition phase 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 elemental metal on the substrate. In some embodiments, the second precursor comprises an oxygen precursor for depositing a metal oxide on the substrate. In some embodiments, the second precursor comprises a nitrogen precursor for depositing a metal nitride on the substrate. In some embodiments, the second precursor comprises a carbon precursor for depositing a metal carbide on the substrate. In some embodiments, the second precursor comprises a silicon precursor for depositing a metal silicide on the substrate. In some embodiments, the second precursor comprises a chalcogen precursor (e.g., a sulfur or selenium precursor) for depositing a metal chalcogenide (e.g., a metal sulfide or a metal selenide) on the substrate. In some embodiments, the second precursor comprises a phosphorus precursor for depositing a metal phosphide on the substrate.

[0104] The stage of providing the metal alkoxide precursor 104 and the stage of providing the second precursor 106 can be performed in any order. The stage of providing the metal alkoxide precursor 104 and the stage of providing the second precursor 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 can be repeated, i.e., providing the metal alkoxide precursor and the second precursor (104 and 106) in the reaction chamber (cycle 108). Such an embodiment comprises a plurality of deposition cycles. The thickness of the deposited metal-containing material can be adjusted by adjusting the number of deposition cycles. The deposition cycle (cycle 108) can be repeated until the desired metal-containing material thickness is achieved. For example, about 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. The layer can be substantially continuous or continuous.

[0105] In some embodiments, the cyclic deposition process includes alternately and sequentially providing a metal precursor and a second precursor in a reaction chamber. Figure 1B As shown, the reaction chamber is purged between precursors 105, 107. In such an embodiment, a deposition cycle can be considered to include stages 104, 105, 106, and 107. As described above, the deposition cycle can be repeated 108 multiple times to achieve a desired thickness of the metal-containing material.

[0106] The metal alkoxide precursor and the second precursor may be provided to the reaction chamber in separate steps (104 and 106). Figure 1BAn embodiment according to the present disclosure is shown in which steps 104 and 106 are separated by purge steps 105 and 107. In such an embodiment, the deposition cycle includes one or more purge steps 103, 105. During the purge 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. The separation of the metal alkoxide precursor and the second precursor can alternatively be spatial.

[0107] Purging the reaction chambers 103, 105 can prevent or mitigate the gas phase reaction between the metal alkoxide precursor and the second precursor and enable a possible self-saturating surface reaction. Before the substrate contacts the next reactive chemical, excess chemicals and reaction byproducts (if any) can be removed from the substrate surface, for example by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate can be moved to contact the metal alkoxide precursor and the second precursor separately. Because in some embodiments, the reaction can be self-saturating, strict temperature control of the substrate and precise dosage control of the precursors may not be required. However, the substrate temperature is preferably such that the incident gas species does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0108] When method 100 is performed, a metal-containing 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 compared to a CVD process. One way to increase the growth rate may be to operate at a higher deposition temperature than typically employed in an ALD process, resulting in some portions of the chemical vapor deposition process, while 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 an overlapping period of time between the two or more precursors in the reaction chamber, resulting in both an ALD component and a CVD component of the deposition. 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 or similar to any of the pressures and temperatures mentioned above in connection with step 102.

[0109] In some embodiments, a metal alkoxide precursor is contacted with the substrate surface 104, excess metal alkoxide precursor is partially or substantially completely removed 105 by an inert gas or vacuum, 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 104 in one or more pulses. In other words, the pulses of the metal alkoxide precursor 104 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 of the second precursor 106 may also be repeated. In some embodiments, the second precursor 106 may be provided in a first reaction chamber. Thereafter, the reaction chamber 105 may be purged, and the metal alkoxide precursor 104 may be provided in the reaction chamber in one or more pulses.

[0110] Figure 2 A deposition assembly 200 according to the present disclosure is illustrated in a schematic manner. The deposition assembly 200 can be used to perform methods as described herein and / or form structures or devices as described herein, or portions thereof.

[0111] 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.

[0112] Reaction chamber 202 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber as described herein.

[0113] The 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., an inert gas). The 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 shown with two source containers 204, 206, the deposition assembly 200 may include any suitable number of source containers. The source containers 204, 206 may be coupled to the reaction chamber 202 via lines 214, 216, which may each include a flow controller, a valve, a heater, and the like. In some embodiments, the metal alkoxide precursor in the metal alkoxide precursor container 204 and the second precursor in the second precursor container 206 may be heated. In some embodiments, the containers are heated so that the precursors or reactants reach a temperature, for example, between about 20°C and about 200°C, depending on the nature of the chemical species in question.

[0114] Exhaust source 210 may include one or more vacuum pumps.

[0115] The 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 corresponding sources. The 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 proper operation of the deposition assembly 200. The controller 212 can include control software to electrically or pneumatically control valves to control the flow of precursors, reactants, and purge gases into and out of the reaction chamber 202. The controller 212 can include modules, such as software or hardware components, that perform certain tasks. The modules can be configured to reside on an addressable storage medium of the control system and to execute one or more processes.

[0116] 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 there are many arrangements of valves, conduits, precursor sources, and auxiliary reactant sources that can be used to achieve the goal of selectively and in a coordinated manner feeding gases into the reaction chamber 202. Furthermore, as a schematic representation of the deposition assembly, many components have been omitted for simplicity of illustration, and such components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0117] During operation of the deposition assembly 200, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to the 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.

[0118] 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 successive pulses of the metal alkoxide precursor and the second precursor.

[0119] The exemplary embodiments of the present disclosure described above do not limit the scope of the present invention, as these embodiments are merely examples of embodiments of the present invention, which are defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to fall within the scope of the present invention. In addition to those shown and described herein, various modifications of the present disclosure, such as alternative useful combinations of the elements, may 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 depositing a material on a substrate by a cyclic deposition process, the method comprising: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into a reaction chamber in a vapor phase; as well as providing a second precursor in a vapor phase into the reaction chamber to form a material on the substrate; Wherein, the second precursor includes a borane compound.

2. 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 into a reaction chamber in a vapor phase; as well as providing a second precursor in a vapor 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 is formed more on the first surface than on the second surface.

3. The method according to claim 1, wherein The first surface is selected from the group consisting of silicon, titanium nitride, and aluminum oxide.

4. The method according to claim 1, wherein The second surface is selected from the group consisting of cobalt and platinum.

5. The method according to claim 1, wherein The metal alkoxide precursor comprises at least one alkoxide ligand.

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

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

8. A method according to any one of the preceding claims, wherein The metal alkoxide precursor is a metal aminoalkoxide precursor.

9. The method according to claim 6, wherein: The metal alkoxide precursor comprises a ligand selected from the group consisting of dmap, dmamp, emamp, deamp, emamb, deamb, dmamb, and dmaeb.

10. A method according to any one of the preceding claims, wherein The metal atom of the metal alkoxide precursor is selected from late transition metals and late transition metals.

11. The method according to claim 1, wherein The metal atom is selected from Ni, Cu, Co, Zn, Fe, Al, Bi, Ga, In, Tl, Sn, Mo, Nb and Pb.

12. The method according to claim 1, wherein The metal atoms include Bi or Cu.

13. The method according to claim 1, wherein 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)2,Zn(O i Pr) 2, Mo2(OCMe3)6,Nb2(OEt) 10 ,Nb(OEt)5,Mo2(O2CMe3)4 and Mo(thd)3.

14. The method according to claim 1, wherein 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)3Cu(OMe) 2, Cu(dmap) 2, Pb(dmamp)2,Tl(OEt),Sn(O t Bu)4, Sn(OEt)2 and Zn(O i Pr)2.

15. The method according to claim 1, wherein The metal alkoxide precursor is selected from Bi(OCMe2 i Pr)3 and Cu(dmap)2.

16. A method according to any one of the preceding claims, wherein The second precursor is a reducing agent.

17. The method according to claim 1, wherein The second precursor is selected from pinacol borane, bis-pinacol boron, 9-BBN, borane morpholine, catechol borane, 2-methylpyridine borane, borane pyridine adduct, 1,4-bis(pinacol boron)-1,4-dihydropyrazine, decaborane and BN(Et) i Pr2.

18. The method according to claim 1, wherein The second precursor includes an alkoxyborane compound.

19. The method according to claim 1, wherein The second precursor includes pinacol borane.

20. A method according to any one of the preceding claims, wherein The metalliferous material comprises elemental metal.

21. A metal-containing layer produced by a cyclic deposition process, the cyclic deposition process comprising: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into a reaction chamber in a vapor phase; as well as providing a second precursor in a vapor phase into the reaction chamber to form a material on the substrate; Wherein, the second precursor includes a borane compound.

22. A semiconductor structure comprising a metal-containing layer deposited by a cyclic deposition process, the cyclic deposition process comprising: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into a reaction chamber in a vapor phase; as well as providing a second precursor in a vapor phase into the reaction chamber to form a material on the substrate; Wherein, the second precursor includes a borane compound.

23. A semiconductor device comprising a metal-containing layer deposited by a cyclic deposition process, the cyclic deposition process comprising: providing a substrate into a reaction chamber; providing a metal alkoxide precursor into a reaction chamber in a vapor phase; as well as providing a second precursor in a vapor phase into the reaction chamber to form a material on the substrate; Wherein, the second precursor includes a borane compound.

24. A deposition assembly for depositing a metal-containing material on a substrate, comprising: one or more reaction chambers constructed and arranged to hold a substrate; a precursor injector system constructed and arranged to provide a metal alkoxide precursor and a second precursor into the reaction chamber in a vapor phase, wherein the second precursor comprises a borane compound; The deposition assembly also includes a precursor vessel constructed and arranged to contain a metal alkoxide precursor; and The deposition assembly is constructed and arranged to provide a metal alkoxide precursor and a second precursor to the reaction chamber via the precursor injector system to deposit a metal-containing material on the substrate.

25. A container comprising a chemical precursor, the chemical precursor comprising a bismuth alkoxide, wherein the container is configured to supply a vapor of the chemical precursor to a semiconductor processing equipment chamber.

26. A metal film deposition product, comprising: a metal-containing chemical precursor comprising a metal alkoxide; a second precursor comprising an alkoxyborane; A first container comprising a chemical precursor; and a second container comprising a 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 device via a reactant delivery system.

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