Method and system for depositing metalloid layers

Abstract

The present disclosure relates to methods and apparatus for depositing a metalloid material on a substrate by a cyclic deposition process. The method includes: providing a substrate in a reaction chamber, providing a first 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 metalloid material on the substrate. At least one of the first precursor and the second precursor includes a metalloid compound.

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 a metalloid material on a substrate by a cyclic deposition process, and layers including the metalloid material. Background Art

[0004] Global demand for computing power and data storage capacity is rapidly increasing. Academia and the semiconductor industry have been conducting research efforts to increase transistor density and reduce device power consumption. This has led to the increasing miniaturization of highly complex structures and device features. Phase change memory (PCM) materials are considered a strong contender to form the basis of new memory technologies.

[0005] The Ge-Sb-Te (GST) ternary compound is considered the most promising candidate for industrial applications. GeTe is also a PCM material with potential use in applications such as automotive. A key aspect of GST and GeTe material development is adjusting the stoichiometry, as changes in the material composition affect the device's data retention time, switching speed, and other key characteristics. Due to the self-limiting nature of the ALD process, stoichiometric adjustment must be primarily accomplished by changing the ALD cycling scheme. Therefore, adding Te cycling to the overall process can be used to adjust the tellurium concentration of the material.

[0006] 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

[0007] This summary is provided to introduce a selection of concepts in a simplified form. These concepts are further described in detail in the detailed description of 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.

[0008] Various embodiments of the present disclosure relate to methods of depositing a metalloid material on a substrate, metalloid layers, semiconductor devices and structures including the layers, and deposition assemblies for depositing a metalloid material on a substrate.

[0009] In a first aspect, a method for depositing an elemental metalloid material on a substrate via a cyclic deposition process is disclosed. The method includes providing the substrate in a reaction chamber; providing a first precursor in the vapor phase into the reaction chamber; and providing a second precursor in the vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0010] In some embodiments, the first precursor includes an alkylsilyl group or a silyl group.

[0011] In some embodiments, the first precursor comprises a metalloid alkylsilyl group or a metalloid silyl group.

[0012] In some embodiments, the alkyl group is a C1-C4 alkyl group.

[0013] In some embodiments, the alkyl group is ethyl.

[0014] In some embodiments, the second precursor comprises a halide.

[0015] In some embodiments, the second precursor comprises a metalloid halide.

[0016] In some embodiments, the halide is selected from chlorine, bromine, fluorine, and iodine.

[0017] In some embodiments, the metalloid is selected from tellurium, germanium, boron, silicon, arsenic, selenium, and antimony.

[0018] In some embodiments, the metalloid is tellurium or germanium.

[0019] In some embodiments, the metalloid in at least one of the first precursor or the second precursor is tellurium.

[0020] In some embodiments, the metalloid in the first precursor and the second precursor is tellurium.

[0021] In some embodiments, the metalloid in the first precursor is tellurium and the metalloid in the second precursor is germanium.

[0022] In some embodiments, the first precursor is selected from (Et3Si)2Te, (Me3Si)2Te, ( i Pr3Si)2Te,( tBuMe2Si)2Te,(Me2Si)2Te2,(Me2SiC2H4SiMe2)Te,(Me2SiSiMe2)2Te2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t BuMe2Ge)2Te, (Me2Ge)2Te2, (Me2GeC2H4GeMe2)Te, (Me2GeGeMe2)2Te2, Me8Ge4Te2, Te(GeMe3)2, (Me3Ge)3Sb, (Et3Ge)3Sb and (Et3Ge)3As.

[0023] In some embodiments, the first precursor comprises (R3Si)2Te, wherein R is a C1-C4 alkyl group.

[0024] In some embodiments, the first precursor comprises a compound selected from the following formulas: (R2Si)2E2, (R2SiC2R4SiR2)E, and (R2SiSiR2)2E, wherein E=Te or Se, and each R is independently selected from C1-C4 alkyl.

[0025] In some embodiments, the first precursor includes (Et3Si)2Te.

[0026] In some embodiments, the second precursor includes BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4 and TeCl2.

[0027] In one aspect, a method for depositing a metalloid-containing material on a substrate via a cyclic deposition process is disclosed. The method includes a supercycle comprising providing a substrate into a reaction chamber and two subcycles. The first subcycle comprises providing a first precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase. The second subcycle comprises providing the first precursor into the reaction chamber in a vapor phase; and providing a third precursor into the reaction chamber in a vapor phase. In the method, the first precursor comprises a metalloid alkylsilyl group, the second precursor comprises a metalloid halide, and the third precursor comprises a metalloid halide, and the second and third precursors are different from each other.

[0028] In some embodiments, the first precursor is selected from (Et3Si)2Te, (Me3Si)2Te, (i Pr3Si)2Te,( t BuMe2Si)2Te,(Me2Si)2Te2,(Me2SiC2H4SiMe2)Te,(Me2SiSiMe2)2Te2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t BuMe2Ge)2Te, (Me2Ge)2Te2, (Me2GeC2H4GeMe2)Te, (Me2GeGeMe2)2Te2, Me8Ge4Te2, Te(GeMe3)2, (Me3Ge)3Sb, (Et3Ge)3Sb and (Et3Ge)3As.

[0029] In some embodiments, the second precursor and the third precursor are selected from BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4 and TeCl2.

[0030] In one aspect, a metalloid-containing layer produced by a cyclic deposition process is disclosed. The deposition process includes providing a substrate in a reaction chamber; providing a first precursor in the vapor phase into the reaction chamber; and providing a second precursor in the vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0031] In some embodiments, the layer comprises an elemental metalloid.

[0032] In one aspect, a semiconductor structure is disclosed that includes a metalloid-containing layer deposited by a cyclic deposition process. The method includes providing a substrate in a reaction chamber; providing a first precursor in a vapor phase into the reaction chamber; and providing a second precursor in a vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0033] In one aspect, a semiconductor device is disclosed that includes a metalloid-containing layer deposited via a cyclic deposition process. The method includes providing a substrate in a reaction chamber; providing a first precursor in a vapor phase into the reaction chamber; and providing a second precursor in a vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0034] In one aspect, a deposition assembly for depositing a metalloid-containing material on a substrate is provided. The 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 first precursor and a second precursor into the reaction chambers in the vapor phase. At least one of the first precursor and the second precursor comprises a metalloid compound. The deposition assembly further includes a precursor container constructed and arranged to contain the first precursor.

[0035] The deposition assembly further includes a precursor container constructed and arranged to contain a second precursor. The assembly is constructed and arranged to provide the first precursor and the second precursor to the reaction chamber via the precursor injector system to deposit the metalloid-containing material on the substrate. 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 2A and Figure 2B A block diagram of an exemplary embodiment of a method according to the present disclosure is shown.

[0039] Figure 3 is a schematic diagram of a deposition assembly according to the present disclosure.

[0040] 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

[0041] 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.

[0042] 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.

[0043] 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.

[0044] In one aspect, a method for depositing a metalloid material on a substrate by a cyclic deposition process is disclosed. In the cyclic deposition process, the stages of providing a first precursor and providing a second precursor are repeated until a desired material thickness is achieved.

[0045] In methods according to the present disclosure, the material deposited on the substrate comprises a metalloid. In some embodiments, the metalloid material comprises tellurium. In some embodiments, the metalloid material comprises germanium. In some embodiments, the metalloid material comprises tin. In some embodiments, the metalloid material comprises antimony. In some embodiments, the metalloid material comprises arsenic. In some embodiments, the metalloid material comprises selenium. In some embodiments, the metalloid material comprises an elemental metalloid. In some embodiments, the metalloid material comprises a metalloid alloy.

[0046] As used herein, the terms "layer" and / or "film" may 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 may comprise 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 may comprise a material or layer having pinholes, which may be at least partially continuous. A seed layer may be a discontinuous layer used to increase the nucleation rate of another material. However, a seed layer may also be substantially or completely continuous. A layer of desired thickness may be deposited by repeatedly providing a first precursor and a second precursor in a reaction chamber a sufficient number of times. The layer produced according to the methods disclosed herein may form a portion of a semiconductor structure and / or a semiconductor device.

[0047] In another aspect, a semiconductor structure is disclosed that includes a metalloid layer deposited via 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.

[0048] In some embodiments, the metalloid material is deposited as a layer on a substrate. In some embodiments, the metalloid layer comprises an elemental metalloid. The thickness of the metalloid material layer can be adjusted by adjusting the number of cycles in the cyclic deposition process. In some embodiments, the cyclic deposition process comprises alternating and sequentially providing a first 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.

[0049] 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 layer of material 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.

[0050] 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 metalloid) 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.

[0051] The method may include one or more cyclic stages. For example, the pulses of the first 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, a 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 the first precursor or the second precursor in the reaction chamber.

[0052] 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 the precursors to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the first precursor to the reaction chamber. In some embodiments, the cyclic deposition process includes purging the reaction chamber after providing the 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.

[0053] 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.

[0054] 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.

[0055] In some embodiments, the cyclic deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, the chemical reaction can be promoted by an elevated temperature relative to the ambient temperature. Typically, the elevated temperature can provide the energy required to form the metalloid 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.

[0056] Methods according to the present invention include providing a substrate in a reaction chamber, providing a first precursor in a vapor phase into the reaction chamber, and providing a second precursor in a vapor phase into the reaction chamber to form an elemental metalloid material on the substrate.

[0057] The method of depositing elemental metalloid materials 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 integrated circuits. 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.

[0058] Furthermore, in methods according to the present disclosure, a first precursor is provided into a reaction chamber in a vapor phase, and a second precursor is provided into the reaction chamber in a vapor phase to form an elemental metalloid material on a substrate.

[0059] In the method according to the present disclosure, when the first precursor is in the reaction chamber, the first precursor can be in a gas phase. The first precursor can be partially gaseous or liquid, or even solid at some time point before being provided in the reaction chamber. In other words, the first 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 being transported into the reaction chamber, various means for making the precursor enter the gas phase can be applied. Such means can include, for example, a heater, an evaporator, an air flow or the pressure applied to reduce or any combination thereof. Therefore, the method according to the present invention can include heating the first precursor before the first precursor is provided to the reaction chamber.

[0060] In the method according to the present disclosure, when the second precursor is in the reaction chamber, the second precursor can be in the gas phase. The second precursor can be partially gaseous or liquid, or even solid at some time point before being provided in the reaction chamber. In other words, the second precursor can be solid, liquid or gas, for example, in a precursor container or other container, and then transported in the reaction chamber. When being transported to the reaction chamber, various means for making the precursor 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 disclosure can include heating the second precursor before the second precursor is provided to the reaction chamber.

[0061] In some embodiments, deposition of elemental metalloid materials according to the present disclosure is performed at a temperature below about 200° C., or below about 170° C., or below about 120° C. In some embodiments, deposition is performed at a temperature of about 70° C. to about 130° C., such as about 85° C. to about 115° C., for example, at a temperature of about 90° C., about 100° C., or about 110° C.

[0062] In some embodiments, the first precursor is heated to at least 20° C., or at least 25° C., or at least 30° C., or at least 35° C., or at least 40° C. before being provided to the reaction chamber. The heating can be performed in the precursor container. In some embodiments, the first precursor is heated to at most 50° C., or at most 45° 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 first precursor to the reaction chamber.

[0063] In some embodiments, the second precursor is heated to at least 50° C., or at least 60° C., or at least 65° C., or at least 70° C., or at least 75° 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 90° C., or at most 85° C., or at most 80° 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.

[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 gas mixture, depending on the context. The first 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 by 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 metalloid material comprises an elemental metalloid. In the present disclosure, "metalloid" includes a group of materials between metals and non-metals in the periodic table. Metalloids include boron, silicon, germanium, arsenic, antimony, selenium, and tellurium. Thus, the deposited metalloid may have, at least in part, an oxidation state of 0. In some embodiments, substantially all or all of the metalloid is deposited as an elemental metalloid. In some embodiments, the deposited metalloid comprises, consists of, or consists essentially of elemental tellurium. In some embodiments, the deposited metalloid comprises, consists of, or consists essentially of elemental germanium. In some embodiments, the deposited metalloid comprises, consists of, or consists essentially of elemental arsenic. In some embodiments, the deposited metalloid comprises, consists of, or consists essentially of elemental antimony. In some embodiments, a layer consisting essentially of, or consisting essentially of, an elemental metalloid is deposited. In some embodiments, a metalloid according to the present disclosure is deposited as a layer, and in addition to the metalloid, the layer also comprises a significant amount of other elements. In such embodiments, the metalloid may exist as an elemental metalloid. In some embodiments, the metalloid deposited according to the present disclosure exists as an alloy with another metalloid.

[0066] The growth rate of the metalloid material can be, for example, from about 0.05 to about / cycle. 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 / cycle, or about / cycle, or about / cycle, or about / cycle, or about / cycle. The growth rate can be varied during the deposition process.

[0067] The deposition cycle, including providing the first precursor into the reaction chamber (i.e., pulsing the first precursor) and providing the second precursor into 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, or at least about 1500 times.

[0068] 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.

[0069] In the method according to the present disclosure, the first precursor comprises an alkylsilyl group and / or a silyl group.

[0070] In some embodiments, the first precursor comprises a metalloid alkylsilyl group or a metalloid silyl group. In some embodiments, the alkyl group is a C1-C4 alkyl group.

[0071] In some embodiments, the metalloid in the first precursor is selected from tellurium, germanium, boron, silicon, arsenic, selenium, and antimony. In some embodiments, the metalloid in the first precursor comprises tellurium or germanium. In some embodiments, the first precursor comprises tellurium.

[0072] In some embodiments, the first precursor comprises a compound selected from the following formulas: (R2Si)2E2, (R2SiC2R4SiR2)E, and (R2SiSiR2)2E, wherein E=is a metalloid selected from the group consisting of tellurium, germanium, boron, silicon, arsenic, antimony, and selenium, and each R is independently selected from a C1-C4 alkyl group. In some embodiments, the first precursor comprises a compound selected from the following formulas: (R2Si)2E2, (R2SiC2R4SiR2)E, and (R2SiSiR2)2E, wherein E=Te or Se, and each R is independently selected from a C1-C4 alkyl group.

[0073] In some embodiments, the first precursor is selected from (Et3Si)2Te, (Me3Si)2Te, ( i Pr3Si)2Te,( t BuMe2Si)2Te,(Me2Si)2Te2,(Me2SiC2H4SiMe2)Te,(Me2SiSiMe2)2Te2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t BuMe2Ge)2Te, (Me2Ge)2Te2, (Me2GeC2H4GeMe2)Te, (Me2GeGeMe2)2Te2, Me8Ge4Te2, Te(GeMe3)2, (Me3Ge)3Sb, (Et3Ge)3Sb and (Et3Ge)3As.

[0074] In some embodiments, the first precursor comprises (R3Si)2Te, wherein R is a C1-C4 alkyl group.

[0075] In some embodiments, the alkyl group is ethyl.

[0076] The method of any preceding claim, wherein the first precursor comprises (Et3Si)2Te.

[0077] The metalloid material is formed by providing the second precursor to the reaction chamber in a vapor phase. The conversion of the first precursor to the desired metalloid material can occur at the surface of the substrate. In some embodiments, the conversion can be at least partially carried out in the vapor phase. In some embodiments, the reaction between the first precursor and the second precursor occurs substantially only at the surface of the substrate.

[0078] In some embodiments, the second precursor comprises a halide. In some embodiments, the second precursor comprises a metalloid halide. In some embodiments, the halide is selected from chlorine, bromine, fluorine, and iodine.

[0079] In some embodiments, the metalloid in the second precursor is selected from tellurium, germanium, boron, silicon, arsenic, selenium, and antimony. In some embodiments, the metalloid comprises tellurium or germanium. In some embodiments, the metalloid in at least one of the first precursor or the second precursor comprises tellurium. In some embodiments, the metalloid in the first precursor and the second precursor is tellurium. In some embodiments, the metalloid in the first precursor is tellurium and the metalloid in the second precursor is germanium.

[0080] In some embodiments, the second precursor is selected from the group consisting of BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4, and TeCl2. The method of any one of the preceding claims, wherein the second precursor comprises TeCl2 or GeCl2·dioxane.

[0081] In one aspect, a method for depositing a metalloid-containing material on a substrate using a cyclic deposition process is disclosed. The method includes a supercycle comprising providing a substrate into a reaction chamber and two subcycles. The first subcycle comprises providing a first precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase. The second subcycle comprises providing the first precursor into the reaction chamber in a vapor phase; and providing a third precursor into the reaction chamber in a vapor phase.

[0082] In the method, the first precursor includes a metalloid alkylsilyl group, the second precursor includes a metalloid halide, the third precursor includes a metalloid halide, and the second precursor and the third precursor are different from each other.

[0083] In some embodiments, the first precursor is selected from (Et3Si)2Te, (Me3Si)2Te, ( i Pr3Si)2Te,( tBuMe2Si)2Te,(Me2Si)2Te2,(Me2SiC2H4SiMe2)Te,(Me2SiSiMe2)2Te2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t In some embodiments, the first precursor includes (Et3Si)2Te.

[0084] In some embodiments, the second precursor and the third precursor are selected from BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4, and TeCl2. The method of any of the preceding claims, wherein the second precursor comprises TeCl2 and the third precursor comprises GeCl2·dioxane.

[0085] In one aspect, a metalloid-containing layer produced by a cyclic deposition process is disclosed. The deposition process includes providing a substrate in a reaction chamber; providing a first precursor in the vapor phase into the reaction chamber; and providing a second precursor in the vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound. In some embodiments, the layer comprises an elemental metalloid.

[0086] In one aspect, a semiconductor structure is disclosed that includes a metalloid-containing layer deposited by a cyclic deposition process. The method includes providing a substrate in a reaction chamber; providing a first precursor in a vapor phase into the reaction chamber; and providing a second precursor in a vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0087] In one aspect, a semiconductor device is disclosed that includes a metalloid-containing layer deposited via a cyclic deposition process. The method includes providing a substrate in a reaction chamber; providing a first precursor in a vapor phase into the reaction chamber; and providing a second precursor in a vapor phase into the reaction chamber. In the method, at least one of the first precursor and the second precursor comprises a metalloid compound.

[0088] In one aspect, a vapor deposition assembly for depositing a metalloid-containing material on a substrate is provided. The 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 first precursor and a second precursor into the reaction chambers in the vapor phase. At least one of the first precursor and the second precursor comprises a metalloid compound. The deposition assembly further includes a precursor container constructed and arranged to contain the first precursor.

[0089] The deposition assembly further includes a precursor container constructed and arranged to contain a second precursor. The assembly is constructed and arranged to provide the first precursor and the second precursor to the reaction chamber via the precursor injector system to deposit the metalloid-containing material on the substrate.

[0090] 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.

[0091] 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.

[0092] The illustrations presented herein are not intended to be actual views of any particular material, structure, or device, but are merely idealized representations used to describe embodiments of the present disclosure.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] Figure 1A and Figure 1B A block diagram of an exemplary embodiment of a method 100 for depositing an elemental metalloid 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 metalloid material according to the present disclosure may be deposited on the surface.

[0097] 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 semi-metallic material according to the present disclosure may be deposited in a cross-flow reaction chamber. The semi-metallic material according to the present disclosure may be deposited in a showerhead reaction chamber.

[0098] A first precursor 104 is provided in a reaction chamber containing a substrate. Without limiting the present disclosure to any particular theory, the first precursor may be chemically adsorbed on the substrate during the time the first precursor is provided to the reaction chamber. The duration of the first precursor provided to the reaction chamber (first precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0099] In the second deposition phase 106 of method 100, a second precursor is provided in the reaction chamber. Without limiting the present disclosure to any particular theory, the second precursor can react with the chemisorbed first precursor. The duration for providing the second precursor to the reaction chamber (second precursor pulse time) can be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0100] The stages of providing the first precursor 104 and providing the second precursor 106 can be performed in any order. The stages of providing the first precursor 104 and providing the second precursor 106 can constitute a deposition cycle, resulting in the deposition of a metalloid material. In some embodiments, the two stages of metalloid material deposition, i.e., providing the first precursor and the second precursor (104 and 106) in the reaction chamber (cycle 108), can be repeated. Such embodiments include multiple deposition cycles. The thickness of the deposited metalloid material can be adjusted by adjusting the number of deposition cycles. The deposition cycle (cycle 108) can be repeated until the desired metalloid 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 metalloid layer. The layer can be substantially continuous or continuous.

[0101] In some embodiments, the cyclic deposition process includes alternately and sequentially providing a first 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 metalloid material.

[0102] The first precursor and the second precursor may be provided to the reaction chamber in separate steps (104 and 106). Figure 1B An 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 first and second precursors can alternatively be spatial.

[0103] Purging the reaction chambers 103 and 105 can prevent or mitigate the gas phase reaction between the first precursor and the second precursor and enable a possible self-saturating surface reaction. Before the substrate contacts the next reactive chemical substance, 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 first precursor and the second precursor respectively. 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 gaseous substance does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0104] When method 100 is performed, a metalloid 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, a particular ALD process may have a lower growth rate compared to a CVD process. One way to increase the growth rate is 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 first 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 overlap period between the two or more precursors in the reaction chamber, resulting in both an ALD component and a CVD component being deposited. 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.

[0105] In some embodiments, a first precursor is contacted with a substrate surface 104, excess first precursor is partially or substantially completely removed by an inert gas or vacuum 105, and a second precursor is contacted with the substrate surface comprising the first precursor. The first precursor may be contacted with the substrate surface in one or more pulses 104. In other words, pulses 104 of the first precursor may be repeated. The first precursor on the substrate surface may react with the second precursor to form a metalloid material on the substrate surface. Pulses 106 of the second precursor 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 first precursor may be provided in the reaction chamber in one or more pulses 104.

[0106] Figure 2A and 2B A block diagram of an exemplary embodiment of a method 200 for depositing a metalloid material on a substrate is shown. In a first stage 202, 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 metalloid material according to the present disclosure may be deposited on the surface.

[0107] 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 semi-metallic material according to the present disclosure may be deposited in a cross-flow reaction chamber. The semi-metallic material according to the present disclosure may be deposited in a showerhead reaction chamber.

[0108] A first precursor 204 is provided in a reaction chamber containing a substrate. Without limiting the present disclosure to any particular theory, the first precursor may be chemically adsorbed on the substrate during the time the first precursor is provided to the reaction chamber. The duration of the first precursor provided to the reaction chamber (first precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0109] In the second deposition phase 206 of method 200, a second precursor is provided in the reaction chamber. Without limiting the present disclosure to any particular theory, the second precursor can react with the chemisorbed first precursor. The duration for providing the second precursor to the reaction chamber (second precursor pulse time) can be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0110] The stages of providing the first precursor 104 and providing the second precursor 206 can be performed in any order. The stages of providing the first precursor 204 and providing the second precursor 206 can constitute a sub-cycle, resulting in the deposition of the first metalloid material. In some embodiments, the two stages of metalloid material deposition, i.e., providing the first precursor and the second precursor (204 and 206) in the reaction chamber, can be repeated (cycle 208). Such embodiments include multiple deposition cycles.

[0111] In the next step 210, a first precursor is provided in the reaction chamber. Without limiting the present disclosure to any particular theory, during the time the first precursor is provided to the reaction chamber, the first precursor may chemisorb onto the previously deposited metalloid. The duration of the first precursor provided to the reaction chamber (first precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0112] In the second deposition phase 212 of method 200, a third precursor is provided in the reaction chamber. Without limiting the present disclosure to any particular theory, the third precursor can react with the chemisorbed first precursor. The duration for providing the third precursor to the reaction chamber (third precursor pulse time) can be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 4 seconds, or 5 seconds.

[0113] The stages of providing the first precursor 210 and providing the third precursor 212 can be performed in any order. The stages of providing the first precursor 210 and providing the third precursor 212 can constitute a sub-cycle, resulting in the deposition of the second metalloid material. In some embodiments, the two stages of metalloid material deposition, i.e., providing the first precursor and the third precursor (210 and 212) in the reaction chamber, can be repeated (cycle 214). Such embodiments include multiple deposition cycles.

[0114] The thickness of the deposited metalloid material can be adjusted by adjusting the number of deposition cycles. The super cycle (cycle 216) can be repeated until the desired thickness of the metalloid material 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 metalloid layer comprising two different metalloids. The layer can be substantially continuous or continuous.

[0115] In some embodiments, the cyclic deposition process includes alternately and sequentially providing a first precursor and a second precursor, and / or a first precursor and a third precursor in the reaction chamber. Figure 2B As shown, the reaction chamber is purged between precursors 205, 207, 211, 213. In such an embodiment, the first sub-cycle can be considered to include stages 204, 205, 206, and 207, and the second sub-cycle can be considered to include stages 210, 211, 212, and 213. As described above, sub-cycles 108, 214 and super-cycle 216 can be repeated multiple times to achieve the desired thickness of the metalloid material.

[0116] The first precursor and the second precursor may be provided in the reaction chamber in separate steps (204 and 206). Figure 2B An embodiment according to the present disclosure is shown in which steps 204 and 206 are separated by purge steps 205 and 207. In such an embodiment, the deposition cycle includes one or more purge steps 203, 205. 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 first and second precursors can alternatively be spatial.

[0117] The first precursor and the third precursor may be provided in the reaction chamber in separate steps (210 and 212). Figure 2B An embodiment according to the present disclosure is shown in which steps 210 and 212 are separated by purge steps 211 and 213. In such an embodiment, the deposition cycle includes one or more purge steps 211, 213. 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 first and second precursors can alternatively be spatial.

[0118] Purging reaction chambers 203, 205, 211, 213 can prevent or mitigate the gas phase reaction between the first precursor and the second precursor, and achieve possible self-saturation surface reaction. Before the substrate contacts the next reactive chemical substance, 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 first precursor and the second precursor respectively. Because in some embodiments, the reaction can be self-saturated, 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 substance does not condense into a monolayer or multiple monolayers, nor does it thermally decompose on the surface.

[0119] When method 200 is performed, a metalloid 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 is 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 first 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 overlap period 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 204 may be the same or similar to any of the pressures and temperatures mentioned above in connection with step 206. The temperature and / or pressure within the reaction chamber during step 210 may be the same as or similar to any of the pressures and temperatures mentioned above in connection with step 212 .

[0120] In some embodiments, a first precursor is contacted with the substrate surface 204, excess first precursor is partially or substantially completely removed 205 by an inert gas or vacuum, and a second precursor is contacted with the substrate surface including the first precursor. The first precursor can be contacted with the substrate surface in one or more pulses 204. In other words, the pulses 204 of the first precursor can be repeated. The first precursor on the substrate surface can react with the second precursor to form a first metalloid material on the substrate surface. The pulses 206 of the second precursor can also be repeated. In some embodiments, the second precursor 206 can be provided in a first reaction chamber. Thereafter, the reaction chamber 205 can be purged, and the first precursor can be provided to the reaction chamber in one or more pulses 204.

[0121] In some embodiments, a first precursor is introduced into a reaction chamber 210, excess first precursor is partially or substantially completely removed by an inert gas or vacuum 211, and a second precursor is contacted with the substrate surface including the first precursor 212. The first precursor can be contacted with the substrate surface in one or more pulses 210. In other words, the pulses 210 of the first precursor can be repeated. The first precursor on the substrate surface can react with the second precursor to form a second metalloid material on the substrate surface. The pulses 212 of the second precursor can also be repeated. In some embodiments, the second precursor 212 can be provided in the first reaction chamber. Thereafter, the reaction chamber 211 can be purged, and the first precursor can be provided to the reaction chamber in one or more pulses 210.

[0122] Figure 3 A deposition assembly 300 according to the present disclosure is shown in schematic form. The deposition assembly 300 can be used to perform methods as described herein and / or form structures or devices as described herein, or portions thereof.

[0123] In the example shown, deposition assembly 300 includes one or more reaction chambers 302, a precursor injector system 301, a first precursor container 304, a second precursor container 306, an exhaust source 310, and a controller 312. Deposition assembly 300 may include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source.

[0124] Reaction chamber 302 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber as described herein.

[0125] The first precursor container 304 can include a container and one or more first precursors as described herein, either alone or mixed with one or more carrier gases (e.g., an inert gas). The second precursor container 306 can 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 304, 306, the deposition assembly 300 can include any suitable number of source containers. The source containers 304, 306 can be coupled to the reaction chamber 302 via lines 314, 316, which can each include a flow controller, a valve, a heater, etc. In some embodiments, the first precursor in the first precursor container 304 and the second precursor in the second precursor container 306 can be heated. In some embodiments, the containers are heated so that the precursors or reactants reach a temperature of, for example, between about 30°C and about 200°C, depending on the nature of the chemical species in question.

[0126] Exhaust source 310 may include one or more vacuum pumps.

[0127] Controller 312 includes electronic circuitry and software to selectively operate valves, manifolds, heaters, pumps, and other components included in deposition assembly 300. Such circuitry and components operate to introduce precursors, reactants, and purge gases from corresponding sources. Controller 312 can control the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber 302, the pressure within reaction chamber 302, and various other operations to provide proper operation of deposition assembly 300. Controller 312 can include control software to electrically or pneumatically control valves to control the flow of precursors, reactants, and purge gases into and out of reaction chamber 302. Controller 312 can include modules, such as software or hardware components, that perform certain tasks. Modules can be configured to reside on an addressable storage medium of the control system and to execute one or more processes.

[0128] Other configurations of the deposition assembly 300 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 302. 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.

[0129] During operation of deposition assembly 300, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to reaction chamber 302. Once the substrate is transferred to reaction chamber 302, one or more gases (such as precursors, reactants, carrier gases, and / or purge gases) from a gas source are introduced into reaction chamber 302.

[0130] In some embodiments, the first precursor is supplied in pulses, the second precursor is supplied in pulses, and the reaction chamber is purged between successive pulses of the first precursor and the second precursor.

[0131] 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 an elemental metalloid material on a substrate by a cyclic deposition process, the method comprising: providing a substrate in a reaction chamber; providing a first precursor into the reaction chamber in a vapor phase; as well as providing a second precursor into the reaction chamber in a vapor phase; Wherein, at least one of the first precursor and the second precursor comprises a metalloid compound.

2. The method according to claim 1, wherein The first precursor includes an alkylsilyl group or a silyl group.

3. The method according to claim 1 or 2, wherein: The first precursor includes a metalloid alkylsilyl group or a metalloid silyl group.

4. The method according to claim 2 or 3, wherein: The alkyl group is a C1-C4 alkyl group.

5. The method according to claim 4, wherein The alkyl group is ethyl.

6. A method according to any one of the preceding claims, wherein The second precursor comprises a halide.

7. A method according to any one of the preceding claims, wherein The second precursor includes a metalloid halide.

8. The method according to claim 6 or 7, wherein: The halide is selected from chlorine, bromine, fluorine and iodine.

9. A method according to any one of the preceding claims, wherein The metalloid is selected from tellurium, germanium, boron, silicon, arsenic, selenium and antimony.

10. The method according to claim 9, wherein: The metalloid is tellurium or germanium.

11. A method according to any one of the preceding claims, wherein The metalloid in at least one of the first precursor or the second precursor is tellurium.

12. A method according to any one of the preceding claims, wherein The metalloid in the first precursor and the second precursor is tellurium.

13. The method according to any one of claims 1 to 11, wherein The metalloid in the first precursor is tellurium, and the metalloid in the second precursor is germanium.

14. A method according to any one of the preceding claims, wherein The first prebody selected (Et3Si)2Te,Te(SiMe3)2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Me3Si)2Te,( i Pr3Si)2Te,( t BuMe2Si)2Te,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t BuMe2Ge)2Te,(Me2Ge)2Te2,(Me2GeC2H4GeMe2)Te,(Me2GeGeMe2)2Te2,Me8Ge4Te2,Te(GeMe3)2,(Me3Ge)3Sb,(Et3Ge)3Sbsum(Et3Ge)3As.

15. A method according to any one of the preceding claims, wherein The first precursor includes (R3Si)2Te, wherein R is a C1-C4 alkyl group.

16. A method according to any one of the preceding claims, wherein The first precursor comprises a compound selected from the following general formulas: (R2Si)2E2, (R2SiC2R4SiR2)E and (R2SiSiR2)2E, wherein E=Te or Se, and each R is independently selected from C1-C4 alkyl.

17. A method according to any one of the preceding claims, wherein The first precursor includes (Et3Si)2Te.

18. A method according to any one of the preceding claims, wherein The second precursor includes BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4 and TeCl2.

19. A method according to any one of the preceding claims, wherein The second precursor includes TeCl2 or GeCl2·dioxane.

20. A method for depositing a metalloid-containing material on a substrate by a cyclic deposition process, the method comprising a super cycle comprising providing the substrate into a reaction chamber and two sub cycles, the first sub cycle comprising: providing a first precursor into the reaction chamber in a vapor phase; and providing a second precursor into the reaction chamber in a vapor phase; The second sub-loop includes: providing a first precursor into the reaction chamber in a vapor phase; and providing a third precursor into the reaction chamber in a vapor phase; wherein the first precursor comprises a metalloid alkylsilyl group; wherein the second precursor comprises a metalloid halide; wherein the third precursor comprises a metalloid halide; and Here, the second precursor and the third precursor are different from each other.

21. The method according to claim 18, wherein The first pre-body selected (Et3Si)2Te,(Me3Si)2Te,( i Pr3Si)2Te,( t BuMe2Si)2Te,(Me2Si)2Te2,(Me2SiC2H4SiMe2)Te,(Me2SiSiMe2)2Te2,Me8Si4Te2,Te(GeMe3)2,(Me3Si)3Sb,(Et3Si)3Sb,(Et3Si)3As,(Et3Ge)2Te,(Me3Ge)2Te,( i Pr3Ge)2Te,( t BuMe2Ge)2Te,(Me2Ge)2Te2,(Me2GeC2H4GeMe2)Te,(Me2GeGeMe2)2Te2,Me8Ge4Te2,Te(GeMe3)2,(Me3Ge)3Sb,(Et3Ge)3Sbsum(Et3Ge)3As.

22. The method according to claim 18, wherein The second precursor and the third precursor are selected from BBr3, BCl3, Si2Cl6, SiCl2H2, Si2Cl5H, SiCl4, SiCl2Me2, SiI4, GeCl4, Ge(thd)Cl, GeCl2·dioxane, HGeCl3, SbCl3, SbCl5, AsCl5, AsCl5, Se2Cl2, SeCl2, SeCl4 and TeCl2.

23. A deposition assembly for depositing a metalloid-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 first precursor and a second precursor into the reaction chamber in a vapor phase, wherein at least one of the first precursor and the second precursor comprises a metalloid compound; The deposition assembly also includes a precursor container constructed and arranged to contain a first precursor; The deposition assembly further includes a precursor container constructed and arranged to contain a second precursor; and The deposition assembly is constructed and arranged to provide a first precursor and a second precursor to the reaction chamber via the precursor injector system to deposit a metalloid-containing material on the substrate.

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