Method for filling recesses on a substrate with a flowable layer structure

Abstract

A method for filling a recess on a substrate is disclosed.SOLUTION: The disclosed method includes depositing a flowable layer structure on a substrate and heating the flowable layer structure above a glass transition temperature of the flowable layer structure. A method of depositing a flowable layer structure includes depositing an aluminum oxide-based flowable layer structure using an atomic layer deposition process.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates generally to the fields of semiconductor processing methods and device and integrated circuit manufacturing. More specifically, the present disclosure relates to methods of forming a flowable layer structure comprising aluminum oxide and methods of filling recesses on a substrate with the flowable layer structure. [Background technology]

[0002] Flowable layers are widely used in semiconductor device manufacturing processes for a variety of purposes. For example, flowable layers can be useful for filling narrow, high-aspect ratio structures in advanced semiconductor devices because they can fill features with high aspect ratios and fill small structures with minimal additional charge. In addition, flowable layers can reduce the complexity and cost of device fabrication, particularly when compared to traditional spin-on techniques such as flowable layers, by significantly reducing the number and associated costs of removal steps, thereby simplifying the manufacturing process. Furthermore, flowable layers can add versatility in certain applications because they can also be used for surface defect masking, planarization using capping films, and the like.

[0003] Borophosphosilicate glass (BPSG) is a common flowable material used in semiconductor manufacturing. For example, in intermetal dielectric (IMD) applications, BPSG can be used as an insulating layer between different metal layers. In metal-to-metal dielectric (PMD) applications, BPSG can function as a dielectric layer before the deposition of a metal layer, thereby helping to separate the silicon substrate from the metal interconnect. In planarization applications, BPSG planarizes the surface of the semiconductor substrate, making it smoother and more uniform for subsequent photolithography steps. Furthermore, in passivation layer applications, BPSG can function as a protective layer on semiconductor devices, shielding them from contaminants and mechanical damage.

[0004] However, there are several common problems associated with the use of flowable BPSG glass. BPSG can be reflowed at high temperatures to aid in planarization, but this characteristic can also lead to thermal stability issues during subsequent processing steps. Furthermore, the incorporation of boron and phosphorus into BPSG can introduce stresses into the glass, potentially resulting in cracking and reliability issues. Therefore, alternative flowable layers and methods for forming and using such layers are desirable.

[0005] The entire discussion, including the discussion of problems and solutions set forth in this section, is included in this disclosure solely for the purpose of providing a context for the disclosure, and 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 otherwise constitutes prior art. Summary of the Invention [Means for solving the problem]

[0006] This summary introduces selected concepts in a simplified form that are described in more detail below. This summary is not necessarily intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0007] Various embodiments of the present disclosure include a method for filling a recess on a substrate disposed in a reaction chamber, depositing a flowable layer structure on the substrate by performing a plurality of deposition supercycles of an atomic layer deposition process, each of the plurality of deposition supercycles performing one or more first subcycles of a first ALD process to deposit an aluminum oxide layer, each of the one or more first subcycles including introducing an aluminum precursor into the reaction chamber and introducing a first oxygen reactant into the reaction chamber; and conducting one or more second sub-cycles of a second ALD process to deposit a metal oxide layer, the one or more second sub-cycles each comprising introducing one or more dopant precursors and introducing a second oxygen reactant, the one or more dopant precursors comprising a doping element having an oxidation state equal to an oxidation state of aluminum and an ionic radius different from an oxidation state of aluminum; depositing a flowable layer structure on the substrate; and heating the flowable layer structure at a temperature at or above the glass transition temperature of the flowable layer structure.

[0008] In some embodiments, the doping element is selected from the group consisting of the lanthanide elements, Group IIIA (Group 13) elements, and Group IIB (Group 12) elements.

[0009] In some embodiments, the doping element is selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), scandium (Sc), lutetium (Lu), erbium (Er), gallium (Ga), dysprosium (Dy), and indium (In).

[0010] In some embodiments, the flowable layer structure comprises a superlattice structure comprising two or more repeating unit layer structures, each unit layer structure comprising an aluminum oxide / doped metal oxide bilayer, and adjacent doped metal oxide layers within the superlattice structure comprise different doping elements having different ionic radii.

[0011] In some embodiments, the difference in ionic radius between doping elements in adjacent doped metal oxide layers of the superlattice structure is between 0.04 Angstroms and 0.74 Angstroms.

[0012] In some embodiments, adjacent doped metal oxide layers in the superlattice structure comprise different doping elements having different coordination numbers.

[0013] In some embodiments, the difference in coordination numbers between doping elements in adjacent doped metal oxide layers of the superlattice structure is 1-6.

[0014] In some embodiments, the method further includes performing one or more first subcycles to deposit an initial aluminum oxide layer on the substrate prior to depositing the superlattice structure, and performing one or more first subcycles to deposit a capping aluminum oxide layer on the superlattice structure.

[0015] In some embodiments, each of the first sub-cycles further includes introducing a silicon precursor into the reaction chamber.

[0016] In some embodiments, heating the flowable layer structure further comprises thermally annealing the flowable layer structure in an environment comprising water vapor.

[0017] Various additional embodiments of the present disclosure include a method for filling recesses on a substrate with a flowable layer structure, comprising two or more repeating aluminum silicate (AlSi x O y ) / Doping Metal Oxide (MO z) conducting an atomic layer deposition (ALD) process to deposit a superlattice structure including a bilayer, the ALD process including a deposition supercycle including alternately and sequentially conducting one or more first subcycles and one or more second subcycles, each of the first subcycles including alternately and sequentially contacting the substrate with an aluminum precursor, a silicon precursor, and a first oxygen precursor, and each of the second subcycles including alternately and sequentially contacting the substrate with a dopant precursor and a second oxygen reactant, and forming adjacent AlSi layers within the superlattice structure. x O y / MO z The double layer is deposited using different dopant precursors, so that the adjacent AlSi x O y / MO z The present invention relates to a method comprising: performing an atomic layer deposition (ALD) process, wherein each of the bilayers comprises a different doping element having a different ionic radius and a different coordination number; and heating the flowable layer structure at a temperature above the glass transition temperature of the flowable layer structure.

[0018] In some embodiments, the difference in ionic radius between doping elements in adjacent doped metal oxide layers of the superlattice structure is between 0.04 Angstroms and 0.74 Angstroms.

[0019] In some embodiments, the difference in coordination numbers between doping elements in adjacent doped metal oxide layers of the superlattice structure is 1-6.

[0020] In some embodiments, the method further comprises depositing an initial AlSi layer on the substrate prior to depositing the superlattice structure. x O y performing one or more first sub-cycles to deposit a capping layer on the superlattice structure; x O y performing one or more first sub-cycles to deposit the layer.

[0021] In some embodiments, the doping element comprises a lanthanide element selected from the group consisting of lanthanum (La), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), lutetium (Lu), erbium (Er), and dysprosium (Dy).

[0022] In some embodiments, the doping element comprises a Group IIIA (Group 13) element selected from the group consisting of gallium (Ga) and indium (In).

[0023] In some embodiments, the doping element comprises a Group IIIB (Group 3) element selected from the group consisting of scandium (Sc) and yttrium (Y).

[0024] Various additional embodiments of the present disclosure are directed to a method for filling recesses on a substrate disposed within a reaction chamber, the method comprising: x O y ) depositing a layer structure at least partially within the recess of the substrate, wherein the doped AlSi x O y The structure is the initial AlSi x O y layer, and the initial AlSi x O y Two or more repeated AlSi layers are arranged on top of each other. x O y / Metal oxides (MO z ) bilayers within the superlattice structure, z ) layers each containing different doping elements having different ionic radii and different coordination numbers; and a capping layer of AlSi disposed on the superlattice structure. x O y and depositing the flowable doped aluminum silicate (AlSi x O y ) layer structure in an environment containing water vapor, x O y) layer structure above the glass transition temperature to form the flowable doped aluminum silicate (AlSi x O y ) inducing a reflow of the layer structure, thereby at least partially filling the recess.

[0025] In some embodiments, the superlattice structure is deposited by performing multiple deposition supercycles of an atomic layer deposition process, each of the multiple deposition supercycles comprising: x O y performing one or more first subcycles to deposit a layer, wherein one or more second subcycles are performed to deposit a doped metal oxide layer, each of the plurality of first subcycles including introducing an aluminum precursor into the reaction chamber, introducing a silicon precursor into the reaction chamber, and introducing a first oxygen reactant into the reaction chamber; and performing one or more second subcycles to deposit a doped metal oxide layer, wherein each of the plurality of second subcycles includes introducing one or more dopant precursors, introducing a second oxygen reactant, and performing one or more second subcycles.

[0026] In some embodiments, the first subcycle is performed 1 to 10 times, and the second subcycle is performed 1 to 5 times.

[0027] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described hereinabove. Of course, it will be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0028] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the accompanying drawings, although the invention is not limited to any particular embodiment(s) disclosed. [Brief explanation of the drawings]

[0029] To easily identify the discussion of any particular element or operation, the most significant digit(s) of a reference number refers to the figure number in which that element is first introduced.

[0030] A more complete understanding of the embodiments of the present disclosure can be obtained by reference to the detailed description and claims in light of the following illustrative drawings.

[0031] [Figure 1] 1A-1D illustrate a method for filling recesses on a substrate with a flowable layer structure, according to one or more embodiments. [Figure 2] 1 illustrates a method of depositing a flowable layer structure according to one or more embodiments. [Figure 3] 1 illustrates a method of depositing a superlattice structure according to one or more embodiments. [Figure 4] 1 illustrates a structure including a substrate having a recess, according to one or more embodiments. [Figure 5]FIG. 1 illustrates a structure including a flowable layer structure on a recessed portion of a substrate, according to one or more embodiments. [Figure 6] 1A-1C illustrate structures including recesses filled with a flowable layer structure according to one or more embodiments. [Figure 7] FIG. 1 illustrates a cross-sectional view of a flowable layer structure according to one or more embodiments. [Figure 8] 1 is a table showing the ionic radii and coordination numbers of various elements that make up the flowable layer structure, according to one or more embodiments.

[0032] It will be understood that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0033] The descriptions of exemplary embodiments of methods and configurations provided below are merely exemplary and intended for illustrative purposes only. The following descriptions are not intended to limit the scope of the present disclosure or the claims. Furthermore, the description of multiple embodiments having shown structures or steps is not intended to exclude other embodiments having additional structures or steps, or other embodiments incorporating different combinations of the described structures or steps.

[0034] For example, layers deposited within recesses, such as trench structures, typically fail to completely fill the recess opening. Incomplete filling of a recess can create seams or multiple voids located below the center of the filled recess. These seams / voids are defects that can adversely affect subsequent manufacturing processes and device performance. For example, the seams / voids can allow the etchant solution to quickly pass through the center of the incompletely filled recess, which can reduce the effective cross-section of the feature in terms of resistivity or other material properties.

[0035] Flowable layers (and flowable layer structures) can address the problem of incomplete filling of recesses by allowing the flowable layer to deform at moderately elevated temperatures to better conform to the underlying substrate and / or fill voids. However, currently available flowable materials are commonly silica-based, such as BPSG, and alternative flowable materials are desirable to develop that offer different material properties while maintaining the desired flow properties.

[0036] Thus, various embodiments provided include a flowable layer structure comprising an aluminum oxide comprising an aluminum silicate material and an aluminum silicate layer structure comprising a doped metal oxide layer. As used herein, the term "aluminum oxide layer" may refer to a layer of a material comprising aluminum and oxygen, and includes aluminum oxide layers (AlO x layer), and aluminum silicate layer (AlSi x O y The aluminum oxide layer may include an aluminum silicate layer (AlSi x O y In embodiments comprising an aluminum silicate layer, the aluminum silicate layer may be aluminum oxide (AlO x ) and silicon oxide (SiO x ) may be alternately arranged.

[0037] In this disclosure, "gas" can include materials that are gaseous at ambient temperature and pressure (NTP), vaporized solids, and / or vaporized liquids, and can be comprised of a single gas or a mixture of gases in some circumstances. Gases other than process gases, i.e., gases introduced without passing through a gas distribution assembly, other gas distribution device, or the like, can be used, for example, to seal the reaction space and can include seal gases. Precursors and reactants can be gases. Exemplary seal gases include noble gases, nitrogen, and the like. In some cases, the term "precursor" can refer to a compound that participates in a chemical reaction to produce another compound, and specifically a compound that constitutes the membrane matrix or main backbone of the membrane, and the term "reactant" can be used interchangeably with the term precursor.

[0038] As used herein, the term "substrate" may refer to any underlying material that can be used to form a device, circuit, or film, or on which a device, circuit, or film can be formed, by a method according to an embodiment of the present disclosure. The substrate may include a bulk material such as silicon (e.g., single crystal silicon), other Group IV materials such as germanium, or other semiconductor materials such as Group II-VI or Group III-V semiconductor materials, and may include one or more layers overlying or underlying the bulk material. Furthermore, the substrate may be configured with various shapes, such as recesses, protrusions, and the like, formed in or on at least a portion of the layer of the substrate. For example, the substrate may include a bulk semiconductor material and an insulating or dielectric material layer overlying at least a portion of the bulk semiconductor material. Furthermore, the term "substrate" may refer to any underlying material that may be used, or on which a device, circuit, or film may be formed. A "substrate" may be continuous or discontinuous, rigid or flexible, solid or porous. The substrate may be in any form, such as a powder, a plate, or a workpiece. Substrates in the form of plates may include wafers of various shapes and sizes. Substrates may be constructed from materials such as silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. Continuous substrates may extend beyond the boundaries of the process chamber in which the deposition process occurs or may be moved through the process chamber so that the process continues until the end of the substrate is reached. Continuous substrates may be supplied from a continuous substrate supply system, which allows for the production and output of continuous substrates in any suitable form. Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, webs, flexible materials, and bundles of continuous filaments or fibers (i.e., ceramic or polymer fibers). Continuous substrates may also include carriers or sheets onto which non-continuous substrates are placed.

[0039] As used herein, the terms "film" and / or "layer" can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, partial or complete molecular layers, partial or complete atomic layers, or clusters of atoms and / or molecules. A film or layer may comprise, or at least partially consist of, multiple dispersed atoms on the surface of a substrate, and / or may be embedded within, or become embedded within, a substrate and / or within a device fabricated on the substrate. A film or layer may comprise a material or layer with pinholes and / or isolated islands. A film or layer may be at least partially continuous. A film or layer may be patterned, e.g., subdivided, and included within multiple semiconductor devices. A film or layer may be selectively grown on some portions of a substrate and not grown on other portions.

[0040] The terms "cyclic deposition process" or "cyclical deposition process" can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit layers on a substrate, and include processing techniques such as atomic layer deposition (ALD), cyclical chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes that include ALD and cyclical CVD components.

[0041] The term "atomic layer deposition" can refer to a deposition process in which deposition cycles, typically multiple consecutive deposition cycles, are performed in a process chamber. As used herein, the term atomic layer deposition is also meant to include processes designated by related terms such as atomic layer chemical vapor deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas-source MBE, metalorganic MBE, and chemical beam epitaxy when performed using alternating pulses of precursor(s), reactive gas(es), and purge (e.g., inert carrier) gas(es). Pulsing can include exposing a substrate to a precursor or reactant. This can be done, for example, by introducing the precursor or reactant into a reaction chamber in which the substrate is present. Additionally or alternatively, exposing a substrate to a precursor can include moving the substrate to a location in a substrate processing system where the reactant or precursor is present.

[0042] 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, which may include previously deposited material or other materials from a previous ALD cycle) to form a monolayer or quasi-monolayer of material that does not readily react with additional precursors (i.e., self-limiting reaction). A reactant (e.g., another precursor or reactant gas) may then be introduced into the process chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. Purging steps may be utilized during one or more cycles (e.g., during each step of each cycle) to remove any excess precursor from the process chamber and / or to remove any excess reactants and / or reaction by-products from the reaction chamber.

[0043] As used herein, "precursor" includes a gas or material that can become gaseous and can be represented by a chemical formula that includes elements that may be incorporated during the deposition process, as described herein. The terms "precursor" and "reactant" can also refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction that produces another compound. A "precursor" typically includes a moiety that is at least partially incorporated into the compound or element that results from the chemical reaction in question. Such a resulting compound or element may be deposited on a substrate. A "reactant" may also be an element or compound that is not incorporated to a significant extent into the resulting compound or element. However, in certain embodiments, a reactant may also contribute to the resulting compound or element.

[0044] A "structure," as used in this disclosure, can be or may include a substrate as described herein. A structure may include one or more layers on or within a substrate, for example, one or more layers formed according to a method as described herein. A structure may include an entire device or partial device portion within or on the structure.

[0045] As used herein, the term "recess" can refer to an opening or depression disposed between two surfaces of a non-planar surface. For example, the term "recess" can refer to an opening or depression disposed between opposing sidewalls or protrusions extending perpendicularly from the surface of a substrate, or between opposing sloping sidewalls of a depression extending perpendicularly into the surface of a substrate.

[0046] As used herein, the term "seam" can refer to a void line or one or more isolated voids formed by the abutment of edges formed in the gap-fill metal. The presence of a "seam" can be confirmed using high-magnification microscopy, such as scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM), and a "seam" is considered to be present when observation reveals a distinct vertical void line or one or more vertical voids in the recess filled with the gap-fill metal.

[0047] It should be noted that many exemplary materials are provided throughout the embodiments of this disclosure, and the chemical formulas provided for each of the exemplary materials should not be construed as limiting, nor should the non-limiting exemplary materials provided be limited by any exemplary stoichiometry.

[0048] In this disclosure, any two numbers of a variable can constitute a workable range for that variable, and any range stated may include or exclude endpoints. Additionally, in some embodiments, any value of a stated variable (whether or not it is stated with "about") may refer to an exact or approximate value, and may include equivalents, and may refer to an average, median, representative, or key value, etc. Furthermore, in this disclosure, the terms "including," "constituted by," and "having" can, in some embodiments, independently refer to "typically or broadly comprising," "comprising," "consisting essentially of," or "consisting of." In this disclosure, any defined meaning does not necessarily exclude the ordinary and customary meaning in some embodiments. In some cases, percentages stated in this disclosure may be relative or absolute percentages.

[0049] It will be understood that the terms "on" or "over" may be used herein to describe relative location relationships. Another element, film, or layer may be directly on top of the layer being referred to, or another layer (intermediate layer) or element may be interposed therebetween, or a layer may be disposed on top of the layer being referred to but not completely cover the surface of the layer being referred to. Thus, unless the term "directly" is used separately, the terms "on" or "over" will be interpreted as relative concepts. Similarly, it will be understood that the terms "under," "underlying," or "below" will be interpreted as relative concepts.

[0050] 1 illustrates a method 100 for filling a recess on a substrate with a flowable layer structure. Briefly, the method 100 includes placing a substrate including a recess in a reaction chamber (step 102), depositing a flowable layer structure on the substrate (e.g., over the recess) (deposition process 104), and heating the flowable layer structure at a temperature above the glass transition temperature of the flowable layer structure (step 106).

[0051] More specifically, the substrate onto which the flowable layer structure is deposited may include a recess or multiple recesses. FIG. 4 illustrates an exemplary structure 400 including a substrate 402 (as described above) and a recess 404. The structure 400 may comprise a portion of a device structure, such as a partially fabricated device structure. The structure 400 may also include a partially fabricated logic device, memory device, integrated circuit, or the like. While the structure 400 is illustrated as including a single recess 404, it should be understood that the provided methods are not so limited, and substrates including multiple recesses can be filled by the methods disclosed in this disclosure. The cross-sectional profile of the recess 404 illustrated in FIG. 4 is exemplary, and various provided embodiments can fill the recess with alternative cross-sectional profiles, such as, but not limited to, curved, scalloped, V-shaped, tapered, re-entrant, and through-silicon via structures. The recess 404 may also be a structure having a high aspect ratio feature, such as, for example, a trench structure, a vertical gap, and / or a fin structure. When referring to a recess having a high aspect ratio, recess 404 has an aspect ratio (e.g., height to width ratio) of greater than 2:1, greater than 5:1, greater than 10:1, greater than 25:1, greater than 50:1, or greater than 300:1.

[0052] According to embodiments of the present disclosure, a substrate is placed in a reaction chamber configured for deposition of a flowable layer structure. In such embodiments, the reaction chamber may comprise components or assemblies of single-wafer or batch ALD reactors, in which deposition occurs simultaneously on multiple substrates. In some embodiments, the reaction chamber may form part of a cluster tool in which various different processes are performed for the fabrication of integrated circuits. In some embodiments, a flow-type reactor and associated reaction chamber may be utilized. In some embodiments, a high-volume manufacturing-capable single-wafer ALD reactor and associated reaction chamber may be used. In other embodiments, a batch reactor containing multiple substrates may be used. For embodiments in which a batch ALD reactor is used, the number of substrates may be in the range of 10 to 300, 50 to 150, or 300 to 130.

[0053] According to embodiments of the present disclosure, depositing the flowable layer structure (deposition process 104 of method 100 as shown in FIG. 1 ) can include heating a substrate to a desired deposition temperature. In some embodiments, the deposition temperature (i.e., substrate temperature) at which the flowable layer structure is deposited can be between 100°C and 600°C, between 150°C and 550°C, between 200°C and 500°C, between 250°C and 450°C, or between 200°C and 400°C. In some embodiments, the deposition temperature can be less than 600°C, less than 500°C, less than 400°C, less than 300°C, less than 250°C, or less than 200°C.

[0054] In addition to controlling the temperature of the substrate, the pressure in the reaction chamber may also be adjusted to enable deposition of a flowable layer structure. For example, the pressure in the reaction chamber may be less than 760 Torr, or between 0.1 Torr and 10 Torr, or between 0.5 Torr and 5 Torr, or between 1 Torr and 4 Torr.

[0055] According to an embodiment of the present disclosure, FIG. 2 illustrates in greater detail a deposition process for depositing a flowable layer structure on a substrate (ie, deposition process 104 of FIG. 1).

[0056] In some embodiments, a deposition process 104 for depositing a flowable layer structure may include depositing an initial aluminum oxide layer on a substrate (step 202), depositing a superlattice structure by performing one or more deposition supercycles of an atomic layer deposition process (ALD supercycle process 204), and depositing a capping aluminum oxide layer on the superlattice structure (step 206). In such embodiments, the flowable layer structure deposited by deposition process 104 includes an initial aluminum oxide layer, a superlattice structure, and a capping aluminum oxide layer, with each of the constituent layers being a flowable layer.

[0057] In some embodiments, the deposition process 104 for depositing the flowable layer structure can omit the deposition of the initial aluminum oxide layer (step 202) and / or the deposition of the capping aluminum oxide layer (step 206). In such embodiments, the flowable layer structure deposited by the deposition process 104 includes a superlattice structure, and the superlattice structure is a flowable superlattice structure.

[0058] 3 illustrates the ALD super cycle process 204 for depositing the superlattice structure in more detail. According to an embodiment of the present disclosure, the ALD super cycle process 204 includes performing multiple deposition super cycles, as illustrated by super cycle loop 306. In such an embodiment, each deposition super cycle includes performing one or more first sub-cycles of a first ALD process 302 to deposit an aluminum oxide layer and performing one or more second sub-cycles of a second ALD process 304 to deposit a doped metal oxide layer.

[0059] 3, the first ALD process 302 (of the ALD super cycle process 204) may include performing one or more first sub-cycles (represented by first cycle loop 308). Each first sub-cycle may include introducing an aluminum precursor into the reaction chamber (substep 312), optionally introducing a silicon precursor into the reaction chamber (optional substep 314), and introducing a first oxygen reactant into the reaction chamber (substep 316). The aluminum oxide layer deposited by the first ALD process 302 may be AlO x In embodiments including a silicon precursor, the optional substep 314 of introducing a silicon precursor can be omitted. x O y In embodiments including a layer, optional substep 314 of introducing a silicon precursor is included. Substep 312, optional substep 314, and substep 316 may be repeated as exemplified by first cyclic loop 308. Moreover, substep 312, optional substep 314, and substep 316 may begin and / or end in any order. Still further, first ALD process 302 may include one or more repetitions (e.g., 1-10 times or 1-5 times) of substep 312, optional substep 314, and / or substep 316 before proceeding to other steps of first ALD process 302.

[0060] Additionally, the ALD super cycle process 204 includes a second ALD process 304, which may include performing one or more second sub-cycles (as illustrated by second cycle loop 310). Each second sub-cycle may include introducing one or more dopant precursors into the reaction chamber (substep 318) and introducing a second oxygen reactant into the reaction chamber (substep 320). The second ALD process 304 may be used to form a doped metal oxide layer (MO), as described in more detail below. z ) can be used to deposit a film of a material. Sub-steps 318 and 320 may be repeated, as exemplified by second cyclic loop 310. Moreover, sub-steps 318 and 320 may begin and / or end in any order. Still further, second ALD process 304 may include one or more repetitions (e.g., 1-10 or 1-5 times) of sub-steps 318 and / or 320 before proceeding to another step of second ALD process 304.

[0061] In various embodiments, the first sub-cycle (of the first ALD process 302) may be performed 1 to 10 times.

[0062] In various embodiments, the second sub-cycle (of the second ALD process 304) may be performed 1 to 5 times.

[0063] In various embodiments, the superlattice structure comprises aluminum oxide (e.g., AlO x or AlSi x O y ) and doped metal oxides (e.g., MO z) repeating layers. Of course, although the superlattice structure is deposited as a superlattice structure, the individual layers of the superlattice structure may not be discernible (e.g., by observation using high magnification methods such as transmission electron microscopy). For example, in some embodiments, the aluminum oxide layer and / or the doped metal oxide layer may be deposited with a thickness that is insufficient to be observable, and in some embodiments, the aluminum oxide layer and the doped metal oxide layer may form a mixed material that includes aluminum, optionally silicon, oxygen, and one or more doping elements.

[0064] In various embodiments, introducing the precursors / reactants (e.g., aluminum precursors, silicon precursors, dopant precursors, and oxygen reactants) can include pulsing the precursors / reactants into the reaction chamber, where the precursors / reactants contact a substrate disposed in the reaction chamber. For example, pulsing can include exposing the substrate to the precursors or reactants. This can be done, for example, by introducing the precursors or reactants into the reaction chamber in which the substrate is present. Additionally or alternatively, exposing the substrate to the precursors can include moving the substrate to a location in the substrate processing system where the reactants or precursors are present.

[0065] According to embodiments of the present disclosure, the precursor and oxygen reactant may be purged from the reaction chamber, for example, after each pulse of precursor / reactant and / or upon completion of the first cycle loop 308 and / or the second cycle loop 310. In some embodiments, each first sub-cycle and each second sub-cycle of the ALD super cycle process 204 may also include one or more additional steps that may be performed during each sub-cycle or during selected deposition sub-cycles.

[0066] As previously mentioned, in some embodiments, the flowable layer structure may include an initial aluminum oxide layer, a superlattice structure, and a capping aluminum oxide layer, each of the constituent layers being a flowable layer. In such embodiments, as illustrated by deposition process 104 in Figure 2, deposition of the flowable layer structure includes depositing an initial aluminum oxide layer by an atomic layer deposition process (step 202), depositing a superlattice structure (as described above) on the initial aluminum oxide layer (step 204), and depositing a capping aluminum oxide layer on the superlattice structure by an atomic layer deposition process (step 206).

[0067] In some embodiments, the ALD process for depositing the initial aluminum oxide layer (step 202) may be the same as or substantially the same as the first ALD process 302 of the ALD supercycle process 204. In such embodiments, depositing the initial aluminum oxide layer (step 202) may include introducing an aluminum precursor into the reaction chamber, optionally introducing a silicon precursor into the reaction chamber, and introducing an oxygen reactant into the reaction chamber. The initial aluminum oxide layer may be AlO x In embodiments including a silicon precursor, the optional step of introducing a silicon precursor may be omitted. x O y In other embodiments involving a layer, a step of introducing a silicon precursor is included. The steps of introducing the silicon precursor, optional silicon precursor, and first oxygen reactant can be repeated in any order and / or can be started and / or ended as described above. Still further, the ALD process for depositing the initial aluminum oxide layer (step 202) can include one or more repetitions (e.g., 1 to 10 times or 1 to 5 times) of the steps of introducing the aluminum precursor, optional silicon precursor, and first oxygen reactant before proceeding with other steps of the ALD process of step 202.

[0068] In various embodiments, the initial aluminum oxide layer may be deposited as a closure layer (e.g., a layer that encapsulates the underlying substrate). In some embodiments, the initial aluminum oxide layer is deposited by performing the first sub-cycle (of the first ALD process 302) 5 or more, 10 or more, 15 or more, or 20 or more, or more than 20, or between 1 and 10 times.

[0069] In some embodiments, the ALD process for depositing the capping aluminum oxide layer (step 206) may be the same as or substantially the same as the first ALD process 302 of the ALD super cycle process 204. In such embodiments, depositing the capping aluminum oxide layer (step 206) may include introducing an aluminum precursor into the reaction chamber, optionally introducing a silicon precursor into the reaction chamber, and introducing an oxygen reactant into the reaction chamber. If the capping aluminum oxide layer is AlO x In embodiments including a capping aluminum oxide layer, the optional step of introducing a silicon precursor can be omitted. x O y In other embodiments involving a layer, a step of introducing a silicon precursor is included. The steps of introducing the silicon precursor, optional silicon precursor, and oxygen reactant can be repeated in any order and / or can be started and / or ended as described above. Still further, the ALD process for depositing the capping aluminum oxide layer (step 206) can include one or more repetitions (e.g., 1 to 10 times or 1 to 5 times) of the steps of introducing the aluminum precursor, optional silicon precursor, and oxygen reactant before proceeding to other steps of the ALD process of step 202.

[0070] In various embodiments, the capping aluminum oxide layer may be deposited as a closure layer (e.g., a layer that encapsulates the underlying superlattice structure). In some embodiments, the capping aluminum oxide layer is deposited by performing the second sub-cycle (of the second ALD process 304) 5 or more, 10 or more, 15 or more, 20 or more, more than 20, or 1 to 10 times.

[0071] The aluminum precursor(s) used in the deposition of the flowable layer structure are selected to be the aluminum precursor(s) used in the deposition of the superlattice structure, as well as the optional initial aluminum oxide layer and optional capping AlSi x O y layer (as described in detail below). In some embodiments, the aluminum precursor is selected from the group consisting of trimethylaluminum (TMA), dimethylaluminum chloride, aluminum trichloride (AlCl), dimethylaluminum isopropoxide (DMAI), tris(tert-butyl)aluminum (TTBA), tris(isopropoxide)aluminum (TIPA), and triethylaluminum (TEA). In some embodiments, the aluminum precursor is dimethylaluminum isopropoxide (DMAI).

[0072] The silicon precursor(s) optionally used in the deposition of the flowable layer structure may be used in the deposition of the superlattice structure, as well as in the deposition of any initial aluminum oxide layer and any capping AlSi x O y In some embodiments, the silicon precursor is selected from the group consisting of silane, organosilane, and chlorosilane. For example, the silicon precursor can include a silicon hydride precursor. In such examples, the silicon hydride precursor can be selected from the group consisting of silane (SiH), disilane (SiH), trisilane (SiH), and tetrasilane (SiH). 10). In further examples, the silicon precursor may comprise a silicon halide precursor. In such examples, the silicon halide precursor may comprise a silicon chloride precursor selected from the group consisting of monochlorosilane (MCS), dichlorosilane (DCS), trichlorosilane (TCS), hexachlorodisilane (HCDS), octachlorotrisilane (OCTS), and silicon tetrachloride (STC). In further examples, the silicon precursor may comprise a silicon iodide precursor. In such examples, the silicon halide precursor may comprise a silicon iodide precursor selected from the group consisting of monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane. In additional examples, the silicon precursor may comprise an organosilane, such as an alkylsilane or an aminosilane. In such examples, the silicon precursor may comprise one or more of tris(dimethylamino)silane, bis(tert-butylamino)silane, di(sec-butylamino)silane, trisilylamine, neopentasilane, bis(dimethylamino)silane, (dimethylamino)silane (DMAS), bis(diethylamino)silane (BDEAS), bis(ethylmethylamino)silane (BEMAS), tetrakis(dimethylamino)silane (TKDMAS), trimethylsilane, tetramethylsilane, silane, tetra(ethoxy)silane (TEOS), tris(tert-butoxy)silanol, tris(tert-pentoxy)silanol, and dimethyldichlorosilane.

[0073] The exemplary deposition methods provided above (see, e.g., deposition process 104 and ALD super cycle process 204) use one or more oxygen reactants in the deposition of the flowable layer structure. In some embodiments, the oxygen reactant may include one or more of water (HO), ozone (O), and hydrogen peroxide (HO).

[0074] 3, the ALD super cycle process 204 can include introducing a first oxygen reactant (substep 316) and introducing a second oxygen reactant (substep 320). In some embodiments, the first oxygen reactant and the second oxygen reactant can include the same oxygen reactant (e.g., HO). In some embodiments, the first oxygen reactant and the second oxygen reactant can include different oxygen reaction chambers (e.g., HO as the first oxygen reactant and HO as the second oxygen reactant).

[0075] During deposition of the superlattice structure, one or more dopant precursors are introduced into the reaction chamber (substep 318 of the ALD supercycle process 204), for example, during deposition of a doped metal oxide layer.

[0076] In some embodiments, the dopant precursor comprises a doping element having an oxidation state equal to the oxidation state of the aluminum content in the flowable layer structure. In certain embodiments, the aluminum content in the flowable layer structure has an oxidation state of +3, and the dopant precursor comprises a doping element having an oxidation state of +3. In such embodiments, the oxidation states of the aluminum and the doping element may be equal to form a flowable layer structure that is neutral, i.e., does not contain mobile charge carriers. In some embodiments, the dopant precursor comprises a doping element having a different ionic radius and / or a different coordination number than aluminum, as described in more detail below.

[0077] In some embodiments, the dopant precursor comprises a doping element selected from the group consisting of lanthanides, Group IIIA (Group 13) elements, and Group IIB (Group 12) elements. In one embodiment, the doping element comprises a lanthanide element selected from the group consisting of lanthanum (La), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), lutetium (Lu), erbium (Er), dysprosium (Dy), neodymium (Nd), samarium (Sm), gadolinium (Gd), terbium (Tb), holmium (Ho), and thulium (Tm). In another embodiment, the doping element comprises a Group IIIA (Group 13) element selected from the group consisting of gallium (Ga) and indium (In). In certain embodiments, the doping element comprises a Group IIIB (Group 3) element selected from the group consisting of scandium (Sc) and yttrium (Y). In some embodiments, the doping element is selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), scandium (Sc), lutetium (Lu), erbium (Er), gallium (Ga), dysprosium (Dy), and indium (In).

[0078] In some embodiments, the dopant precursor is an organometallic precursor, and in such embodiments, the dopant precursor may comprise a doping element and a ligand selected from the group consisting of a cyclopentadienyl, a β-diketonate, an amidinate, or an amidate.

[0079] The exemplary methods provided above for depositing a flowable layer structure may also include configuring various layers of a superlattice structure to improve the reflow characteristics of the flowable structure.

[0080] 7 illustrates an exemplary flowable layer structure 700 deposited by the above-described method. The flowable layer structure 700 may include an initial aluminum oxide layer 702, a superlattice structure 704 deposited on the initial aluminum oxide layer 702, and a capping aluminum oxide layer 706 deposited on the superlattice structure 704.

[0081] In various embodiments, the flowable layer structure 700 of FIG. 7 comprises a superlattice structure 704 comprising two or more repeating unit layer structures 708. For example, each unit layer structure 708 can comprise an aluminum oxide layer 710 and a doped metal oxide layer 712 forming an aluminum oxide / doped metal oxide bilayer. In such examples, adjacent doped metal oxide layers within the superlattice structure 704 can include different doping elements having different ionic radii. Furthermore, in such examples, adjacent doped metal oxide layers within the superlattice structure 704 can include different doping elements having different coordination numbers. While not intending to be bound by any theory, it is believed that a superlattice structure with a large variation in ionic radii and coordination numbers between adjacent doped metal oxide layers increases the disorder in the superlattice structure, thereby keeping the flowable layer structure amorphous and having improved reflow characteristics, such as a lower glass transition temperature at which the flowable layer structure is mobile.

[0082] In one or more embodiments, flowable layer structure 700 (FIG. 7) includes two or more aluminum oxide / doped metal oxide bilayers (as exemplified by unit layer structure 708). In such embodiments, adjacent doped metal oxide layers within superlattice structure 704, such as first doped metal oxide layer 714 and second doped metal oxide layer 716, include different doping elements having different ionic radii.

[0083] The table shown in FIG. 8 lists various elements in the flowable layer structure of the present disclosure, along with their corresponding ionic radii in angstroms (Å) and their coordination numbers. In one or more embodiments, the difference in ionic radii between doping elements in adjacent doped metal oxide layers (e.g., layers 714 and 716) of superlattice structure 704 is between 0.04 Å and 0.74 Å. In some embodiments, the difference in ionic radii between doping elements in adjacent doped metal oxide layers (e.g., between layers 714 and 716) is greater than 0.04 Å, greater than 0.11 Å, greater than 0.21 Å, greater than 0.34 Å, greater than 0.37 Å, greater than 0.42 Å, greater than 0.49 Å, or 0.74 Å or greater. In one or more embodiments, the difference in coordination numbers between doping elements in adjacent doped metal oxide layers (e.g., layers 714 and 716) of superlattice structure 704 is between 3 and 6. In some embodiments, the difference in coordination number between doping elements in adjacent doped metal oxide layers (eg, layers 714 and 716) is 1 or more, greater than 2, greater than 3, greater than 4, or six.

[0084] Further, in one or more embodiments, each of the two or more aluminum oxide / doped metal oxide bilayers (as exemplified by unit layer structure 708) includes a doped metal oxide layer (e.g., doped metal oxide layer 712) having a difference in ionic radius and / or coordination number with the adjacent aluminum oxide layer (e.g., aluminum oxide layer 710). In one or more embodiments, the difference in ionic radius between the aluminum oxide layer and the doped metal oxide layer comprising unit layer structure 708 is between 0.22 Å and 0.82 Å. In some embodiments, the difference in ionic radius between the aluminum oxide layer and the doped metal oxide layer comprising unit layer structure 708 is greater than 0.22 Å or less than or equal to 0.82 Å. In one or more embodiments, the difference in coordination number between the aluminum oxide layer and the doped metal oxide layer comprising unit layer structure 708 is between 2 and 6. In some embodiments, the difference in coordination number between the aluminum oxide layer and the doped metal oxide layer comprising unit layer structure 708 is greater than 2 or less than or equal to 6.

[0085] In various embodiments, the flowable layer structure includes a structure having an aluminum content of 50 atomic percent (at%) to 90 at%, 60 at% to 90 at%, or 80 at% to 90 at%. In some embodiments, the flowable layer structure includes a structure having a silicon content of 0 at% to 45 at%. In some embodiments, the flowable layer structure includes a structure having a silicon content of 1 at% to 45 at%, 1 at% to 30 at%, or 1 at% to 25 at%. In some embodiments, the flowable layer structure includes a structure having a doping element content of 1 at% to 20 at%.

[0086] In various embodiments, the flowable layer structure includes structures having a total average layer thickness of less than 1000 Å, less than 750 Å, less than 500 Å, less than 250 Å, less than 150 Å, less than 100 Å, less than 50 Å, less than 25 Å, less than 10 Å, or between 10 Å and 1000 Å.

[0087] In certain embodiments, a flowable layer structure (such as the flowable layer structure 700 of FIG. 7 ) is formed by performing 10 or more repetitions of the first sub-cycle of the first ALD process 302 to form an initial aluminum oxide layer 702 (e.g., AlO x layer or AlSi x O y The structure may include a layer.

[0088] In certain embodiments, a superlattice structure 704 may be deposited on the initial aluminum oxide layer 702. In such embodiments, the superlattice structure may include four or more aluminum oxide / doped metal oxide bilayers (i.e., unit layer structures). In such examples, the aluminum oxide component of the superlattice structure may be deposited by performing one to five repetitions of the first subcycle of the first ALD process 302, and the doped metal oxide component of the superlattice structure may be deposited by performing one to five repetitions of the second subcycle of the second ALD process 304. In certain embodiments, the first bilayer (deposited on the initial aluminum oxide layer) may include a lanthanum oxide-doped metal oxide layer and an aluminum oxide layer. In certain embodiments, the second bilayer (deposited on the first bilayer) may include a scandium oxide-doped metal oxide layer and an aluminum oxide layer. In certain embodiments, the third bilayer (deposited on the second bilayer) may comprise an aluminum oxide layer and at least one of an yttrium oxide-doped metal oxide layer, an europium oxide-doped metal oxide layer, a cerium oxide-doped metal oxide layer, a praseodymium oxide-doped metal oxide layer, an ytterbium oxide-doped metal oxide layer, or a dysprosium oxide-doped metal oxide layer. In certain embodiments, the fourth bilayer (deposited on the third bilayer) may comprise an aluminum oxide layer and at least one of a lutetium oxide-doped metal oxide layer, an erbium oxide-doped metal oxide layer, a gallium oxide-doped metal oxide layer, or an indium oxide-doped metal oxide layer.

[0089] In certain embodiments, a capping aluminum oxide layer 706 (e.g., AlO x layer or AlSi x O y layer) may be deposited on the superlattice structure 704 by performing 10 or more repetitions of the first sub-cycle of the first ALD process 302.

[0090] 5 illustrates a structure 500 comprising the aforementioned structure 400 of FIG. 4 (including substrate 402 and recess 404) after deposition of a flowable layer structure 700 over substrate 402, and specifically over recess 404. As shown in FIG. 5, flowable layer structure 700 is conformally deposited on non-planar substrate 402. In various embodiments, flowable layer structure 700 is deposited in an amorphous state. In such embodiments, flowable layer structure 700 is a conformal amorphous glass.

[0091] Returning to the method 100 of FIG. 1 of depositing a flowable layer structure on a substrate, the method 100 may further include heating the flowable layer structure at a temperature equal to or greater than the glass transition temperature of the flowable layer structure (step 106). As used in this disclosure, "glass transition temperature (T g The term "temperature" can refer to the temperature at which flow is initiated within the flowable layer structure. In certain embodiments, the glass transition temperature of the flowable layer structure is less than 1000°C, less than 900°C, less than 800°C, less than 700°C, less than 600°C, less than 500°C, or between 500°C and 1000°C.

[0092] In one or more embodiments, the flowable layer structure is heated above the glass transition temperature of the flowable layer structure in an environment comprising water vapor. In some embodiments, step 106 of method 100, which includes heating the flowable layer structure above the glass transition temperature, is performed in an environment comprising water vapor to induce reflow of the flowable layer structure, thereby at least partially filling the recesses on the substrate. In some embodiments, the flowable layer structure is heated in a reaction chamber having a steam environment. In such embodiments, steam is introduced into the reaction chamber prior to heating the substrate having the flowable layer structure thereon.

[0093] For example, Figure 6 shows structure 600 including the aforementioned structure 500 of Figure 5 (including substrate 402, recess 404, and flowable layer structure) after heating the flowable layer structure above its glass transition temperature, i.e., after completing step 106 of method 100. As shown in Figure 6, flowable layer structure 700 fills recess 404 without forming undesirable seams. In various embodiments, flowable layer structure 700 fills the recess in a seamless manner, i.e., without forming voids in the recess.

[0094] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described hereinabove. Of course, it will be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0095] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments, taken in conjunction with the accompanying drawings, although the invention is not limited to any particular embodiment(s) disclosed.

Claims

1. 1. A method for filling a recess on a substrate disposed in a reaction chamber, comprising: Depositing a flowable layer structure on the substrate by performing a plurality of deposition super-cycles of an atomic layer deposition process, each of the plurality of deposition super-cycles comprising: conducting one or more first sub-cycles of a first ALD process to deposit an aluminum oxide layer, each of the one or more first sub-cycles including introducing an aluminum precursor into the reaction chamber and introducing a first oxygen reactant into the reaction chamber; performing one or more second sub-cycles of a second ALD process to deposit a doped metal oxide layer, each of the one or more second sub-cycles comprising: introducing one or more dopant precursors; and introducing a second oxygen reactant, wherein the one or more dopant precursors comprise a doping element having an oxidation state equal to that of aluminum and an ionic radius different from that of aluminum; depositing a flowable layer structure onto the substrate; heating the flowable layer structure at a temperature above the glass transition temperature of the flowable layer structure.

2. 2. The method of claim 1, wherein the doping element is selected from the group consisting of the lanthanides, Group IIIA (Group 13) elements, and Group IIB (Group 12) elements.

3. 3. The method of claim 2, wherein the doping element is selected from the group consisting of lanthanum (La), yttrium (Y), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), scandium (Sc), lutetium (Lu), erbium (Er), gallium (Ga), dysprosium (Dy), and indium (In).

4. 4. The method of claim 3, wherein the flowable layer structure comprises a superlattice structure comprising two or more repeating unit layer structures, each unit layer structure comprising an aluminum oxide / doped metal oxide bilayer, and adjacent doped metal oxide layers within the superlattice structure comprise a plurality of different doping elements having different ionic radii.

5. 5. The method of claim 4, wherein the difference in ionic radius between the doping elements in adjacent doped metal oxide layers of the superlattice structure is between 0.04 Angstroms and 0.74 Angstroms.

6. The method of claim 5 , wherein adjacent doped metal oxide layers in the superlattice structure comprise different doping elements having different coordination numbers.

7. 7. The method of claim 6, wherein the difference in coordination numbers between the doping elements in adjacent doped metal oxide layers of the superlattice structure is 1-6.

8. performing one or more first sub-cycles to deposit an initial aluminum oxide layer on the substrate prior to depositing the superlattice structure; 5. The method of claim 4, further comprising: performing one or more first sub-cycles to deposit a capping aluminum oxide layer on the superlattice structure.

9. The method of claim 1 , wherein each of the first sub-cycles further comprises introducing a silicon precursor into the reaction chamber.

10. The method of claim 1 , wherein heating the flowable layer structure further comprises thermally annealing the flowable layer structure in an environment comprising water vapor.

11. 1. A method for filling recesses on a substrate with a flowable layer structure, comprising: Two or more repeating aluminum silicates (AlSi ｘ O ｙ ) / Doping Metal Oxide (MO ｚ 2.) conducting an atomic layer deposition (ALD) process for depositing a superlattice structure including a bilayer, the ALD process including a deposition supercycle including alternately and sequentially conducting one or more first subcycles and one or more second subcycles; each cycle of the first subcycle includes alternately and sequentially contacting the substrate with an aluminum precursor, a silicon precursor, and a first oxygen precursor; each cycle of the second subcycle includes alternately and sequentially contacting the substrate with a dopant precursor and a second oxygen reactant; Adjacent AlSi within the superlattice structure ｘ O ｙ / MO ｚ performing an atomic layer deposition (ALD) process in which bilayers are deposited using different dopant precursors, such that each of the adjacent AlSi x O y / MO z bilayers contains different doping elements with different ionic radii and different coordination numbers; heating the flowable layer structure at a temperature above the glass transition temperature of the flowable layer structure.

12. 12. The method of claim 11, wherein the difference in ionic radius between the doping elements in adjacent doped metal oxide layers of the superlattice structure is between 0.04 Angstroms and 0.74 Angstroms.

13. 13. The method of claim 12, wherein the difference in coordination numbers between the doping elements in adjacent doped metal oxide layers of the superlattice structure is 1-6.

14. Prior to depositing the superlattice structure, one or more first sub-cycles are performed to deposit initial AlSi ｘ O ｙ depositing a layer; A capping AlSi layer is formed on the superlattice structure. ｘ O ｙ The method of claim 13 , further comprising: performing one or more first sub-cycles to deposit a layer.

15. 12. The method of claim 11, wherein the doping element comprises a lanthanide element selected from the group consisting of lanthanum (La), cerium (Ce), ytterbium (Yb), praseodymium (Pr), europium (Eu), lutetium (Lu), erbium (Er), and dysprosium (Dy).

16. 12. The method of claim 11, wherein the doping element comprises a Group IIIA (Group 13) element selected from the group consisting of gallium (Ga) and indium (In).

17. 12. The method of claim 11, wherein the doping element comprises a Group IIIB (Group 3) element selected from the group consisting of scandium (Sc) and yttrium (Y).

18. 1. A method for filling a recess on a substrate disposed in a reaction chamber, comprising: Flowable doped aluminum silicate (AlSi ｘ O ｙ ) depositing a layer structure at least partially within the recess of the substrate, wherein the doped AlSi ｘ O ｙ The structure is Initial AlSi ｘ O ｙ Layers and The initial AlSi ｘ O ｙ Two or more repeated AlSi layers are arranged on the layer. ｘ O ｙ / Metal oxide (MO ｚ 1. A superlattice structure comprising a bilayer of metal oxides (MOs) adjacent to each other within said superlattice structure. ｚ a superlattice structure in which each of the layers comprises a different doping element having a different ionic radius and a different coordination number; A capping AlSi layer disposed on the superlattice structure ｘ O ｙ Layers and and depositing The flowable doped aluminum silicate (AlSi ｘ O ｙ ) layer structure in an environment containing water vapor, ｘ O ｙ ) layer structure above the glass transition temperature to form the flowable doped aluminum silicate (AlSi ｘ O ｙ ) inducing a reflow of the layer structure, thereby at least partially filling said recess.

19. The superlattice structure is deposited by performing a plurality of deposition supercycles of an atomic layer deposition process, each of the plurality of deposition supercycles comprising: AlSi ｘ O ｙ performing one or more first subcycles to deposit a layer, each of the plurality of first subcycles including introducing an aluminum precursor into the reaction chamber, introducing a silicon precursor into the reaction chamber, and introducing a first oxygen reactant into the reaction chamber; 20. The method of claim 18, comprising: performing one or more second subcycles to deposit a doped metal oxide layer, wherein each of the plurality of second subcycles comprises introducing one or more dopant precursors and introducing a second oxygen reactant.

20. 20. The method of claim 19, wherein the first subcycle is performed 1 to 10 times and the second subcycle is performed 1 to 5 times.

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