Method for forming indium molybdenum oxide layer and related indium molybdenum oxide layer

Abstract

Methods of forming an indium molybdenum oxide layer (IMO) by vapor deposition are provided. In some embodiments, a cyclic deposition process for forming an IMO layer includes alternately and sequentially contacting a substrate with a vapor phase indium precursor, a vapor phase molybdenum precursor, and one or more oxygen reactants in a reaction chamber.

Description

Technical Field

[0001] The present disclosure generally relates to the field of semiconductor processing methods and to the field of device and integrated circuit manufacturing. More specifically, the present disclosure relates to a vapor deposition process for forming an indium molybdenum oxide layer. Background Art

[0002] Conductive oxides are increasingly used in the semiconductor industry. For example, a conductive oxide can be used as an active layer in a thin film transistor (TFT), an access transistor in 3D NAND / 3D DRAM applications, a contact layer of a device, and a semiconductor layer in a metal-semiconductor-metal (MSM) type photodetector. However, the performance of devices and / or integrated circuits incorporating certain potential conductive oxide materials may be negatively affected by, for example, a lack of stability of the materials, high resistivity, and low carrier mobility. Therefore, improved conductive oxide materials and methods for forming such materials are needed.

[0003] Any discussion set forth in this section, including discussions of problems and solutions, has been included in the present disclosure merely to provide a background for the present disclosure. Such discussion should not be construed as an admission that any or all of the information was known at the time the invention was made or constitutes prior art. Summary of the Invention

[0004] This summary of the invention may introduce some concepts in a simplified form that will be further described in detail below. This summary of the invention is not necessarily intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] Various embodiments of the present disclosure relate to a method for forming an indium molybdenum oxide layer on a substrate surface. As will be elaborated in more detail below, the methods described herein may employ a cyclic deposition process, particularly an atomic layer deposition process, to form the indium molybdenum oxide layer. For example, such an indium molybdenum oxide layer can be used as an electrical contact in a semiconductor device structure.

[0006] In particular, the present disclosure includes a method for forming an indium molybdenum oxide layer on a substrate in a reaction chamber. According to an example of the present disclosure, the disclosed method includes performing a cyclic deposition process that includes a plurality of repeated deposition cycles. In such an example, a deposition cycle includes (a) contacting the substrate with a gaseous indium precursor, (b) contacting the substrate with a gaseous molybdenum precursor, and (c) contacting the substrate with an oxygen reactant.

[0007] In some embodiments, the cyclic deposition process is an atomic layer deposition process.

[0008] In some embodiments, the deposition cycle includes an indium oxide sub-cycle.

[0009] In some embodiments, the indium molybdenum oxide layer includes molybdenum-doped indium oxide.

[0010] In some embodiments, the deposition cycle includes an indium oxide sub-cycle and a molybdenum oxide sub-cycle.

[0011] In some embodiments, an oxygen reactant contacts the substrate after step (a) and after step (b).

[0012] In some embodiments, the indium molybdenum oxide layer is a mixture of indium oxide and molybdenum oxide.

[0013] In some embodiments, the indium oxide sub-cycle is carried out in a first reaction chamber and the molybdenum oxide sub-cycle is carried out in a second reaction chamber.

[0014] In some embodiments, the substrate is heated to a substrate temperature below 250 °C.

[0015] In some embodiments, the indium molybdenum oxide layer has a molybdenum content between 0.001 atomic % and 40 atomic %.

[0016] In some embodiments, the gaseous indium precursor includes a ligand selected from the group consisting of alkyl, alkylamino, alkoxy, halide, cyclopentadienyl (Cp), alkoxide, amide, amidino, guanidine, β-diketonate, and triazenyl.

[0017] In some embodiments, the gaseous indium precursor is selected from: trimethylindium, triethylindium, ethyldimethylindium, InMe2(CH2CH2CH2NMe2), InEt2(CH2CH2CH2NMe2), InMe2(CH2CH2CH2NEt2), InEt2(CH2CH2CH2NEt2), InCl, InCl3, InMe2Cl, In(CpCH2CH2NMe2), In(CpCH2CH2CH2NMe2), InMe2(CpCH2CH2NMe2), InMe2(CpCH2CH2CH2NMe2), In(CpCH2CH2OMe), In(CpCH2CH2CH2OMe), InMe2(CpCH2CH2OMe), InMe2(CpCH2CH2CH2OMe, tris(tert-pentyloxy)indium(III), tris(tert-butoxy)indium(III), tris(isopropoxy)indium(III), In(dmap)3, In(dmamp)3, In(dmamb)3, InMe2(dmap), InMe2(dmamp), InMe2(dmamb), InEt2(dmap), InEt2(dmamp), InEt2(dmamb), In(dmamp)2(OiPr), InMe2(NMe2), InMe2(NEt2), InMe2(NEtMe), InEt2(NMe2), InEt2(NEt2), InEt2(NEtMe), InMe2[N(SiMe3)2], InEt2[N(SiMe3)2], In(sBu2AMD)3, In(tBu2AMD)3, In(iPr2AMD)3 or In(tPn2AMD)3, In(tBu2FMD)3, In(iPr2FMD)3, In(tPn2FMD)3, In(thd)3, In(acac)3, In(hfac)3 and tris(di-tert-butyltriazenyl)indium(III) In(sBu2FMD)3 and indium precursors represented by InR2L, where R is a methyl or ethyl ligand and where L is selected from tBu2AMD, iPr2AMD, tPn2AMD, sBu2AMD, tBu2FMD, iPr2FMD, tPn2FMD and sBu2FMD.

[0018] In some embodiments, the gaseous molybdenum precursor is selected from Mo(CO)6, (Mo(NMe2)2(N t Bu)2), MoCl4O, MoO2(acac)2, Mo(EtBz)2, molybdenum isopropoxide, MoO2(acac)2, Mo(O i Pr)5 and MoCl2O2.

[0019] In some embodiments, the gaseous oxygen reactant includes one or more of the following: oxygen (O), molecular oxygen (O2), water (H2O), ozone (O3), and hydrogen peroxide (H2O2).

[0020] The present disclosure also includes an atomic layer deposition (ALD) process for forming an indium molybdenum oxide layer. According to an example of the present disclosure, the ALD process includes alternately and sequentially contacting a substrate with trimethylindium, a molybdenum precursor, and an oxygen reactant in a reaction chamber, and repeating the deposition cycle until the indium molybdenum oxide layer has been formed to a desired thickness and composition.

[0021] In some embodiments, the molybdenum precursor is selected from Mo(CO)6, (Mo(NMe2)2(N t Bu)2), MoCl4O, MoO2(acac)2, Mo(EtBz)2, molybdenum isopropoxide, MoO2(acac)2, Mo(O i Pr)5, and MoCl2O2.

[0022] In some embodiments, the molybdenum precursor includes Mo(NMe2)2(N t Bu)2.

[0023] In some embodiments, the indium molybdenum oxide layer (IMO layer) includes molybdenum-doped indium oxide with a molybdenum content of less than 40 atomic %. In some embodiments, the indium molybdenum oxide layer has a molybdenum content between 0.001 atomic % and 40 atomic %.

[0024] In some embodiments, the deposition cycle includes an indium oxide sub-cycle and a molybdenum oxide sub-cycle. The indium oxide sub-cycle includes contacting the substrate with trimethylindium and a first oxygen reactant, and the molybdenum oxide sub-cycle includes contacting the substrate with a molybdenum precursor and a second oxygen reactant.

[0025] In some embodiments, the first oxygen reactant includes ozone (O3), and the second oxygen reactant includes water vapor (H2O).

[0026] To summarize the present invention and the advantages achieved over the prior art, certain objects and advantages of the present invention have been described above. Of course, it should be understood that not all of these objects or advantages may be achieved in accordance with any particular embodiment of the present invention. Thus, for example, those skilled in the art will recognize that the present invention may be implemented or carried out in a manner that achieves or optimizes one advantage or a group of advantages taught or suggested herein, without necessarily achieving other objects or advantages taught or suggested herein.

[0027] All of these embodiments are within the scope of the present invention disclosed herein. From the following detailed description of certain embodiments with reference to the accompanying drawings, these and other embodiments will become apparent to those skilled in the art. The present invention is not limited to any particular embodiment disclosed. Description of the Drawings

[0028] To facilitate the discussion of any particular element or action, the most significant digit in a reference number refers to the figure number in which the element is first introduced.

[0029] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by referring to the detailed description and the claims when considered in conjunction with the following illustrative drawings.

[0030] Figure 1 An exemplary method in accordance with an embodiment of the present disclosure is shown.

[0031] 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 of the elements in the figures may be exaggerated relative to other elements to assist in improving understanding of the illustrated embodiments of the present disclosure. Detailed Description

[0032] The following description of exemplary embodiments of the methods and structures provided is merely exemplary and for illustrative purposes only. The following description is not intended to limit the scope of the present disclosure or the claims. Additionally, the recitation of multiple embodiments having the noted features or steps is not intended to exclude other embodiments having additional features or steps, or other embodiments incorporating different combinations of the recited features or steps.

[0033] As elaborated more fully hereinafter, various embodiments of the present disclosure provide methods for forming an indium molybdenum oxide layer (also referred to herein as an IMO layer, a molybdenum-doped indium oxide layer, and a mixed oxide of indium oxide and molybdenum oxide). Exemplary methods can be used to form an IMO layer on a substrate surface via a cyclic deposition process, particularly an atomic layer deposition process. The cyclic deposition process of the present invention can include performing two or more deposition cycles, where each deposition cycle includes the following steps: (a) contacting the substrate with a gaseous indium precursor; (b) contacting the substrate with a gaseous molybdenum precursor, and (c) contacting the substrate with an oxygen reactant. The steps (a-c) of the deposition cycle can be performed in any order in parallel (or at least partially in parallel), each step being repeated multiple times, and additional steps can be optionally included within the deposition cycle. Additionally, the deposition cycle can include supercycles, where a supercycle includes one or more subcycles, each subcycle for forming a component of the IMO layer. Thus, the cyclic deposition process of the present invention allows for the controlled formation of an IMO layer having desired material properties, such as but not limited to composition, thickness, stoichiometry, conductivity, dopant concentration, etc.

[0034] In the present disclosure, a gas can include a material that is a gas at normal temperature and pressure (NTP), an evaporated solid, and / or an evaporated liquid, and can consist of a single gas or a gas mixture, depending on the context.

[0035] As used herein, the terms "precursor" and "reactant" can refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction to produce another compound. A precursor typically contains at least a portion that is incorporated into the compound or element produced by the chemical reaction. The resulting compound or element can be deposited on a substrate. A reactant can be an element or compound that is not incorporated to a large extent into the resulting compound or element. In some cases, the term reactant can be used interchangeably with the term precursor.

[0036] As used herein, the term "substrate" can refer to any one or more underlying materials that can be used to form or on which a device, circuit, or film can be formed. A substrate can include a bulk material, such as silicon (e.g., single-crystalline silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials, and can include one or more layers covering or underlying the bulk material. Additionally, a substrate can include various features, such as depressions, protrusions, etc., formed within or on at least a portion of the substrate layer. For example, a substrate can include a semiconductor material. The semiconductor material can include or be used to form one or more of the source, drain, or channel regions of a device. A substrate can also include an interlayer dielectric (e.g., silicon oxide) and / or a high-k dielectric material layer covering the semiconductor material. In the present context, a high-k dielectric material or high-k dielectric is a material having a dielectric constant greater than that of silicon dioxide.

[0037] As used herein, the terms "film" and / or "layer" can be used interchangeably and can refer to any continuous or discontinuous structure and material, such as a material deposited by the methods disclosed herein. For example, a film and / or layer can include two-dimensional materials, three-dimensional materials, nanoparticles, partial or complete molecular layers, or partial or complete atomic layers, or atomic and / or molecular clusters. A film or layer can be composed in part or in whole of a plurality of dispersed atoms on the surface of a substrate and / or embedded in the substrate and / or embedded in a device fabricated on the substrate. A film or layer can include a material or layer having pinholes and / or islands. A film or layer can be at least partially continuous. A film or layer can be patterned, e.g., subdivided, and can be included in a plurality of semiconductor devices.

[0038] As used herein, the term "cyclic deposition process" or "cyclic deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate and includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include an ALD component and a cyclic CVD component. In some cases, a cyclic deposition process can include continuously flowing one or more precursors, reactants, or inert gases, and pulsing other precursors or reactants.

[0039] As used herein, the term "atomic layer deposition" can refer to a vapor deposition process that performs deposition cycles (usually multiple consecutive deposition cycles) in a processing chamber. The term atomic layer deposition as used herein also means to include processes designated by related terms, such as chemical vapor atomic layer deposition, when performed with alternating pulses of precursor / reaction gas and purge gas (e.g., an inert carrier gas). Generally, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemisorbed onto the deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other material), forming a monolayer or sub-monolayer of material that does not readily react with additional precursor (i.e., a self-limiting reaction). Thereafter, in some cases, a reactant (e.g., another precursor or reaction gas) can then be introduced into the processing chamber to convert the chemisorbed precursor into the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more cycles, e.g., during each step of each cycle, a purge step can be utilized to remove any excess precursor from the processing chamber and / or any excess reactant and / or reaction by-products from the reaction chamber.

[0040] As used herein, the term "purge" can refer to the process of providing an inert or substantially inert gas to the reaction chamber between two gas pulses that otherwise might react with each other. For example, a purge can be provided between a precursor pulse and a reactant pulse, e.g., using an inert gas such as a noble gas, to reduce possible gas-phase interactions that might occur between the precursor and the reactant. It should be understood that the purge can be performed temporally or spatially, or both. For example, in the case of a temporal purge, a purge step can be used, e.g., in the chronological order of providing a precursor to the reaction chamber, providing a purge gas to the reaction chamber, and providing a reactant or another precursor to the reaction chamber, where the substrate on which the layer is deposited does not move. In the case of a spatial purge, the purge step can take the form of moving the substrate from a first location (e.g., continuously) where the precursor is supplied through a purge gas curtain to a second location (e.g., continuously) where the reactant or other precursor is supplied.

[0041] Furthermore, in the present disclosure, any two numbers of a variable can constitute a viable range of that variable, and any indicated range can include or exclude the endpoints. Additionally, any value of the indicated variable (regardless of whether it is denoted by the term "about") can refer to an exact value or an approximate value and includes equivalents, and can refer to an average value, a median value, a representative value, a majority value, etc. Moreover, in the present disclosure, the terms include, consist of, and have independently refer to generally or broadly include, contain, consist essentially of, or consist of in some embodiments.

[0042] In the present disclosure, the meaning of any defined term does not necessarily exclude the ordinary and customary meaning in some embodiments.

[0043] According to examples of the present disclosure, a method of forming an indium molybdenum oxide layer by a vapor deposition process (such as atomic layer deposition) is provided. In some embodiments, an IMO layer can be formed on a substrate by a vapor deposition process that includes alternately and sequentially contacting the substrate with a vapor-phase indium precursor, a vapor-phase molybdenum precursor, and one or more oxygen reactants. In some embodiments, the IMO layer includes molybdenum-doped indium oxide and / or a mixed oxide of indium oxide and molybdenum oxide.

[0044] As described below, in some embodiments, the cyclic deposition process of the present disclosure includes deposition cycles, which can include (a) contacting the substrate with a vapor-phase indium precursor, (b) contacting the substrate with a vapor-phase molybdenum precursor, and (c) contacting the substrate with one or more oxygen reactants.

[0045] As described below, in some embodiments, the deposition cycle includes contacting the substrate with each of the indium precursor and the molybdenum precursor, and after the substrate is contacted with the indium precursor and the molybdenum precursor, contacting the substrate with an oxygen reactant, wherein the indium precursor and the molybdenum precursor can be provided in any order.

[0046] As described below, in some embodiments, the deposition cycle includes contacting the substrate with the indium precursor and the molybdenum precursor in a time overlap (i.e., in parallel or at least partially in parallel), and after the substrate is contacted with the indium precursor and the molybdenum precursor, contacting the substrate with an oxygen reactant.

[0047] As described below, in some embodiments, the cyclic deposition process of the present disclosure includes deposition cycles, which include one or more sub-cycles of depositing oxides. According to examples of the present disclosure, in some embodiments, a binary oxide of one of indium oxide or molybdenum oxide can be deposited in a sub-cycle, and then the substrate is contacted with a molybdenum precursor or an indium precursor, respectively. According to examples of the present disclosure, the binary oxide of each individual precursor can be deposited in two deposition sub-cycles. In such an example, the deposition cycle (i.e., the super-cycle) includes a first sub-cycle and a second sub-cycle. In the first sub-cycle, indium oxide is deposited from a vapor-phase indium precursor, and in the second sub-cycle, molybdenum oxide is deposited from a vapor-phase molybdenum precursor. According to examples of the present disclosure, the binary oxide of each individual precursor can be deposited in two deposition sub-cycles using a first oxygen reactant and a second oxygen reactant, wherein the first oxygen reactant and the second oxygen reactant are different from each other. In such an example, the first sub-cycle using the first oxygen reactant can be carried out in a first reaction chamber, and the second sub-cycle using the second oxygen reactant can be carried out in a second reaction chamber, wherein the first reaction chamber and the second reaction chamber are different from each other.

[0048] In some embodiments, additional reactant gases, such as gases including NH3, N2O, NO2, and / or H2O2, can be provided in one or more deposition cycles to improve layer properties.

[0049] In some embodiments, the IMO layer may comprise a mixture of one or more individual oxides, such as indium oxide and molybdenum oxide.

[0050] In some embodiments, the IMO layer may comprise molybdenum-doped indium oxide. In some embodiments, the IMO layer comprises molybdenum-doped In2O3.

[0051] In some embodiments, the IMO layer may comprise a mixture of one or more binary oxides, such as indium oxide and molybdenum oxide. Various oxides can be used to tune the IMO layer to obtain desired results. For example, the respective amounts of indium and molybdenum in the IMO layer can be adjusted.

[0052] In some embodiments, post-deposition annealing and / or post-deposition processing may be performed, for example, to improve the electrical properties of the layer. Post-deposition annealing may include annealing in an oxygen environment, for example. The disclosed method enables high conformality and full stoichiometric control of the IMO layer, for example, on high aspect ratio 3D structures, as required for some memory applications.

[0053] In some embodiments, the indium molybdenum oxide layer deposited by the disclosed method can be used as a contact layer for semiconductor devices (such as transistors). This can allow for contacts with low resistivity and high carrier mobility. In some embodiments, the IMO layer is deposited at a low temperature (<250 °C), thus allowing it to be used in back-end-of-line (BEOL) devices. In some embodiments, the IMO layer of the present disclosure can be deposited with high conformality and high uniformity on three-dimensional structures. This can allow the use of the IMO layer in high aspect ratio devices such as DRAM.

[0054] Other environments in which the IMO layer can be utilized will be apparent to those skilled in the art. In some embodiments, the IMO layer is not used as a transparent layer transistor (TFT) used in a display.

[0055] As described above, a vapor deposition process is used to deposit the IMO layer. In some embodiments, a cyclic deposition process, particularly atomic layer deposition (ALD) technology, is employed to deposit a conformal IMO layer. Among vapor deposition techniques, ALD has the advantage of providing high conformality at low temperatures. In some embodiments, a cyclic CVD process can be utilized. Thus, in some embodiments, the reaction temperature can be higher than the decomposition temperature of at least one precursor. In a cyclic CVD reaction, at least partial mixing of one or more precursors and reactants may occur. For example, the ALD process described below can be modified to provide precursors and reactants simultaneously or in at least partially overlapping pulses in each sub-cycle.

[0056] The ALD process is based on controlled surface reactions of precursor chemicals. The surface reactions may or may not be self-limiting. Gas-phase reactions can be avoided by alternately and sequentially introducing the precursors into the reaction chamber. The gas-phase reactants are typically separated from each other in the reaction chamber, for example, by removing excess reactants and / or reactant by-products from the reaction chamber between reactant pulses, and this process can be referred to as purging.

[0057] Briefly, the substrate is loaded and positioned in the reaction chamber and is typically heated to a suitable substrate temperature (i.e., deposition temperature) under reduced pressure. The substrate can be, for example, a semiconductor substrate. The deposition temperature can be maintained below the thermal decomposition temperature of the precursors but at a high enough level to avoid reactant condensation and to provide activation energy for the desired surface reactions. Of course, for any given ALD reaction, the suitable temperature window will depend on the surface termination and the reactant species involved.

[0058] In some embodiments, the deposition temperature (i.e., substrate temperature) is about 20 °C to about 600 °C, about 100 °C to about 400 °C, or about 150 °C to about 300 °C, or about 200 °C to about 250 °C. In some embodiments, the deposition temperature is below about 600 °C, or below about 500 °C, or below about 400 °C, or below about 300 °C, or below about 250 °C, or below about 225 °C, or below about 200 °C. In some embodiments, the deposition temperature is from room temperature to 250 °C.

[0059] The indium precursor and the molybdenum precursor can be separately introduced into the chamber in the form of gas-phase pulses and brought into contact with the substrate surface. In some embodiments, the substrate surface includes a three-dimensional structure. In some embodiments, conditions are selected such that no more than about one monolayer of each precursor is adsorbed on the substrate surface in a self-limiting manner.

[0060] One or more gaseous oxygen reactants are pulsed into the chamber where they react with the indium and / or molybdenum species on the surface to form their respective oxides.

[0061] Excess precursors or reactants and reaction by-products (if any) can be removed from the substrate and the substrate surface and in the vicinity of the substrate and the substrate surface between pulses of each precursor or reactant. In some embodiments, the reactants and reaction by-products (if any) can be removed by purging. Purging can be accomplished, for example, with pulses of an inert gas such as nitrogen or argon.

[0062] Purging the reaction chamber means removing gaseous precursors or reactants and / or gaseous by-products from the reaction chamber, for example by evacuating the reaction chamber with a vacuum pump and / or by replacing the gas inside the reactor with an inert gas such as argon or nitrogen. Typical purge times are from about 0.05 seconds to about 20 seconds, between about 1 second and about 10 seconds, or between about 1 second and about 2 seconds. However, other purge times can also be used, for example when depositing a layer on a structure with an extremely high aspect ratio or other structures with a complex surface morphology. A person skilled in the art can easily determine the appropriate pulse time according to the specific situation.

[0063] In other embodiments, excess precursors (or reactants and / or reaction by-products, etc.) are removed from the substrate surface or substrate region by physically moving the substrate from a location containing the precursors, reactants, and / or reaction by-products.

[0064] The steps of, for example, contacting the substrate with each precursor and reactant by pulsing and removing excess precursors or reactants and reaction by-products are repeated until an IMO layer of the desired thickness is formed on the substrate, and each complete deposition cycle typically leaves no more than about one molecular monolayer.

[0065] As described above, each pulse or stage of each deposition cycle can be self-limiting. An excess of reactant precursor can be provided in each stage to saturate the surface of the susceptible structure. Surface saturation ensures that the reactants substantially occupy all or most of the available reaction sites (e.g., limited by physical size or "steric hindrance"), thus ensuring excellent step coverage. In some arrangements, the degree of self-limiting behavior can be adjusted, for example, by allowing some overlap of the reactant pulses to trade off between deposition rate (by allowing some CVD-type reactions) and conformality. The ideal ALD conditions where the reactants are sufficiently separated in time and space provide nearly perfect self-limiting behavior, thus providing maximum conformality, but steric hindrance results in less than one molecular layer per cycle. Mixing limited CVD reactions with self-limiting ALD reactions can increase the deposition rate. As described above, in some embodiments, a pulsed CVD process is used.

[0066] In some embodiments, the reaction space can be in a single-wafer ALD reactor or a batch ALD reactor, where deposition on multiple substrates occurs simultaneously. In some embodiments, the substrate (e.g., a semiconductor workpiece) on which deposition is desired is loaded into the reaction space of the reaction chamber. The reaction chamber can be part of a cluster tool in which various different processes in integrated circuit formation are carried out. In some embodiments, a flow-type reactor is used. In some embodiments, a single-wafer ALD reactor with high-volume manufacturing capabilities is used. In other embodiments, a batch reactor including multiple substrates is used. For embodiments using a batch ALD reactor, the number of substrates is in the range of 10 to 200, in the range of 50 to 150, or in the range of 100 to 130.

[0067] In addition to these ALD reactors, many other types of reactors capable of performing ALD layer growth can be used, including CVD reactors equipped with appropriate equipment and pulsed precursor devices. In some embodiments, a flow-type ALD reactor is used. The reactants are typically kept separate until they reach the reaction chamber, minimizing the common piping for the precursors. However, other arrangements are possible.

[0068] Suitable batch reactors include, but are not limited to, reactors specifically designed to enhance the ALD process. In some embodiments, a vertical batch reactor is used, where the boat rotates during processing. Thus, in some embodiments, the wafer rotates during processing. In some embodiments using a batch reactor, the uniformity between wafers is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0069] The IMO layer deposition process described herein can optionally be carried out in a reaction chamber connected to a cluster tool. In a cluster tool, since each reaction chamber is dedicated to one type of process, the temperature of the reaction chamber in each module can be kept constant, which can increase the throughput compared to a reactor where the substrate is heated to the processing temperature before each run.

[0070] Now turning to the drawings, Figure 1 A cyclic deposition process 100 including a deposition cycle 104 is shown. Briefly, according to an example of the present disclosure, the cyclic deposition process 100 includes placing a substrate in a reaction chamber and heating the substrate to a suitable deposition temperature (step 102), followed by performing a plurality of repeated deposition cycles 104, where the deposition cycle includes the following steps: (a) contacting the substrate with a gaseous indium precursor (step 106), (b) contacting the substrate with a gaseous molybdenum precursor (step 108), and (c) contacting the substrate with an oxygen reactant (step 110). The deposition cycle 104 can be repeated (as shown by the loop 112) to deposit an IMO layer of a desired thickness and composition.

[0071] According to an example of the present disclosure, the deposition cycle 104 may include an indium oxide sub-cycle and / or a molybdenum oxide sub-cycle. In such an example, the oxygen reactant contacts the substrate after step (a) (step 106) and / or after step (b) (step 108). In such an example, the indium oxide sub-cycle may use a first oxygen reactant, and the molybdenum oxide sub-cycle may use a different second oxygen reactant. In such an example, the indium oxide sub-cycle may be performed in a first reaction chamber, and the molybdenum oxide sub-cycle may be performed in a different second reaction chamber. In such an example, the first reaction chamber and the second reaction chamber may be part of a cluster-type semiconductor processing system, and in such a system, the substrate may be transferred back and forth between the first and second reaction chambers under a controlled environment (e.g., under an inert gas and / or in a vacuum) in order to maintain the quality of the deposited layer.

[0072] More specifically, according to an example of the present disclosure, in some embodiments, at least one of an indium precursor and a molybdenum precursor is provided before the oxygen reactant. In some embodiments, each of the indium precursor and the molybdenum precursor is provided before the oxygen reactant. The indium precursor and the molybdenum precursor may be provided in any order. In some embodiments, the precursors are provided in sequence in the deposition cycle, wherein the substrate is alternately contacted with the indium precursor, the molybdenum precursor, and the oxygen reactant in sequence. The deposition cycle is repeated to deposit an IMO layer of a desired thickness. The deposition cycle may be written as [indium precursor + molybdenum precursor + oxygen reactant] x N1, where N1 is an integer, and the square brackets represent one deposition cycle, e.g., an ALD deposition cycle.

[0073] In some embodiments, an oxygen reactant may be provided after one or more of the indium precursor and the molybdenum precursor. For example, in some embodiments, an IMO layer deposition cycle includes a supercycle that includes two subcycles, each subcycle forming a respective oxide. In a first indium oxide subcycle, the substrate is alternately and sequentially contacted with the indium precursor and the oxygen reactant. The first subcycle may be repeated one, two, or more times. In a second molybdenum oxide subcycle, the substrate is alternately and sequentially contacted with the molybdenum precursor and the oxygen reactant. The second subcycle may be repeated one, two, or more times. The oxygen reactant may be the same in each subcycle, or may be different in one or more subcycles. Although referred to as the first and second subcycles, the subcycles may be performed in any order within the supercycle. Additionally, the number of times each subcycle is performed may vary independently within the supercycle. For example, the number of times one or more subcycles are performed may be varied to achieve a desired composition. The number of times each subcycle is performed within each supercycle may be the same or different. The supercycle may be repeated one, two, or more times to obtain an IMO layer of a desired thickness and composition. A deposition supercycle that includes two subcycles may be written as {[indium precursor + oxygen reactant]xN1 + [molybdenum precursor + oxygen reactant]xN2}xN3, where N1, N2, and N3 are integers. As will be used in the detailed description below, square brackets denote an ALD subcycle, while curly brackets denote a supercycle.

[0074] In some embodiments, annealing in an oxygen environment includes being within a supercycle, and a deposition supercycle that includes two subcycles may be written as {[indium precursor + oxygen reactant]xN1 + [molybdenum precursor + oxygen reactant]xN2 + [oxygen reactant annealing]xN3} xN4, where N1, N2, N3, and N4 are integers. Such an oxygen reactant annealing step may be included in any of the deposition cycles described herein.

[0075] As described above, in some embodiments, the IMO layer may include a mixture of one or more individual oxides, such as indium oxide and molybdenum oxide. In some embodiments, the IMO layer includes a mixture of one or more individual oxides, or consists of or consists essentially of one or more individual oxides, such as indium oxide and molybdenum oxide. In some embodiments, the IMO layer includes a molybdenum-doped indium oxide layer, or consists of or consists essentially of a molybdenum-doped indium oxide layer. In some embodiments, the IMO layer includes a molybdenum-doped In2O3 layer.

[0076] In some embodiments, the stoichiometry of the IMO layer may be adjusted by adjusting the ratio of the individual oxides in the layer. In some embodiments, the desired stoichiometry of the IMO layer is achieved by selecting the number of each subcycle within the supercycle, such as to provide a desired In / Mo ratio.

[0077] In some embodiments, additional reactants are included in one or more supercycles. For example, the additional reactants can improve the desired electrical properties of the IMO layer. In some embodiments, the additional reactants can be used to control the carrier density or concentration. In some embodiments, the additional reactants can be used to control defect formation during the deposition of the IMO layer. In some embodiments, the additional reactants can passivate oxygen vacancies in the grown IMO layer. In some embodiments, the additional reactants can include one or more of NH3, N2O, NO2, and H2O2.

[0078] In some embodiments, the additional reactants are included in one or more subcycles within the supercycle. In some embodiments, in at least one supercycle, the additional reactants are included in each subcycle. In some embodiments, the additional reactants are provided separately in at least one supercycle, such as after completion of one subcycle and before the start of the next subcycle.

[0079] In each of the above subcycles, the additional reactants can be provided together with the oxygen reactant or after the oxygen reactant. In some embodiments, the additional reactants can be provided alternately and sequentially after the oxygen reactant. For example, a subcycle including the additional reactants can be written as [metal precursor (indium or molybdenum) + oxygen reactant + additional reactant]xN1, where N is an integer. In some embodiments, the additional reactants can be provided together with the oxygen reactant, such as in the sequence: [metal precursor (indium or molybdenum) + (oxygen reactant + additional reactant)]xN1, where N1 is an integer. That is, in some embodiments, the additional reactants are provided simultaneously with the oxygen reactant. In some embodiments, the additional reactants can flow continuously throughout the deposition subcycle or even throughout the deposition supercycle.

[0080] In some embodiments, the additional reactants are provided in one or more binary oxide subcycles. In some embodiments, the additional reactants are provided in an indium oxide subcycle. For example, the indium oxide subcycle can be written as [indium precursor + oxygen reactant + additional reactant]xN1, where N1 is an integer. In some embodiments, the additional reactants are provided in a molybdenum oxide subcycle. For example, the molybdenum oxide subcycle can be written as [molybdenum precursor + oxygen reactant + additional reactant]xN1, where N1 is an integer. As described above, in some embodiments, the additional reactants can be provided simultaneously with the oxygen reactant.

[0081] In some embodiments, the IMO layer deposition supercycle includes a surface modification step in which the substrate is contacted with a surface modifier. The surface modification can activate or deactivate the surface state on the substrate, thereby affecting the amount of precursor chemisorbed on the substrate in subsequent steps where the precursor is provided. The surface modification step can be performed at any suitable moment in the IMO layer deposition supercycle. For example, before the substrate is contacted with the indium precursor, the substrate can be contacted with the surface modifier. Additionally or alternatively, before the substrate is contacted with the molybdenum precursor, the substrate can be contacted with the surface modifier. Additionally or alternatively, before the substrate is contacted with the oxygen reactant, the substrate can be contacted with the surface modifier. This can advantageously reduce the growth of each cycle of one or more layer composition subcycles, so as to be able to achieve a given composition with a minimum number of total subcycles in the supercycle. In other words, using a surface modifier can improve internal mixing and avoid or reduce compositional variations along the growth direction.

[0082] In some embodiments, the surface modification step is performed before the substrate is contacted with any precursor. In other words, in some embodiments, before the substrate is contacted with the indium precursor and / or the molybdenum precursor, the substrate is contacted with the surface modifier. In other embodiments, the surface modification step is performed after any of the aforementioned subcycles are executed, such that the surface modification step is performed on the metal oxide (such as indium oxide and molybdenum oxide).

[0083] In some embodiments, the surface modifier can react with the OH groups on the substrate surface. Exemplary surface modifiers include alcohols and acid anhydrides. Suitable alcohols include methanol, ethanol, and / or isopropanol. Suitable acid anhydrides include formic anhydride and acetic anhydride.

[0084] In some embodiments, the indium precursor includes an alkyl ligand. In some embodiments, the alkyl ligand includes a branched or straight-chain hydrocarbon group containing 1-10 carbon atoms. In some embodiments, the alkyl ligand includes an alkylamino or alkoxy substituent that can be bonded to the indium atom through a heteroatom (i.e., N or O). In some embodiments, the ligand is 3-(dimethylamino)propyl or 3-(diethylamino)propyl. In some embodiments, the indium precursor is trimethylindium. In some embodiments, the indium precursor is triethylindium. In some embodiments, the indium precursor is ethyldimethylindium. In some embodiments, the indium precursor is InMe2(CH2CH2CH2NMe2), InEt2(CH2CH2CH2NMe2), InMe2(CH2CH2CH2NEt2) or InEt2(CH2CH2CH2NEt2).

[0085] In some embodiments, the indium precursor includes a halogen ligand. In some embodiments, the halogen ligand is chloride. In some embodiments, the indium precursor includes InCl or InCl3. In some embodiments, the indium precursor is InMe2Cl.

[0086] In some embodiments, the indium precursor includes a cyclopentadienyl (Cp) or a substituted cyclopentadienyl ligand. In some embodiments, the substituents on the Cp include one or more of the following groups: methyl, ethyl, isopropyl, n-propyl, isobutyl, tert-butyl, n-butyl, sec-butyl, trimethylsilyl, pentyl, cyclopentyl, hexyl, cyclohexyl, 2-dimethylaminoethyl, 3-dimethylaminopropyl, 2-methoxyethyl, or 3-methoxypropyl. In some embodiments, the indium molybdenum precursor is InCp. In some embodiments, the indium precursor is In(EtCp). In some embodiments, the indium precursor is In(CpCH2CH2NMe2) or In(CpCH2CH2CH2NMe2). In some embodiments, the indium precursor is InMe2(CpCH2CH2NMe2) or InMe2(CpCH2CH2CH2NMe2). In some embodiments, the indium precursor is In(CpCH2CH2OMe) or In(CpCH2CH2CH2OMe). In some embodiments, the indium precursor is InMe2(CpCH2CH2OMe) or InMe2(CpCH2CH2CH2OMe).

[0087] In some embodiments, the indium precursor includes an alkoxide ligand. In some embodiments, the alkoxide ligand is isopropanol. In some embodiments, the alkoxide ligand is tert-butoxide. In some embodiments, the alkoxide ligand is ditertiary pentoxide. In some embodiments, the ligand is 1-(dimethylamino)-2-propoxide (dmap). In some embodiments, the ligand is 1-(dimethylamino)-2-methyl-2-propanol (dmamp). In some embodiments, the ligand is 1-(dimethylamino)-2-methyl-2-butoxide (dmamb). In some embodiments, the precursor is tris(tert-pentoxy)indium(III). In some embodiments, the indium precursor is tris(tert-butoxy)indium(III). In some embodiments, the indium precursor is tris(isopropoxy)indium(III). In some embodiments, the indium precursor is In(dmap)3, In(dmamp)3, or In(dmamb)3. In some embodiments, the indium precursor is InMe2(dmap), InMe2(dmamp), or InMe2(dmamb). In some embodiments, the indium precursor is InEt2(dmap), InEt2(dmamp), or InEt2(dmamb). In some embodiments, the indium precursor is In(dmamp)2(OiPr).

[0088] In some embodiments, the indium precursor includes an amide ligand. In some embodiments, the ligand is dimethylamide. In some embodiments, the ligand is diethylamide. In some embodiments, the ligand is ethylmethylamide. In some embodiments, the ligand is bis(trimethylsilyl)amide. In some embodiments, the indium precursor is InMe2(NMe2), InMe2(NEt2) or InMe2(NEtMe). In some embodiments, the indium precursor is InEt2(NMe2), InEt2(NEt2) or InEt2(NEtMe). In some embodiments, the indium precursor is InMe2[N(SiMe3)2]. In some embodiments, the indium precursor is InEt2[N(SiMe3)2].

[0089] In some embodiments, the indium precursor includes an amidino or guanidino ligand. In some embodiments, the ligand is N,N'-di-tert-butylethylamidine (tBu2AMD). In some embodiments, the ligand is N,N'-diisopropylethylamidine (iPr2AMD). In some embodiments, the ligand is N,N'-di-tert-pentylethylamide (tPn2AMD). In some embodiments, the ligand is N,N'-di-sec-butylethylamidine (sBu2AMD). In some embodiments, the ligand is N,N'-di-tert-butylformamidine (tBu2FMD). In some embodiments, the ligand is N,N'-diisopropylformamidine (iPr2FMD). In some embodiments, the ligand is N,N'-di-tert-pentylformamide (tPn2FMD). In some embodiments, the ligand is N,N'-di-sec-butylformamide (sBu2FMD). In some embodiments, the indium precursor is In(sBu2AMD)3, In(tBu2AMD)3, In(iPr2AMD)3 or In(tPn2AMD)3. In some embodiments, the indium precursor is In(tBu2FMD)3, In(iPr2FMD)3, In(tPn2FMD)3 or In(sBu2FMD)3. In some embodiments, the indium-molybdenum precursor is a molecule of the formula InR2L, where R is a methyl or ethyl ligand, and where L is selected from tBu2AMD, iPr2AMD, tPn2AMD, sBu2AMD, tBu2FMD, iPr2FMD, tPn2FMD or sBu2FMD.

[0090] In some embodiments, the indium precursor includes a β-diketonate ligand. In some embodiments, the ligand is acetylacetonate (acac), 2,2,6,6-tetramethyl-3,5-heptanedionate (thd) or 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac). In some embodiments, the indium precursor is In(thd)3. In some embodiments, the indium precursor is In(acac)3. In some embodiments, the indium precursor is In(hfac)3.

[0091] In some embodiments, the indium precursor includes a triazene ligand. In some embodiments, the indium precursor is tris(di-tert-butyltriazenyl)indium(III).

[0092] According to an example of the present disclosure, the molybdenum precursor may include one or more of molybdenum halides, molybdenum oxyhalides, molybdenum organometallic compounds, molybdenum metal organic compounds, and the like.

[0093] In some embodiments, the molybdenum precursor may include a molybdenum halide precursor. In a further example, the molybdenum halide precursor may include a molybdenum chalcogenide, and in some embodiments, the molybdenum halide precursor may include a molybdenum chalcogenide halide. For example, the molybdenum chalcogenide halide precursor may include an oxohalide of molybdenum selected from molybdenum oxychloride, molybdenum oxyiodide, and molybdenum oxybromide. In an exemplary embodiment, the molybdenum halide precursor may include molybdenum oxychloride, including but not limited to molybdenum(V) oxychloride (MoOCl3), molybdenum(VI) oxychloride (MoOCl4), and molybdenum(IV) oxychloride (MoO2Cl2).

[0094] In some embodiments, the molybdenum precursor includes one or more cyclic moieties. For example, the molybdenum precursor may include one or more benzene rings. In some embodiments, the molybdenum precursor includes two benzene rings. One or both benzene rings may include (e.g., C1-C6) hydrocarbon substituents. In some embodiments, each benzene ring of the molybdenum precursor includes an alkyl substituent. The alkyl substituent may be methyl, ethyl, or a straight-chain or branched alkyl containing three, four, five, or six carbon atoms. For example, the alkyl substituent of the benzene ring may be n-propyl or isopropyl. Additionally, the alkyl substituent may be in the n-, i-, t-, or s- form of a butyl, pentyl, or hexyl moiety. In some embodiments, the molybdenum precursor includes bis(ethylbenzene)molybdenum (Mo(EtBz)2), consisting of or consisting essentially of.

[0095] In some embodiments, the molybdenum precursor includes a cyclopentadienyl (Cp) ligand. For example, the molybdenum precursor may include MoCp2Cl2 or MoCp2H2, Mo(iPrCp)2Cl2, Mo(iPrCp)2H2, Mo(EtCp)2H2, consisting of or consisting essentially of.

[0096] In some embodiments, the molybdenum precursor includes at least one alkyl ligand, such as a C1 to C4 alkyl, such as methyl, ethyl, propyl, or butyl. In some embodiments, the molybdenum precursor contains at least one alkoxide ligand, such as a C2 to C4 alkoxide, such as ethoxide, propoxide, isopropoxide, n-butoxide. In some embodiments, the molybdenum may include molybdenum isopropoxide, consisting of or consisting essentially of.

[0097] In some embodiments of the present disclosure, the molybdenum precursor comprises a metal-organic compound containing nitrogen. In some embodiments, the molybdenum precursor comprises a metal-organic compound that includes at least one of an amido group and an imino group. In some embodiments, the molybdenum precursor comprises a metal-organic compound that includes at least one of a tert-butylimino group and a dimethylamino group. In some embodiments, the molybdenum precursor comprises a molybdenum atom attached to nitrogen. In some embodiments, the attached molybdenum is attached to the imino nitrogen in the molybdenum precursor. In some embodiments, the molybdenum precursor comprises bis(tert-butylimino)bis(dimethylamino)molybdenum (Mo(NMe2)2(N t Bu)2). In some embodiments, the molybdenum precursor consists of or consists essentially of bis(tert-butylimino)bis(dimethylamino)molybdenum.

[0098] Other exemplary molybdenum precursors include molybdenum hexacarbonyl (Mo(CO)6), tetrachloro(cyclopentadienyl)molybdenum, Mo(tBuN)2(NMe2)2, Mo(NBu)2(StBu)2, (Me2N)4Mo, (iPrCp)2MoH2, Mo(NMe2)4, Mo(NEt2)4, Mo2(NMe2)6, Mo(tBuN)2(NMe2)2, Mo(NtBu)2(StBu)2, Mo(NtBu)2(iPr2AMD)2, Mo(thd)3, MoO2(acac)2, MoO2(thd)2, MoO2(iPr2AMD)2, Mo(Cp)2H2, Mo(iPrCp)2H2, Mo(η6-ethylbenzene)2, MoCp(CO)2(η3-allyl), and MoCp(CO)2(NO).

[0099] In some embodiments, the oxygen reactant includes one or more of water, ozone, H2O2, oxygen (O), molecular oxygen (O2), oxygen radicals, oxygen plasma, NO2, N2O, and other compounds containing N and O but not containing a metal or a metalloid. In some embodiments, the oxygen reactant is water. In some embodiments, the oxygen reactant is ozone. In some embodiments, such as those described above, one or more oxygen reactants are used during the deposition process to react with one or more indium or molybdenum precursors to form an indium molybdenum oxide layer. For example, the oxygen reactant can be used with one of the indium or molybdenum precursors in a binary oxide sub-cycle. According to an example of the present disclosure, a first oxygen reactant is used in the indium oxide sub-cycle and a second oxygen is used in the molybdenum oxide sub-cycle. In some embodiments, the first oxygen reactant and the second oxygen reactant are the same. In some embodiments, the first oxygen reactant and the second oxygen reactant are different.

[0100] In some embodiments, the IMO layer is deposited to a thickness of 200 nm or less, about 100 nm or less, about 50 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm or less, about 5 nm or less, or about 3 nm or less. In some embodiments, the IMO is deposited to a thickness less than 1000 nm, less than 750 nm, less than 500 nm, less than 250 nm, or less than 100 nm. The IMO layer will contain materials deposited in at least one deposition cycle, or at least 2 deposition cycles, or at least 10 deposition cycles, or at least 100 deposition cycles, or at least 1000 deposition cycles.

[0101] Atomic layer deposition allows for conformal deposition of the IMO layer. In some embodiments, the IMO layer is deposited on a three-dimensional structure, and the IMO layer has a conformality of at least 90%, 95% or higher. In some embodiments, the IMO layer is approximately 100% conformal.

[0102] In some embodiments, in a structure with a high aspect ratio, the formed IMO layer has a step coverage greater than about 80%, greater than about 90%, and greater than about 95%. In some embodiments, when comparing the depth or height of a feature to its width, a high aspect ratio structure has an aspect ratio greater than about 3:1. In some embodiments, the structure has an aspect ratio greater than about 5:1, 10:1, 20:1, 40:1, 60:1, 80:1, 100:1, 150:1, 200:1 or greater.

[0103] In some embodiments, the carbon impurity concentration of the formed IMO layer is less than 20 atomic%, less than 10 atomic%, less than 5 atomic%, less than 2 atomic%, less than 1 atomic%, or less than 0.5 atomic%. In some embodiments, the formed IMO layer has less than 30 atomic%, less than 20 atomic%, less than 10 atomic%, less than 5 atomic%, less than 3 atomic%, or less than 1 atomic%.

[0104] In some embodiments, the IMO layer formed by the methods of the present disclosure has an indium content (atomic%) of less than 80 atomic%, or less than 70 atomic%, or less than 60 atomic%, or less than 50 atomic%, or less than 40 atomic%, or less than 30 atomic%, or less than 20 atomic%, or less than 10 atomic%. In some embodiments, the MIZO layer formed by the methods of the present disclosure has an indium content (atomic%) between 80 atomic% and 10 atomic%, or between 70 atomic% and 20 atomic%, or between 60 atomic% and 30 atomic%.

[0105] In some embodiments, the IMO layer formed by the method of the present disclosure has a molybdenum content (atomic %) of less than 40 atomic %, or less than 30 atomic %, or less than 20 atomic %, or less than 15 atomic %, or less than 10 atomic %, or less than 5 atomic %, or less than 1 atomic %, or less than 0.1 atomic %, or less than 0.01 atomic %, or less than 0.001 atomic %, or between 0.001 atomic % and 40 atomic %.

[0106] In some embodiments, in a 200 or 300 mm wafer or other substrate such as a square substrate, the formed IMO layer has a thickness non-uniformity (1 sigma standard deviation) of less than 10%, less than 5%, less than 2%, less than 1%, or less than 0.5%.

[0107] In some embodiments, in a 200 or 300 mm wafer or other substrate such as a square substrate, the formed IMO layer has an elemental composition non-uniformity (metal atom concentration non-uniformity) of less than 30%, less than 20%, less than 10%, less than 5%, less than 2%, less than 1%, or less than 0.5% in the substrate surface direction.

[0108] In some embodiments, depending on the application requirements, the IMO layer deposited by the process disclosed herein is annealed after deposition. In some embodiments, the IMO layer is annealed in an oxygen environment. For example, these layers can be annealed at high temperature in water, O2, or any other oxygen reactant mentioned above. In some embodiments, these layers can be annealed in an oxygen reactant including oxygen plasma, oxygen radicals, atomic oxygen, or excited oxygen species. In some embodiments, the IMO layer is annealed in a hydrogen-containing environment or an inert atmosphere, such as an N2, Ar, or He atmosphere. In some embodiments, these layers are annealed in a synthesis gas. In some embodiments, no annealing step is performed.

[0109] In some embodiments, after the deposition of the IMO layer, other layers are deposited. The additional layers can be deposited directly on and in contact with the ALD-deposited IMO layer.

[0110] Although certain embodiments and examples have been discussed, those skilled in the art will understand that the scope of the claims extends beyond the specifically disclosed embodiments to other alternative embodiments and / or uses and their obvious modifications and equivalents. Indeed, various modifications of the present disclosure, such as alternative useful combinations of the described elements, will be 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.

[0111] In the present disclosure, in the absence of specified conditions and / or structures, those skilled in the art can readily provide such conditions and / or structures as routine experiments in view of the present disclosure.

Claims

1. A method for forming an indium molybdenum oxide layer (IMO layer) on a substrate in a reaction chamber, the method comprising: A cyclic deposition process comprising a plurality of repeated deposition cycles is performed, wherein the deposition cycles comprise: (a) contacting a substrate with a vapor phase indium precursor; (b) contacting the substrate with a vapor phase molybdenum precursor; and (c) contacting the substrate with an oxygen reactant.

2. The method according to claim 1, wherein: The cyclic deposition process includes an atomic layer deposition process.

3. The method according to claim 2, wherein: The deposition cycle includes an indium oxide sub-cycle.

4. The method according to claim 3, wherein: The molybdenum indium oxide layer includes molybdenum-doped indium oxide.

5. The method according to claim 2, wherein: The deposition cycle includes an indium oxidation sub-cycle and a molybdenum oxidation sub-cycle.

6. The method according to claim 5, wherein: The oxygen reactant contacts the substrate after step (a) and after step (b).

7. The method according to claim 6, wherein: The indium molybdenum oxide layer is a mixture of indium oxide and molybdenum oxide.

8. The method according to claim 7, wherein: The indium oxidation sub-cycle is carried out in the first reaction chamber, and the molybdenum oxidation sub-cycle is carried out in the second reaction chamber.

9. The method according to claim 2, wherein: The substrate is heated to a substrate temperature below 250°C.

10. The method according to claim 1, wherein: The indium molybdenum oxide layer has a molybdenum content between 0.001 atomic % and 40 atomic %.

11. The method according to claim 1, wherein: The vapor phase indium precursor includes a ligand selected from the group consisting of alkyl, alkylamino, alkoxy, halide, cyclopentadienyl (Cp), alkoxide, amide, amidine, guanidinyl, β-diketonate, and triazene.

12. The method according to claim 11, wherein: The gas phase indium precursor is selected from: trimethyl indium, triethyl indium, ethyl dimethyl indium, InMe2(CH2CH2CH2NMe2), InEt2(CH2CH2CH2NMe2), InMe2(CH2CH2CH2NEt2), InEt2(CH2CH2CH2NEt2), InCl, InCl3, InMe2Cl, In(CpCH2CH2NMe2), In(CpCH2CH2CH2NMe2), InMe2(CpCH2CH2NMe2), InMe2(CpCH2CH2CH2NMe2), In(CpCH2CH2OMe), In(CpCH2CH2CH2OMe), InMe2(CpCH2CH2OMe), InMe2(CpCH2CH2OMe), InMe2(CpCH2CH2OMe, tri(tert-pentyloxy)indium(III), tri(tert-butoxy)indium(III), tri(isopropoxy)indium(III), In(dmap)3, In(dmamp3), In(dmamb)3、InMe2(dmap)、InMe2(dmamp)、InMe2(dmamb)、InEt2(dmap)、InEt2(dmamp)、InEt2(dmamb), In(dmamp)2(OiPr), InMe2(NMe2), InMe2(NEt2), InMe2(NEtMe), InEt2(NMe2), InEt2(NEt2), InEt2(NEt Me), InMe2[N(SiMe3)2], InEt2[N(SiMe3)2], In(sBu2AMD)3, In(tBu2AMD)3, In(iPr2AMD)3 or In(tPn2AMD)3, In(tBu2FMD)3, In(iPr2FMD)3, In(tPn2FMD)3, In(thd)3, In(acac)3, In(hfac)3 and tri(di-tert-butyltriazene)indium(III) In(sBu2FMD)3 and an indium precursor represented by InR2L, wherein R is a methyl or ethyl ligand and wherein L is selected from tBu2AMD, iPr2AMD, tPn2AMD, sBu2AMD, tBu2FMD, iPr2FMD, tPn2FMD and sBu2FMD.

13. The method according to claim 1, wherein: The gas phase molybdenum precursor is selected from Mo(CO)6, (Mo(NMe2)2(N t Bu)2), MoCl4O, MoO2(acac)2, Mo(EtBz)2, molybdenum isopropoxide, MoO2(acac)2, Mo(O i Pr)5 and MoCl2O2.

14. The method according to claim 1, wherein: The gas-phase oxygen reactant includes one or more of the following: oxygen (O), molecular oxygen (O2), water (H2O), ozone (O3) and hydrogen peroxide (H2O2).

15. An atomic layer deposition (ALD) process for forming an indium molybdenum oxide layer, the ALD process comprising a deposition cycle, the deposition cycle comprising alternately and sequentially contacting a substrate with trimethylindium, a molybdenum precursor, and an oxygen reactant in a reaction chamber, and repeating the deposition cycle until the indium molybdenum oxide layer has been formed to a desired thickness and composition.

16. The process of claim 15, wherein: The molybdenum precursor is selected from Mo(CO)6, (Mo(NMe2)2(N t Bu)2), MoCl4O, MoO2(acac)2, Mo(EtBz)2, molybdenum isopropoxide, MoO2(acac)2, Mo(O i Pr)5 and MoCl2O2.

17. The process of claim 16, wherein: The molybdenum precursor includes Mo(NMe2)2(N t Bu)2.

18. The process of claim 15, wherein: The indium molybdenum oxide layer includes molybdenum-doped indium oxide having a molybdenum content between 0.001 atomic % and 40 atomic %.

19. The process of claim 15, wherein: The deposition cycle includes an indium oxidation sub-cycle including contacting the substrate with trimethylindium and a first oxygen reactant and a molybdenum oxidation sub-cycle including contacting the substrate with a molybdenum precursor and a second oxygen reactant.

20. The process of claim 19, wherein: The first oxygen reactant includes ozone (O 3 ) and the second oxygen reactant includes water vapor (H 2 O).

Images