Methods for forming microelectronic devices and related systems and additional methods

Abstract

This application relates to methods and related systems for forming microelectronic devices and additional methods. A method of forming a microelectronic device includes processing a base structure with a first precursor to adsorb the first precursor to a surface of the base structure and form a first material. The first precursor includes a hydrazine-based compound including Si-N-Si bonds. The first material is processed with a second precursor to convert the first material to a second material. The second precursor includes a Si-centered radical. The second material is processed with a third precursor to convert the second material to a third material including Si and N. The third precursor includes an N-centered radical.

Description

[0001] Cross-reference of related applications

[0002] This application is the entry into the national phase of international patent application PCT / US2021 / 062665, filed on December 9, 2021, designating the People's Republic of China, and published in English on July 28, 2022, as international patent publication WO 2022 / 159195 A1, which claims the benefit of U.S. patent application serial number 17 / 248,376 filed on January 22, 2021, pursuant to Article VIII of the Patent Cooperation Treaty. Technical Field

[0003] In various embodiments, this disclosure generally relates to the field of microelectronic device design and fabrication. More specifically, this disclosure relates to methods of forming microelectronic devices and related atomic layer deposition (ALD) systems and methods of forming sealing materials via ALD. Background Technology

[0004] Microelectronic device designers typically aim to increase the level or density of feature integration within a microelectronic device by reducing the size of individual features and by decreasing the spacing between adjacent features. Furthermore, microelectronic device designers often expect designs that are not only compact but also offer performance advantages and a simplified design architecture.

[0005] Reducing the size and spacing of features places increasingly higher demands on methods used to form microelectronic devices. One solution is to form three-dimensional (3D) microelectronic devices, such as 3D memory devices, where features are arranged vertically rather than horizontally. To form features, multiple materials are positioned above each other and etched to form a material stack. For some memory devices (e.g., 3D cross-point memory devices), the materials include chalcogenide materials and electrode materials. Some of the stacked materials are sensitive to subsequent process actions, such as the processing temperature and / or etching conditions of subsequent processes. Stacked materials may, for example, be thermosensitive and / or sensitive to etching chemistry.

[0006] To protect the stacked materials, a sealant comprising silicon nitride (SiN) has been formed on or over the stack. This sealant is conventionally formed using one or more of plasma-enhanced chemical vapor deposition (PECVD) and plasma-enhanced atomic layer deposition (PEALD) processes. However, conventional PECVD and conventional PEALD processes for high aspect ratio structures can result in one or more of the following: a relatively slow rate of sealant formation (e.g., for PEALD, less than or equal to 0.5 Å sealant / deposition cycle); unwanted damage to sensitive materials due to exposure to plasmas with relatively high ion energy density (IEDF) and / or due to exposure to relatively high processing temperatures; unwanted material modification (e.g., contamination) resulting from unwanted thermodynamically favorable reactions with halide-containing reactants; and incomplete or non-uniform sealant coverage. Summary of the Invention

[0007] In some embodiments, a method of forming a microelectronic device includes treating a substrate structure with a first precursor to adsorb the first precursor onto the surface of the substrate structure and form a first material. The first precursor comprises an hydrazine compound containing Si-N-Si bonds. The first material is treated with a second precursor to convert the first material into a second material. The second precursor comprises a Si-centered radical. The second material is treated with a third precursor to convert the second material into a third material comprising Si and N. The third precursor comprises an N-centered radical.

[0008] In an additional embodiment, an ALD system according to embodiments of the present disclosure includes a first source, a second source, a third source, and an ALD device downstream of and in fluid communication with each of the first, second, and third sources. The first source is configured to contain a hydrazine compound comprising Si-N-Si bonds. The third source is configured to contain N-containing molecules. The ALD device includes a housing structure, a dispensing assembly, and a substrate support. The housing structure defines an internal chamber. The dispensing assembly is configured to receive and direct each of the gaseous hydrazine compound, the Si-containing compound, and the N-containing molecules into the internal chamber. The substrate support is located within the internal chamber and is configured to hold a substrate structure thereon.

[0009] In a further embodiment, a method for forming a sealing material via an ALD includes directing a first gas flow comprising a hydrazine compound containing Si-N-Si bonds into an internal chamber of an ALD device to chemisorb the hydrazine compound onto a substrate structure immobilized within the internal chamber. A second gas flow comprising one or more of a Si-containing compound and Si-centered radicals is directed into the internal chamber to react with the chemisorbed hydrazine compound and form an intermediate material. A third gas flow comprising one or more of an N-containing compound and N-centered radicals is directed into the internal chamber to react with the intermediate material and form at least a portion of the sealing material. Attached Figure Description

[0010] Figure 1 The general structure of an hydramine compound used as a first precursor in the ALD process is shown according to embodiments of the present disclosure.

[0011] Figure 2 The material exposure sequence of the deposition cycle of the ALD process according to embodiments of the present disclosure is shown.

[0012] Figure 3A This is a simplified schematic diagram of a spatial ALD system according to an embodiment of the present disclosure.

[0013] Figure 3B During the use and operation of the space ALD system according to embodiments of this disclosure Figure 3A A simplified schematic diagram of the internal chamber of the space ALD device in the space ALD system shown in the image.

[0014] Figure 4 This is a simplified schematic diagram of a time-sharing ALD system according to an embodiment of the present disclosure. Detailed Implementation

[0015] The following description provides specific details, such as material compositions and processing conditions (e.g., temperature), to provide an exhaustive description of embodiments of this disclosure. However, those skilled in the art will understand that embodiments of this disclosure can be practiced without necessarily employing these specific details. In fact, embodiments of this disclosure can be practiced in conjunction with conventional systems and methods used in the industry. Furthermore, only the process components and actions necessary for understanding embodiments of this disclosure are described in detail below. Those skilled in the art will understand that some process components (e.g., pipes, line filters, valves, temperature detectors, flow detectors, pressure detectors, and the like) are inherently disclosed herein, and adding various conventional process components and actions will be consistent with this disclosure. Moreover, the description provided below does not form a complete process flow for manufacturing microelectronic devices. The structures described below do not form a complete microelectronic device. Additional actions to form a complete microelectronic device from the structures can be performed using conventional manufacturing techniques.

[0016] The drawings presented herein are for illustrative purposes only and are not intended to be actual views of any particular material, component, structure, device, or system. Variations in the shapes depicted in the drawings are expected due to, for example, manufacturing techniques and / or limitations. Therefore, the embodiments described herein should not be construed as limited to the specific shapes or areas illustrated, but include, for example, deviations from shapes derived from manufacturing processes. For example, an area illustrated or described as box-shaped may have rough and / or non-linear features, and an area illustrated or described as circular may contain some rough and / or linear features. Furthermore, acute angles illustrated may be rounded, and vice versa. Therefore, the areas illustrated in the figures are schematic in nature, and their shapes are not intended to illustrate the precise shape of the areas and do not limit the scope of the claims. The drawings are not necessarily drawn to scale. Furthermore, common elements between figures may retain the same element symbols.

[0017] As used herein, the term "substrate" means and includes a substrate or structure on which additional material is formed. A substrate can be a semiconductor substrate, a base semiconductor layer on a support structure, a metal electrode, or a semiconductor substrate on which one or more layers, structures, or regions are formed. A substrate can be a conventional silicon substrate or other bulk substrate comprising layers of semiconductor material. As used herein, the term "bulk substrate" means and includes not only silicon wafers but also silicon-on-insulator (SOI) substrates, such as silicon-on-sapphire (SOS) and silicon-on-glass (SOG) substrates, silicon epitaxial layers on a base semiconductor, and other semiconductor or optoelectronic materials, such as silicon-germanium, germanium, gallium arsenide, gallium nitride, and indium phosphide. Substrates can be doped or undoped. By way of non-limiting examples, the substrate may include at least one of silicon, silicon dioxide, silicon having a natural oxide, silicon nitride, silicon carbonitride, glass, semiconductor, metal oxide, metal, titanium nitride, titanium carbonitride, tantalum, tantalum nitride, tantalum carbonitride, niobium, niobium nitride, niobium carbonitride, molybdenum, molybdenum nitride, molybdenum carbonitride, tungsten, tungsten nitride, tungsten carbonitride, copper, cobalt, nickel, iron, aluminum, and noble metals.

[0018] As used herein, the term "uniform" means that the relative amounts of elements contained in a feature (e.g., material, structure) remain constant across different parts of the feature (e.g., different horizontal parts, different vertical parts). Conversely, as used herein, the term "non-uniform" means that the relative amounts of elements contained in a feature (e.g., material, structure) vary across different parts of the feature. If a feature is non-uniform, then the amounts of one or more elements contained in the feature may vary gradually (e.g., abruptly) or continuously (e.g., gradually (e.g., linearly, parabolically)) across different parts of the feature. A feature may, for example, be formed by and comprise a stack of at least two different materials.

[0019] As used herein, “memory device” means and includes, but is not limited to, microelectronic devices that exhibit memory functionality. In other words, and only by way of non-limiting example, the term “memory device” includes not only conventional memory (e.g., conventional volatile memory, such as conventional dynamic random access memory (DRAM); conventional non-volatile memory, such as conventional NAND memory), but also application-specific integrated circuits (ASICs) (e.g., system-on-a-chip (SoC)), microelectronic devices with combinational logic and memory, and graphics processing units (GPUs) incorporated into memory.

[0020] As used herein, the term “configured” refers to the size, shape, material composition, orientation, and arrangement of one or more of at least one structure and at least one device in a predetermined manner to facilitate the operation of one or more of the structure and device.

[0021] As used herein, the terms “vertical,” “longitudinal,” “horizontal,” and “lateral” refer to the principal plane of the structure and are not necessarily defined by the Earth’s gravitational field. A “horizontal” or “lateral” direction is generally parallel to the principal plane of the structure, while a “vertical” or “longitudinal” direction is generally perpendicular to the principal plane of the structure. The principal plane of the structure is defined by the surface of the structure that has a relatively large area compared to the other surfaces of the structure. Referring to the figures, a “horizontal” or “lateral” direction may be perpendicular to the indicated “Z” axis and parallel to the indicated “X” axis and / or parallel to the indicated “Y” axis; and a “vertical” or “longitudinal” direction may be parallel to the indicated “Z” axis, perpendicular to the indicated “X” axis, and perpendicular to the indicated “Y” axis.

[0022] As used herein, for ease of description, spatial relative terms such as “below,” “under,” “below,” “bottom,” “above,” “top,” “front,” “back,” “left,” “right,” and the like may be used to describe the relationship of one element or feature to another element(s), as illustrated in the figures. Unless otherwise specified, spatial relative terms are intended to cover different orientations of material in addition to those depicted in the figures. For example, if the material in the figures were reversed, then an element described as “below,” “below,” “down,” or “on the bottom” of another element or feature would then be oriented “above” or “on the top” of that other element or feature. Thus, depending on the context in which the terms are used, the term “below” may cover both above and below orientations, as will be apparent to one of ordinary skill in the art. Material may be oriented in other ways (e.g., rotated 90 degrees, reversed, flipped, etc.) and the spatial relative descriptors used herein shall be interpreted accordingly.

[0023] As used herein, a feature described as “adjacent” to each other (e.g., area, structure, device) means and includes the feature of the disclosed identifier (or identifiers) positioned closest to each other (e.g., closest to each other). Additional features (e.g., additional areas, additional structures, additional devices) of the disclosed identifier (or identifiers) that do not match “adjacent” features may be placed between “adjacent” features. In other words, “adjacent” features may be positioned directly adjacent to each other such that no other features intervene between “adjacent” features; or “adjacent” features may be positioned indirectly adjacent to each other such that at least one feature having an identifier different from the identifier associated with at least one “adjacent” feature is positioned between “adjacent” features. Thus, a feature described as “vertically adjacent” to each other means and includes the feature of the disclosed identifier (or identifiers) positioned most vertically close to each other (e.g., closest to each other). Furthermore, a feature described as “horizontally adjacent” to each other means and includes the feature of the disclosed identifier (or identifiers) positioned most horizontally close to each other (e.g., closest to each other).

[0024] As used herein, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly indicates otherwise.

[0025] As used in this article, "and / or" includes any and all combinations of one or more of the items listed in connection with the document.

[0026] As used herein, the term "generally" with respect to a given parameter, property, or condition means and includes the degree to which a given parameter, property, or condition is satisfied with a range of variation (e.g., within acceptable tolerances), as would be understood by one of ordinary skill in the art. By way of example, depending on the specific parameter, property, or condition that is generally satisfied, it may be satisfied by at least 90.0%, at least 95.0%, at least 99.0%, at least 99.9%, or even 100.0%.

[0027] As used herein, “about” or “approximate” with respect to a particular parameter includes the value and the degree of variation of the value within acceptable tolerances for the particular parameter, as would be understood by one of ordinary skill in the art. For example, “about” or “approximate” with respect to a value may include additional values ​​within the range of 90.0% to 110.0%, such as 95.0% to 105.0%, 97.5% to 102.5%, 99.0% to 101.0%, 99.5% to 100.5%, or 99.9% to 100.1%.

[0028] According to embodiments of this disclosure, a method of forming a microelectronic device (e.g., a memory device) includes forming a sealing material on or over at least one additional material (e.g., a material stack) via an atomic layer deposition (ALD) process (e.g., a so-called "space" ALD process, a so-called "time-division" ALD process). The sealing material may at least partially encapsulate the additional material. For example, the sealing material may substantially surround and cover the upper surface (e.g., top surface) and side surfaces (e.g., sidewalls) of the additional material. Compared to conventional processes used to form sealing materials (e.g., conventional PEALD processes, conventional PECVD processes), the ALD process may require relatively less plasma exposure to form the sealing material. Furthermore, the ALD process can mitigate many undesirable reactions (e.g., thermodynamically favorable reactions, reactions chemistried by halide-containing reactants) that would otherwise occur during conventional processes for forming sealing materials, which can contribute to undesirable deviations from the desired material composition of the sealing material (e.g., impurities therein). Compared to conventional processes for forming sealing materials, the ALD process can also be carried out at relatively low temperatures (e.g., in the range of about 200°C to about 550°C).

[0029] Additional materials used to form the sealing material of this disclosure using the systems, apparatus, and methods of this disclosure may have the desired material composition. In some embodiments, the additional material includes a chalcogenide material. The chalcogenide material may include one or more of chalcogenide glasses, chalcogenide metal ion glasses, or other chalcogenide-containing materials. The chalcogenide material may be a binary or multi-component (e.g., ternary, quaternary) compound comprising at least one chalcogenide atom and at least one or more positively charged elements. As used herein, the term "chalcogenide" means and includes elements of Group VI of the periodic table, such as oxygen (O), sulfur (S), selenium (Se), or tellurium (Te). The positively charged elements may include (but are not limited to) one or more of nitrogen (N), silicon (Si), nickel (Ni), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), indium (In), tin (Sn), antimony (Sb), gold (Au), lead (Pb), and bismuth (Bi). By way of example only, chalcogenide materials may comprise compounds containing Ge, Sb, and Te (i.e., GST compounds), such as Ge₂Sb₂Te₅; however, this disclosure is not limited thereto, and chalcogenide materials may comprise other compounds containing at least one chalcogenide element. Chalcogenide materials may be doped or undoped and may contain mixed metal ions. By way of example only, chalcogenide materials may be alloys comprising indium, selenium, tellurium, antimony, arsenic, bismuth, germanium, oxygen, tin, or combinations thereof. In additional embodiments, additional materials may include one or more of electrically insulating materials, conductive materials, and semiconductor materials. Additional materials may be non-uniform or substantially uniform.

[0030] The sealing material formed by the methods of this disclosure may include a silicon-containing material configured and formulated to protect underlying additional material (e.g., a chalcogenide material) during and / or after subsequent processing to form the microelectronic device of this disclosure. The sealing material may, for example, be configured and formulated to provide an airtight barrier that inhibits (e.g., prevents) water from traveling through the sealing material and into the additional material. The sealing material may also be configured and formulated to protect the additional material from unwanted oxidation and / or damage that would otherwise occur without the formation of the sealing material during subsequent processing operations. Additionally, the sealing material may substantially confine (e.g., contain) the chalcogenide material to a specific (e.g., localized) area to maintain desired physical conditions and their stoichiometry. In some embodiments, the sealing material is formed to include silicon (Si) and nitrogen (N). By a non-limiting example, the sealing material may be formed to include a silicon nitride material (e.g., SiN). x ), silicon oxynitride materials (e.g., SiO2) y N x ) and silicon carbide (SiO2) materials x C z N y One or more of the following. This document contains one or more of the following formulas (e.g., SiN...). y SiO x N y SiO y C z N x The formula (x) represents a material containing an average ratio of "x" atoms of one element (for each atom of another element, e.g., Si), "y" atoms of another element (if any), and "z" atoms of an additional element (if any). Because the formula represents relative atomic ratios and is not a strict chemical structure, insulating materials may include one or more stoichiometric compounds and / or one or more non-stoichiometric compounds, and the values ​​of "x", "y" (if any), and "z" (if any) may be integers or non-integers. As used herein, the term "non-stoichiometric compound" means and includes chemical compounds having elemental compositions that cannot be expressed by a well-defined ratio of natural numbers and violate the law of definite proportions.

[0031] The ALD process for forming a sealing material comprises multiple deposition cycles performed within an ALD apparatus of this disclosure (e.g., a spatial ALD apparatus, a time-sharing ALD apparatus). At least one (e.g., at least some) of the deposition cycles comprises a processing sequence (e.g., a material exposure sequence) containing a first precursor, a second precursor, and a third precursor. The first precursor comprises a first chemical species comprising silicon and nitrogen. The second precursor comprises a second chemical species different from the first chemical species and comprising silicon. The third precursor comprises a third chemical species different from each of the first and second chemical species and comprising nitrogen. At least two (2) of the first, second, and third precursors (e.g., each) may be introduced sequentially (e.g., temporally and / or spatially) relative to each other. For example, each of the second and third precursors may be introduced (e.g., sequentially or simultaneously) after the first precursor within a deposition cycle of the ALD process. A first precursor may be chemisorbed onto at least one surface of at least one additional material (e.g., at least one chalcogenide material), and then a second and third precursor may be introduced (e.g., sequentially or simultaneously) onto and react with the chemisorbed first precursor and / or a chemisorbed material comprising the reaction product of the chemisorbed first precursor and one of the second and third precursors. As used herein, the terms “chemisorb” and “chemisorption” mean and encompass a mechanism in which at least one precursor is adsorbed or bound to at least one surface of the material via chemical bonding (e.g., one or more of covalent and ionic bonding). The processing sequence of a deposition cycle may also include the introduction of at least one other material (e.g., an inert gas, N2 gas, plasma), followed by the introduction of at least one of the first, second, and third precursors (e.g., each). The first, second, third, and other materials and their potential sequences in one or more deposition cycles of the ALD process are further described in detail below.

[0032] The first precursor may comprise a compound containing silicon (e.g., at least one Si-N bond, such as at least one Si-N single bond) bonded to nitrogen, which is capable of chemisorption to an additional material (e.g., a chalcogenide material) to which a sealing material will be formed. The compound may also contain nitrogen (e.g., at least one N-N bond, such as at least one N-N single bond) bonded to nitrogen. In some embodiments, the first precursor comprises a hydrazine compound containing Si-N-Si bonds. By way of non-limiting examples, the first precursor may comprise having… Figure 1The compounds shown herein have a general structure in which each R group is individually hydrogen; contains a substituted or unsubstituted alkyl group (e.g., straight-chain, branched, or cyclic) from (1) carbon atom to ten (10) carbon atoms; or a substituted or unsubstituted aryl or heteroaryl group. Each R group may be individually selected such that the first precursor exhibits the desired properties (e.g., reactivity, volatility, toxicity) for use in the ALD process. In some embodiments, at least one (e.g., each) R group is methyl. As a non-limiting example, the first precursor may comprise 1,2-bis(trimethylsilyl)hydrazine (C6H 20 N2Si2). The first precursor may be free of (e.g., may not contain) any halogens (e.g., fluorine (F), chlorine (Cl), bromine (Br), iodine (I)).

[0033] The first precursor reacts with uncoordinated sites of an additional material (e.g., a chalcogenide material) on which a sealing material will be formed through the ALD process of this disclosure, and also reacts with the second and third precursors used in the ALD process. For example, if the first precursor is having Figure 1 The hydrazine compounds with the general structure shown in the diagram have N-N bonds, Si-N bonds, and / or Si-R bonds that can readily break at relatively low temperatures (e.g., less than or equal to 550 °C, for example, in the temperature range from about 200 °C to about 550 °C) to form free radicals (e.g., N-centered free radicals, Si-centered free radicals), which individually readily react with the uncoordinated sites of the material, the second precursor, or the third precursor. This is in contrast to forming the desired sealing material (e.g., SiN) on an additional material (e.g., a chalcogenide material). x SiO y N x SiO y C z N x Compared to conventional precursors used in the conventional process of forming the sealing material, the first precursor can have a superior adhesion coefficient and enhanced reactivity (at least at relatively low temperatures). For example, compared to the Si-NR2 bonding properties of many conventional precursors used to form the sealing material, Figure 1 The N-NR2 bonding characteristics of the hydrazine compounds shown in the paper can promote faster reactivity and enhance the adhesion coefficient. Additionally, Figure 1 The absence of Si-Si bonds in the hydrazine compounds shown reduces the need for plasma (e.g., N-containing plasma) to form the desired sealing material. Furthermore, the absence of halogens in the first precursor avoids unwanted reactions that could otherwise interfere with the efficiency of the ALD process and / or the desired material composition of the sealing material and / or any additional materials below it (e.g., chalcogenide materials).

[0034] The first precursor may be in a solid, liquid, or gaseous state at room temperature and atmospheric pressure. In some embodiments, the first precursor is in a liquid state (e.g., in liquid form) at room temperature and atmospheric pressure. If the first precursor is in a liquid or solid state at room temperature and atmospheric pressure, then the first precursor may vaporize before being introduced into the additional material on which a sealing material will be formed. This vaporization of the first precursor is described in further detail below.

[0035] The second precursor can serve as at least a silicon source for the sealing material. In some embodiments, the second precursor comprises a silicon-centered radical (also referred to as "silyl group"). For example, it can be obtained by processing (e.g., plasma treatment) silicon-containing compounds (e.g., silanes (SiH4), disilanes (Si2H6), higher silane compounds, hydrated hydrogen compound molecules (e.g., tetramethylsilylhydrazine (H2H6)). 12 H2Si4), organoamino silanes (e.g., bis(diethylamino)silane (C8H) 22 The second precursor is formed by one or more of the following: N2Si, silicon tetrahalides (e.g., silicon tetraiodide (SiI4)), disilicides hexahalides (e.g., hexachlorosilane (SiCl3)2), trimethylsilaneamine (H9NSi3), and hydrohalosilanes (e.g., diiodosilane (H2I2Si)). As described in further detail below, in some embodiments, one or more of distal plasma excitation and direct plasma excitation of the silicon-containing compound are used to form the second precursor. The silicon-containing compound can be in a solid, liquid, or gaseous state at room temperature and atmospheric pressure. If the silicon-containing compound is in a liquid or solid state at room temperature and atmospheric pressure, then the silicon-containing compound vaporizes before being processed to form silicon-centered radicals.

[0036] The third precursor can be used as at least a nitrogen source for the sealing material. In some embodiments, the third precursor comprises a nitrogen-centered radical. The third precursor can be formed, for example, by treating (e.g., plasma treatment) nitrogen-containing molecules (e.g., one or more of molecular nitrogen (N2) and ammonia (NH3)). As described in further detail below, in some embodiments, the third precursor is formed using one or more of distal plasma excitation and direct plasma excitation of nitrogen-containing molecules.

[0037] Other materials (if any) used in one or more deposition cycles of the ALD process may be used to flush at one or more points in one or more of the deposition cycles at at least one chamber of the ALD apparatus used in the ALD process of one or more of the first precursor, second precursor, third precursor, their unbound reaction products, and other materials. In additional embodiments, other materials are used to treat (e.g., plasma treatment) one or more of the first precursor, second precursor, third precursor, and sealing materials formed by other steps of individual deposition cycles of the ALD process. By non-limiting examples, other materials may include one or more of the following: at least one inert gas (e.g., at least one rare gas), such as one or more of helium (He), neon (Ne), and argon (Ar); nitrogen (N2); and plasma (e.g., N-containing plasma). In further embodiments, other materials may be omitted from the deposition cycle of the ALD process. By way of non-limiting examples, negative pressure (e.g., vacuum) can be used to flush at one or more points in an individual deposition cycle of the ALD process at at least one chamber of an ALD device used in the ALD process of one or more of the first precursor, second precursor, third precursor, their unbound reaction products and other materials.

[0038] Figure 2 This illustrates a non-limiting example of a material exposure sequence during the deposition cycle of an ALD process used to form the sealing material of this disclosure. For example... Figure 2 As shown, an individual deposition cycle of the ALD process may include: a first action (e.g., a first step, a first stage) which includes treatment with a first precursor P1 (e.g., exposure to the first precursor P1); a second action (e.g., a second step, a second stage) which begins after the completion of the first action and includes treatment with a second precursor P2 (e.g., exposure to the second precursor P2); a third action (e.g., a third step, a third stage) which begins after the completion of the second action and includes treatment with a third precursor P3 (e.g., exposure to the third precursor P3); and a fourth action (e.g., a fourth step, a fourth stage) which begins after the completion of the third action and includes treatment with another material X (e.g., exposure to another material X). Figure 2 The first precursor P1, the second precursor P2, the third precursor P3, and other materials X shown herein correspond to the first precursor, the second precursor, the third precursor, and other materials previously described herein (e.g., the same as them). Figure 2 The first precursor P1 shown in the text can be used as a reference in the previous sections of this paper. Figure 1 The first precursor described). Figure 2The deposition cycle shown can be repeated a desired number of times to at least partially form a sealing material with the desired thickness. Different actions (e.g., first action, second action, third action, fourth action) of the deposition cycle of the ALD process can be implemented using spatial and / or time-sharing methods (e.g., using a spatial ALD process and associated spatial ALD equipment, using a time-sharing ALD process and associated time-sharing ALD equipment), as described in further detail below.

[0039] In some embodiments, Figure 2 The deposition cycle shown in the diagram is performed one or more times to begin (e.g., initiate) the formation of the sealing material, and then employs a process with... Figure 2 The different characteristics of the deposition cycles shown (e.g., using different material exposure sequences and / or different precursors) are illustrated in the diagram, with one or more additional deposition cycles to continue and complete the formation of the sealing material. For example, one could use... Figure 2 The deposition cycle shown is used to form a seed layer of sealing material on an additional material (e.g., a chalcogenide material), and the seed layer can then be used to form an additional amount of sealing material (e.g., increasing the thickness of the sealing material) on top of the additional material using additional deposition cycles. Due to the advantageous properties of the first precursor P1 (e.g., adhesion coefficient, reactivity), compared to conventional methods of forming sealing materials using the ALD process, Figure 2 The deposition cycle illustrated, at least the first action (including treatment with a first precursor P1), can accelerate the formation of the sealing material to the desired thickness. In some embodiments, the first action of the deposition cycle facilitates the formation of more than 0.5 angstroms per deposition cycle. (For example, greater than or equal to) Greater than or equal to The sealing material. In contrast, a conventional deposition cycle of a conventional ALD process that does not include a first action (e.g., does not include a treatment using the first precursor P1) may only promote the formation of less than or equal to the sealing material in each deposition cycle. The corresponding sealing material.

[0040] In an additional embodiment, a method with... Figure 2The ALD process, which demonstrates different material exposure sequences but still includes at least one deposition cycle containing a first action of treatment using a first precursor P1, is used to at least partially form the sealing material of this disclosure. As a non-limiting example, a deposition cycle according to an additional embodiment of this disclosure may include: a first action comprising treatment using the first precursor P1; a second action, which begins after the completion of the first action and includes treatment using a third precursor P3; a third action, which begins after the completion of the second action and includes treatment using a second precursor P2; and a fourth action, which begins after the completion of the third action and includes treatment using another material X. As an additional non-limiting example, a deposition cycle according to an additional embodiment of this disclosure may include multiple (e.g., more than one) sub-cycles comprising a first action of treatment using the first precursor P1 and a second action of treatment using the second precursor P2, preceding the third action of treatment using the third precursor P3. An initial first action may include a first process using a first precursor P1. An initial second action, including a first process using a second precursor P2, may be performed after the initial first action. Another first action, including a second process using the first precursor P1, may be performed after the initial second action. Another second action, including a second process using the second precursor P2, may be performed after completing the other first action. And at least a third action, including a process using a third precursor P3, may be performed after completing the other second action. As a further non-limiting example, a deposition cycle according to a further embodiment of this disclosure may include a first action involving processing using the first precursor P1, followed by a second action involving simultaneous (e.g., parallel) processing using the second precursor P2 and the third precursor P3.

[0041] When using a method that includes applying a first precursor (e.g., a previous reference), Figure 1 At least one deposition cycle (e.g., the first precursor described) is processed. Figure 2 After the deposition cycle shown in the diagram forms at least one seed layer of the sealing material, the ALD process may optionally employ one or more additional deposition cycles that do not include an action involving treatment with the first precursor (e.g., the first action). For example, using the previously referenced... Figure 2 After the described deposition cycle forms at least a seed layer of the sealing material, the ALD process may include at least one additional deposition cycle in which a first action involving treatment with a first precursor P1 is omitted. Instead, the first action of this additional deposition cycle may involve treatment with a second precursor P2 (or a third precursor P3), and the second action of this additional deposition cycle may involve treatment with a third precursor P3 (or, if the third precursor P3 is used in the first action, the second precursor P2).

[0042] As previously discussed, according to embodiments of this disclosure, the ALD-based formation of the sealing material can be implemented using a spatial ALD process and associated spatial ALD equipment, or using a time-sharing ALD process and associated time-sharing ALD equipment. References below... Figure 3A and 3B The present disclosure provides a space ALD system that includes a space ALD device that facilitates the formation of sealing material through the space ALD process. Reference is made below. Figure 4 The present disclosure provides a time-sharing ALD system that includes a time-sharing ALD device that facilitates the formation of sealing material through a time-sharing ALD process.

[0043] Figure 3A This is a simplified schematic diagram of a spatial ALD system 100 according to an embodiment of the present disclosure. The spatial ALD system 100 can be used to form microelectronic devices incorporating the sealing materials of the present disclosure through a spatial ALD process, as described in further detail below. Figure 3A As shown, a space ALD system 100 may include a first precursor source 102, a second precursor source 104, a third precursor source 106, and at least one space ALD device 108. The space ALD device 108 may be selectively (e.g., controlled by an operator or system) fluidly communicated with each of the first precursor source 102, the second precursor source 104, and the third precursor source 106. The space ALD system 100 may further include additional devices operatively associated with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and the space ALD device 108, as described in further detail below.

[0044] The first precursor source 102 includes components configured and operable to contain (e.g., store) and / or generate the previously described first precursor (e.g., previously referenced) Figure 1 At least one device (e.g., a containment container) for the described hydrazine compound. The first precursor may be contained in one or more of the following states: gaseous, liquid, and flowable solid. In some embodiments, the first precursor source 102 is configured and operated to contain the liquid first precursor.

[0045] The spatial ALD system 100 may include a single (i.e., only one) first precursor source 102, or may include multiple (i.e., more than one) first precursor sources 102. If the spatial ALD system 100 includes multiple first precursor sources 102, then the first precursor sources 102 may be substantially similar to each other (e.g., may exhibit substantially similar components, component sizes, component shapes, component material compositions, component material distributions, component locations, component orientations) and may operate under substantially similar conditions (e.g., substantially similar temperatures, pressures, flow rates), or at least one of the first precursor sources 102 may be different from at least another of the first precursor sources 102 (e.g., exhibiting different components, different component sizes, different component shapes, different component material compositions, different component material distributions, different component locations, different component orientations) and / or may operate under conditions different from at least another of the first precursor sources 102 (e.g., different temperatures, different pressures, different flow rates, etc.). For example, a spatial ALD system 100 may include at least two (2) first precursor sources 102, wherein one of the first precursor sources 102 is configured to contain a first precursor, and the other of the first precursor source 102 is configured to contain another different first precursor. In some embodiments, two or more first precursor sources 102 are arranged in parallel with each other within the spatial ALD system 100. In additional embodiments, two or more first precursor sources 102 are arranged in series with each other within the spatial ALD system 100.

[0046] The second precursor source 104 includes at least one device (e.g., a containment container) configured and operated to contain (e.g., store) and / or generate material for forming the second precursor (e.g., a silicon-centered radical) previously described herein. By non-limiting example, the second precursor source 104 may be configured and operated to contain one or more silicon-containing compounds, such as SiH4, Si2H6, silicon tetrahalides (e.g., SiI4), disilicide hexahalides (e.g., (SiCl3)2), H9NSi3, and hydrohalosilanes (e.g., H2I2Si). The material for forming the second precursor may be contained within the second precursor source 104 in one or more gaseous, liquid, and flowable solid states. In some embodiments, the second precursor source 104 is configured and operated to contain material for forming a liquid second precursor.

[0047] The spatial ALD system 100 may include a single (i.e., only one) second precursor source 104, or may include multiple (i.e., more than one) second precursor sources 104. If the spatial ALD system 100 includes multiple second precursor sources 104, then the second precursor sources 104 may be substantially similar to each other and may operate under substantially similar conditions, or at least one of the second precursor sources 104 may be different from at least one other of the second precursor sources 104 and / or may operate under conditions different from at least one other of the second precursor sources 104. For example, the spatial ALD system 100 may include at least two (2) second precursor sources 104, wherein one of the second precursor sources 104 is configured to contain a material for forming a second precursor, and the other of the second precursor sources 104 is configured to contain another different material for forming another different second precursor. In some embodiments, two or more second precursor sources 104 are arranged in parallel with each other within the spatial ALD system 100. In an additional embodiment, two or more second precursor sources 104 are arranged in series within the spatial ALD system 100.

[0048] The third precursor source 106 includes at least one device (e.g., a containment container) configured and operated to contain (e.g., store) and / or generate material for forming the third precursor (e.g., a nitrogen-centered radical) previously described herein. By non-limiting example, the third precursor source 106 may be configured and operated to contain one or more nitrogen-containing molecules, such as N2 and NH3. The material for forming the third precursor may be contained within the third precursor source 106 in one or more of a gaseous, liquid, and flowable solid state. In some embodiments, the third precursor source 106 is configured and operated to contain material for forming a gaseous third precursor.

[0049] The spatial ALD system 100 may include a single (i.e., only one) third precursor source 106, or may include multiple (i.e., more than one) third precursor sources 106. If the spatial ALD system 100 includes multiple third precursor sources 106, then the third precursor sources 106 may be substantially similar to each other and may operate under substantially similar conditions, or at least one of the third precursor sources 106 may be different from at least one other of the third precursor sources 106 and / or may operate under conditions different from at least one other of the third precursor sources 106. For example, the spatial ALD system 100 may include at least two (2) third precursor sources 106, wherein one of the third precursor sources 106 is configured to contain a material for forming a third precursor, and the other of the third precursor sources 106 is configured to contain another different material for forming another different third precursor. In some embodiments, two or more third precursor sources 106 are arranged in parallel with each other within the spatial ALD system 100. In an additional embodiment, two or more third precursor sources 106 are arranged in series within the spatial ALD system 100.

[0050] Still referencing Figure 3A The space ALD system 100 may also include at least one other material source 110 that is selectively (e.g., controlled by an operator or system) in fluid communication with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and the space ALD device 108 (e.g., each). The other material source 110 includes at least one device (e.g., a confinement container) configured and operated to contain (e.g., store) and / or generate other materials (e.g., inert gases, nitrogen, nitrogen-containing plasma) previously described herein. By way of non-limiting example, the other material source 110 may be configured and operated to contain one or more of inert gases, such as He, Ne, and Ar. Inert gases may, for example, be used as carrier gases within the space ALD system 100 (e.g., for a first precursor within a first precursor source 102, for materials within a second precursor source 104), and / or to generate desired radicals within the space ALD system 100 (e.g., generating one or more Si-centered radicals from materials within the second precursor source 104, acting as a second precursor; generating one or more N-centered radicals from materials within the third precursor source 106, acting as a third precursor). Other material sources 110 may, for example, be used to generate plasma (e.g., remotely from the space ALD device 108, directly within the space ALD device 108), which may at least be used to form the second and third precursors previously described herein from materials respectively housed within the second precursor source 104 and the third precursor source 106.

[0051] The space ALD system 100 may optionally further include one or more heating devices operatively associated with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and the additional material source 110 (e.g., one or more of the following: at least one heat exchanger, such as a shell-and-tube heat exchanger; at least one combustion heater; at least one nuclear heater; at least one ultrasonic heater; at least one resistance heater; at least one inductive heater; at least one electromagnetic heater, such as an infrared heater and / or a microwave heater). By way of non-limiting examples, such as Figure 3A As shown, the spatial ALD system 100 may include a first heating device 112 operatively associated with a first precursor source 102 and a second heating device 114 operatively associated with a second precursor source 104. The first heating device 112 may be used to heat or maintain the first precursor at a desired temperature within the first precursor source 102, such as a temperature that promotes the flowability of the first precursor. The second heating device 114 may be used to heat or maintain the material used to form the second precursor at a desired temperature within the second precursor source 104, such as a temperature that promotes the flowability of the material used to form the second precursor.

[0052] Still referencing Figure 3A The space ALD system 100 may optionally further include one or more vaporization devices (e.g., one or more glass tubes) operatively associated with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and other material sources 110. By way of non-limiting example, if the first precursor source 102 and the second precursor source 104 are configured and operated to contain liquid material (e.g., the first precursor, the material to be used to form the second precursor) held therein, then the space ALD system 100 may include a first vaporization device 116 downstream of the first precursor source 102 and a second vaporization device 118 downstream of the second precursor source 104. The first vaporization device 116 may be configured and operated to receive a first fluid flow containing the first precursor in liquid form from the first precursor source 102 and vaporize the first precursor in liquid form to form the first precursor in gaseous form, which may then be directed toward the space ALD device 108. The second vaporization device 118 may be configured and operated to receive a second fluid flow from the second precursor source 104 containing a material in liquid form to be used to form the second precursor, and to vaporize the liquid material to form a gaseous material, which may then be directed toward the space ALD device 108.

[0053] Optionally, the space ALD system 100 may further include one or more radical generating devices (e.g., remote plasma sources, laser energy sources, microwave energy sources) operatively associated with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and other material sources 110. By a non-limiting example, the space ALD system 100 may include a first radical generating device 120 downstream of the second precursor source 104 (and a second vaporization device 118 if present) and a second radical generating device 122 downstream of the third precursor source 106. In some embodiments, one or more of the first radical generating device 120 and the second radical generating device 122 are also downstream of other material sources 110. The first radical generating device 120 may be configured and operated to receive a material in gaseous form (e.g., a Si-containing compound) contained in the second precursor source 104 (e.g., from the second vaporization device 118) and generate a second precursor (e.g., a Si-centered radical) previously described herein. Next, the second precursor can be directed toward the space ALD device 108. The second radical generating device 122 can be configured and operated to receive a material in gaseous form (e.g., containing N molecules) contained in the third precursor source 106 and generate the third precursor (e.g., an N-centered radical) previously described herein. The third precursor can then be directed toward the space ALD device 108. In additional embodiments (e.g., embodiments where one or more of the second and third precursors (e.g., each) are formed within the space ALD device 108 (e.g., relative to those distant from the space ALD device 108), one or more of the first radical generating device 120 and the second radical generating device 122 are omitted (e.g., missing) from the space ALD system 100.

[0054] like Figure 3A As shown, the space ALD system 100 may further include various valves 124 operatively associated with one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, and other material sources 110. Some valves 124 may, for example, be configured and positioned to selectively (e.g., under operator or system control) establish (and, as needed, terminate) fluid communication between the other material sources 110 and one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, the first radical generating device 120 (if any), the second radical generating device 122 (if any), and the space ALD device 108. For clarity and ease of understanding of the figures and associated descriptions, Figure 3AThe configuration and location of all potential valves (and therefore pipes) that may be used to selectively establish (and, if necessary, terminate) fluid communication between other material sources 110 and one or more of the first precursor source 102, the second precursor source 104, the third precursor source 106, the first free radical generating device 120 (if any), the second free radical generating device 122 (if any), and the spatial ALD device 108 are not depicted.

[0055] Continue to refer to Figure 3A The spatial ALD device 108 is located downstream of a first precursor source 102 (and a first vaporization device 116 (if any)), a second precursor source 104 (and a second vaporization device 118 (if any); a first radical generating device 120 (if any)), a third precursor source 106 (and a second radical generating device 122 (if any)), and other material sources 110. The spatial ALD device 108 includes a housing structure 126, and each of at least one dispensing assembly 128 (e.g., a dispensing manifold) and at least one substrate support 130 within the housing structure 126. The dispensing assembly 128 and the substrate support 130 may be spaced apart from each other within the housing structure 126 (e.g., separated, isolated). The spatial ALD device 108 may further include additional features (e.g., additional structures, additional devices), as described in further detail below.

[0056] The housing structure 126 of the space ALD device 108 exhibits: multiple inlets fluidly connected to and configured and positioned with respect to a first precursor source 102, a second precursor source 104, a third precursor source 106, and other material sources 110 to receive multiple gaseous feed (e.g., inflow) streams; and at least one outlet positioned to guide at least one discharge (e.g., outflow) fluid stream comprising reaction byproducts and unreacted materials from the space ALD device 108. The gaseous feed streams may, for example, comprise at least: a first gaseous feed stream containing a first precursor previously described herein (e.g., an hydrazine compound containing Si-N-Si bonds); a second gaseous feed stream containing a second precursor previously described herein (e.g., a Si-centered radical), and / or materials for forming the second precursor (e.g., Si-containing compounds); and a third gaseous feed stream containing a third precursor previously described herein (e.g., an N-centered radical), and / or materials for forming the third precursor (e.g., N-containing molecules). The housing structure 126 may at least partially define at least one internal chamber 132 of the spatial ALD device 108. The internal chamber 132 may surround and hold the dispensing assembly 128 and substrate support 130 of the spatial ALD device 108. The housing structure 126 may further include one or more sealable structures (e.g., covers, doors, windows) that facilitate access to the internal chamber 132 to allow insertion and removal of structures (e.g., substrates) into and from the internal chamber 132. By way of non-limiting examples, such as Figure 3AAs shown, the housing structure 126 may expose a sealable door 134. The housing structure 126 may be formed of and comprise any material (e.g., metal, alloy, glass, polymer, ceramic, composite, or combination thereof) compatible with the operating conditions of the space ALD device 108 (e.g., temperature, pressure, material exposure, generated electric field, generated magnetic field). In some embodiments, the housing structure 126 is formed of and comprises stainless steel.

[0057] The substrate support 130 is configured and positioned to support and temporarily hold at least one substrate 136. For example... Figure 3A As shown, a substrate support 130 may be mounted on at least one rod structure 138 operatively associated with a motor assembly 140. The rod structure 138 and the motor assembly 140 may, for example, be configured and operated to rotate the substrate support 130 (and thus the substrate 136 thereon) during use and operation. In some embodiments, the rod structure 138 and the motor assembly 140 may also adjust the position of the substrate support 130 (and thus the substrate 136 thereon) between a relatively low position (e.g., for loading and unloading the substrate 136) and a relatively high position (e.g., for handling the substrate 136). Optionally, the substrate support 130 may be electrically connected to at least one signal generator 142 of the space ALD system 100. The signal generator 142 may include at least one power source (e.g., a DC power source, an RF power source, an AC power source). The signal generator 142 may also include additional components, such as at least one waveform modulator having a circuitry configured to modulate the waveform, frequency, and amplitude of an output signal. In an additional embodiment, the signal generator 142 is omitted (e.g., missing) from the spatial ALD system 100.

[0058] The dispensing assembly 128 is configured and positioned to guide the material of the gaseous feed stream received by the space ALD device 108 into the internal chamber 132 of the space ALD device 108. For example... Figure 3AAs shown, the dispensing assembly 128 may include a plurality of ports 144 (e.g., vents) configured and positioned to introduce a gaseous feed stream of material into an internal chamber 132. For example, the dispensing assembly 128 may include: at least one first port 144A in fluid communication with a first precursor source 102 (and a first vaporization device 116 (if any)); at least one second port 144B in fluid communication with a second precursor source 104 (and a second vaporization device 118 (if any); and a first radical generating device 120 (if any)); at least one third port 144C in fluid communication with a third precursor source 106 (and a second radical generating device 122 (if any)); and at least one fourth port 144D in fluid communication with other material sources 110 (if any). Port 144 of the dispensing assembly 128 may individually have a cross-sectional shape for a desired portion (e.g., a wedge-shaped portion) of a substrate 136 held within the space ALD device 108 (e.g., on a substrate support 130) to facilitate material handling using a gaseous feed stream, as described below. Figure 3B Further detailed description.

[0059] Still referencing Figure 3A The spatial ALD device 108 further includes a plurality of separator structures 146 within its internal chamber 132. The separator structures 146 can divide (e.g., partition) the internal chamber 132 into a plurality of distinct processing zones 148 at least partially separated from each other by the separator structures 146. Each processing zone 148 can be horizontally demarcated by some of the separator structures 146 and can be operatively associated with at least one of the ports 144 of the dispensing assembly 128. The separator structures 146 can at least partially define the horizontal cross-sectional shape of the processing zone 148 thereby demarcated. Some of the separator structures 146 can be interposed between horizontally adjacent ports 144 of the dispensing assembly 128. The separator structures 146 can be used to effectively limit the material exiting the gaseous feed stream from the ports 144 of the dispensing assembly 128, applied during deposition cycles of the ALD process of this disclosure to process different portions (e.g., different wedge-shaped portions) of the substrate 136 held within the spatial ALD device 108, as referenced. Figure 3B Further detailed description.

[0060] like Figure 3AAs shown, in some embodiments, the partition structure 146 divides (e.g., partitions) the internal chamber 132 of the spatial ALD device 108 into at least one first processing area 148A, at least one second processing area 148B, at least one third processing area 148C, and at least one fourth processing area 148D. At least one first processing area 148A may be operatively associated with and may include at least one first port 144A of the dispensing assembly 128 in its horizontal region. At least one second processing area 148B may be operatively associated with and may include at least one second port 144B of the dispensing assembly 128 in its horizontal region. At least one third processing area 148C may be operatively associated with and may include at least one third port 144C of the dispensing assembly 128 in its horizontal region. At least one fourth processing area 148D may be operatively associated with and may include at least one fourth port 144D of the dispensing assembly 128 in its horizontal region.

[0061] A separator structure 146 within the internal chamber 132 of the spatial ALD device 108 may be vertically positioned above the substrate support 130 of the spatial ALD device 108. Additionally, the separator structure 146 may be configured and positioned to vertically cover and offset from the substrate 136 held on the substrate support 130 during use and operation of the spatial ALD device 108. In some embodiments, the separator structure 146 is an integrated feature of the dispensing assembly 128 of the spatial ALD device 108. In additional embodiments, the separator structure 146 is separate from the dispensing assembly 128 of the spatial ALD device 108 (e.g., not integrated with and continuous with it).

[0062] In some embodiments, instead of or in conjunction with the separator structure 146, one or more air curtains are used to divide (e.g., partition) the internal chamber 132 of the spatial ALD device 108 into multiple processing zones (e.g., first processing zone 148A, second processing zone 148B, third processing zone 148C, fourth processing zone 148D). If used, the air curtain may comprise a gaseous material (e.g., inert gas, N2 gas) flowing in the internal chamber 132 in a desired pattern to divide the internal chamber 132 into different processing zones, or supplement (e.g., enhance) the division of the internal chamber 132 provided by the separator structure 146.

[0063] Still referencing Figure 3AIn some embodiments, one or more portions of the dispensing assembly 128 and / or the separator structure 146 are configured to generate a glow discharge when a voltage is applied thereto. The glow discharge can be used to generate plasma from one or more materials guided into the gaseous feed stream of the space ALD device 108. One or more portions of the dispensing assembly 128 and / or the separator structure 146 may, for example, act as electrodes of the space ALD device 108. Figure 3A As shown, one or more portions of the distribution assembly 128 and / or separator structure 146 may be electrically connected to at least one additional signal generator 150 of the space ALD system 100. The additional signal generator 150 may include at least one power supply (e.g., a variable DC power supply, a variable RF power supply). The additional signal generator 150 may also include additional components, such as at least one waveform modulator having a circuitry configured to modulate the waveform, frequency, and amplitude of the output signal. In an additional embodiment, the additional signal generator 150 is omitted (e.g., missing) from the space ALD system 100.

[0064] Figure 3B Demonstrates the use and operation of the space ALD system 100 according to embodiments of the present disclosure. Figure 3A A simplified schematic diagram of the internal chamber 132 of the space ALD device 108 of the space ALD system 100 shown in the image. Figure 3B As shown, within the internal chamber 132, the partition structure 146 can be configured and positioned to provide a wedge-shaped horizontal cross-sectional shape for the individual processing areas 148 of the internal chamber 132. For example, the partition structure 146 can divide the internal chamber 132 into eight (8) different processing areas 148 (e.g., two (2) first processing areas 148A, two (2) second processing areas 148B, two (2) third processing areas 148C, and two (2) fourth processing areas 148D), each exhibiting a wedge-shaped horizontal cross-sectional shape. Additionally, the distribution assembly 128 ( Figure 3A The ports 144 (e.g., first port 144A, second port 144B, third port 144C, and fourth port 144D) of the internal chamber 132 may each exhibit a horizontal cross-sectional shape complementary to the horizontal cross-sectional shape of the processing area 148. For example, the first port 144A, second port 144B, third port 144C, and fourth port 144D may each exhibit a wedge-shaped horizontal cross-sectional shape. In an additional embodiment, one or more of the processing areas 148 of the internal chamber 132 and / or the distribution assembly 128 ( Figure 3A One or more of ports 144 may exhibit different characteristics than those in other ports. Figure 3B The horizontal cross-sectional shape depicted (e.g., a non-wedge-shaped horizontal cross-sectional shape).

[0065] During the use and operation of the space ALD device 108, the substrate support 130 ( Figure 3A It can be rotated along direction D1 (e.g., counterclockwise) so that it is held in place by the substrate support 130. Figure 3A Individual portions of the substrate 136 on the substrate travel through different processing regions (e.g., first processing region 148A, second processing region 148B, third processing region 148C, and fourth processing region 148D) within the internal chamber 132 of the spatial ALD device 108 to facilitate previous references herein. Figure 2 The material deposition sequence is described. For example, for an individual deposition cycle in the spatial ALD process of this disclosure, a given portion of substrate 136 may be treated with a first precursor P1 in one of the first processing regions 148A. Subsequently, substrate support 130 may be rotated along direction D1 to position the portion of substrate 136 in one of the second processing regions 148B adjacent to one of the first processing regions 148A, wherein the portion may be treated with a second precursor P2. Next, substrate support 130 may again be rotated along direction D1 to position the portion of substrate 136 in one of the third processing regions 148C adjacent to one of the second processing regions 148B, wherein the portion may be treated with a third precursor P3. Next, substrate support 130 may again be rotated along direction D1 to position the portion of substrate 136 in one of the fourth processing regions 148D adjacent to one of the third processing regions 148C, wherein the portion may be treated with another material X (if any) to complete one deposition cycle of the spatial ALD process of this disclosure. During the space ALD process, the first precursor P1, the second precursor P2, the third precursor P3, and other materials X (if any) can flow substantially continuously, such that different portions of the substrate are processed substantially simultaneously with each other, but using different precursors or additional materials (if any). For example, while one portion of substrate 136 is being processed in one of the second processing regions 148B using the second precursor P2 (e.g., after a portion of the first processing region 148A has been processed using the first precursor P1), another portion of substrate 136 is being processed in one of the first processing regions 148A using the first precursor P1. Thus, different portions of substrate 136 can be in a previously referenced state during the use and operation of the space ALD device 108. Figure 2 (As a non-limiting example) describes the different stages of a depositional cycle. Previous references Figure 2 The described deposition cycle can be repeated a desired number of times for each portion of substrate 136 to form the sealing material of this disclosure. Furthermore, non-limiting details of the space ALD process of this disclosure facilitated by the space ALD system 100 are provided below.

[0066] Within each first processing zone 148A of the internal chamber 132 of the spatial ALD device 108, a first precursor P1 (e.g., an hydrazine compound containing Si-N-Si bonds, such as those previously referenced herein) may be used. Figure 1 The compound described is treated and held in place on a substrate support 130. Figure 3A The first precursor P1 is a portion of the substrate 136 on the substrate 136, and the first precursor P1 can react with uncoordinated sites at the surface of the substrate 136 to adsorb the first precursor P1 onto the surface of the substrate 136. The surface of the substrate 136 may include the surface of a material (e.g., a chalcogenide material) formed independently of the spatial ALD process used to form the sealing material of the present disclosure, or may include a temporary surface of the sealing material formed by an earlier deposition cycle of the spatial ALD process.

[0067] Within each second processing region 148B of the internal chamber 132 of the spatial ALD device 108, a portion of the substrate 136 on which the first precursor is adsorbed can be treated with a second precursor P2 (e.g., a Si central radical), and the second precursor P2 can react with the adsorbed first precursor to form a secondary intermediate material containing Si. The secondary intermediate material can then be treated with at least a third precursor P3, as described in further detail below.

[0068] In some embodiments, the second precursor P2 is formed as a second processing region 148B of the internal cavity 132 of the spatial ALD device 108 (e.g., in the first free radical generation device 120). Figure 3A (inside) (e.g., formed on its exterior), and via the distribution assembly 128 of the spatial ALD device 108 ( Figure 3A At least one of the second ports 144B is introduced (e.g., guided, delivered) into the second processing area 148B. In an additional embodiment, at least some of the second precursors P2 are introduced (e.g., guided, delivered) into the second processing area 148B via the distribution assembly 128. Figure 3A At least one of the second ports 144B is introduced into the second processing region 148B, where at least one Si-containing compound is directly formed within (e.g., formed therein) the internal chamber 132 of the space ALD device 108. For example, one or more of the signal generators (e.g., one or more of signal generator 142 and additional signal generator 150) can apply voltage to one or more components of the space ALD device 108 to generate plasma within at least the second processing region 148B from materials (e.g., inert gas), and the plasma can interact with and excite the Si-containing compound to form a second precursor P2.

[0069] Still referencing Figure 3BWithin each third processing zone 148C of the internal chamber 132 of the spatial ALD device 108, a portion of a substrate 136 having a secondary intermediate material thereon may be treated with a third precursor P3 (e.g., an N-centered free radical), and the third precursor P3 may react with the secondary intermediate material to form at least partially an N-containing sealing material from the third precursor P3. Optionally, the sealing material may subsequently be treated with other materials X, as described in further detail below.

[0070] In some embodiments, the third precursor P3 is formed as a third processing region 148C of the internal cavity 132 of the spatial ALD device 108 (e.g., in the first free radical generation device 120). Figure 3A (inside) (e.g., formed on its exterior), and via the distribution assembly 128 of the spatial ALD device 108 ( Figure 3A At least one of the third ports 144C is introduced into the third processing area 148C. In an additional embodiment, at least some of the third precursors P3 are introduced into the third processing area 148C by means of the distribution assembly 128. Figure 3A At least one of the third ports 144C is introduced into the third processing region 148C, where at least one N-containing molecule is directly formed within (e.g., formed inside) the third processing region 148C. For example, one or more of the signal generators (e.g., one or more of signal generator 142 and additional signal generator 150) can apply voltage to one or more components of the spatial ALD device 108 to generate plasma within at least the third processing region 148C from materials within the third processing region 148C (e.g., inert gas, Ni-containing molecules), and the plasma can interact with and excite the N-containing molecules to form a third precursor P3.

[0071] If the generated plasma is used to form a third precursor P3 within the third processing region 148C of the internal chamber 132 of the space ALD device 108, then a relatively high frequency can be used to drive the plasma, for example, a frequency greater than or equal to about 20 MHz (e.g., in the range from about 20 MHz to about 2.45 GHz (e.g., from about 27 MHz to about 2.45 GHz, or from about 60 MHz to about 2.45 GHz)). Such a relatively high frequency can limit the ion energy function (IEDF) and promote radical reactions.

[0072] Additionally, if the generated plasma is used to form a third precursor P3 within the third processing region 148C of the internal chamber 132 of the space ALD device 108, the continuity (or discontinuity) of the bias applied to a given component of the space ALD device 108 within a given time period can also be used to control the properties of the sealing material formed on or above the substrate 136. Pulsed signals (e.g., pulsed RF (PRF) signals, pulsed DC (PDC) signals) can be used to bias different components of the space ALD device 108, and / or non-pulsed signals (e.g., continuous signals, such as continuous RF signals, continuous DC signals) can be used to bias different components of the space ALD device 108. In some embodiments, pulsed signals comprising current bursts (e.g., RF current, DC) are used to bias one or more components of the space ALD device 108. Pulsing the applied current can, for example, facilitate heat dissipation during silent periods. If a pulsed signal is used, the duration of the applied bias waveform (t1 / T1, where t1 is the pulse width and T1 is the frequency of the pulsed or modulated signal) can be controlled to promote desired characteristics in the sealing material formed on or above the substrate 136. For example, increasing the duration of the bias waveform applied to the substrate support 130 can reduce (or even eliminate) unwanted impurities and / or void spaces within the sealing material (e.g., caused by at least some impurities after annealing).

[0073] Furthermore, if the generated plasma is used to form a third precursor P3 within the third processing zone 148C of the internal chamber 132 of the space ALD device 108, one or more ion filter structures may be included in the third processing zone 148C to at least partially separate the formed ions (e.g., formed nitrogen ions, other formed ions) from the third precursor P3 (e.g., N-centered radicals). The third precursor P3 may continue to move toward and interact with the secondary intermediate material (e.g., react), while preventing at least some ions from continuing to move toward and interact with the secondary intermediate material. Therefore, the ion filter structures reduce the exposure of the secondary intermediate material to ions formed in the third processing zone 148C relative to the third precursor P3 formed in the third processing zone 148C.

[0074] Still referencing Figure 3BOptionally, within each fourth processing zone 148D of the internal chamber 132 of the spatial ALD device 108, a portion of the substrate 136 having a sealing material thereon may be treated with an additional material X. In some embodiments, the additional material X is used as a flushing material to remove unwanted materials (e.g., reaction byproducts, residual precursors) from the internal chamber 132 of the spatial ALD device 108. As a non-limiting example, the additional material X may include N2 gas and / or an inert gas. In additional embodiments, the additional material X is used to further process the sealing material to modify one or more of its properties (e.g., physical properties). As a non-limiting example, the additional material X may include plasma (e.g., N-containing plasma). In such embodiments, if the additional material X includes plasma, then the plasma may be formed away from the fourth processing zone 148D (e.g., formed outside it) or may be formed directly within the fourth processing zone 148D (e.g., formed inside it).

[0075] In some embodiments, due to the use of at least a first precursor in the spatial ALD process of this disclosure (e.g., an hydrazine compound containing Si-N-Si bonds, such as those previously referenced herein), Figure 1 The operating temperature of the spatial ALD device 108 during the formation of the sealing material described herein (of the compound) may be less than or equal to about 550°C, for example, in the range from about 200°C to about 550°C. The operating temperature of the spatial ALD device 108 may be significantly lower than the operating temperatures required by many conventional ALD devices and conventional ALD processes used to form sealing materials on or over a substrate.

[0076] Although this article has referenced Figure 3B Description of the use and operation space of ALD system 100 ( Figure 3A (Including the use and operation of its space ALD device 108) to implement Figure 2 The material deposition sequence of the deposition cycle described herein is not limited thereto. Rather, the space ALD system 100 (including its space ALD device 108) is operable to implement different material deposition sequences of different deposition cycles (e.g., different sequences of first precursor P1, second precursor P2, third precursor P3, and other materials X (if any)), and may include, as needed (but not limited to), other material deposition sequences of other potential deposition cycles previously described herein.

[0077] Figure 4 This is a simplified schematic diagram of a time-sharing ALD system 200 according to an embodiment of the present disclosure. The time-sharing ALD system 200 can be used to produce microelectronic device structures incorporating the sealing materials of the present disclosure through a time-sharing ALD process, as described in further detail below. Figure 4As shown, the time-sharing ALD system 200 may include a first precursor source 202, a second precursor source 204, a third precursor source 206, and at least one time-sharing ALD device 208. The time-sharing ALD device 208 may be selectively (under operator or system control) in fluid communication with each of the first precursor source 202, the second precursor source 204, and the third precursor source 206. The time-sharing ALD system 200 may further include additional devices operatively associated with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and the time-sharing ALD device 208, as described in further detail below.

[0078] The first precursor source 202, the second precursor source 204, and the third precursor source 206 can be substantially similar to the previously referenced sources. Figure 3A The first precursor source 102, the second precursor source 104, and the third precursor source 106 are described and may contain substantially the same material. Additionally, optionally, the time-sharing ALD system 200 may also include at least one other material source 210 in selective (e.g., controlled by an operator or system) fluid communication with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and the time-sharing ALD device 208. If present, the other material source 210 may be substantially similar to the previously referenced material. Figure 3A Other material sources 110 are described and may contain substantially the same materials.

[0079] The time-sharing ALD system 200 may optionally further include one or more heating devices operatively associated with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and other material sources 210. By way of non-limiting examples, such as Figure 4 As shown, the time-sharing ALD system 200 may include a first heating device 212 operatively associated with a first precursor source 202 and a second heating device 214 operatively associated with a second precursor source 204. The first heating device 212 may be used to heat or maintain the first precursor (e.g., an hydrazone compound containing Si-N-Si bonds) at a desired temperature within the first precursor source 202, such as a temperature that promotes the flowability of the first precursor. The second heating device 214 may be used to heat or maintain the material (e.g., a Si-containing compound) used to form the second precursor (e.g., a Si-centered radical) at a desired temperature within the second precursor source 204, such as a temperature that promotes the flowability of the material used to form the second precursor.

[0080] Still referencing Figure 4The time-sharing ALD system 200 may optionally further include one or more vaporization devices (e.g., one or more glass tubes) operatively associated with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and other material sources 210. By way of non-limiting example, if the first precursor source 202 and the second precursor source 204 are configured and operated to contain liquid material (e.g., the first precursor, the material to be used to form the second precursor) held therein, then the time-sharing ALD system 200 may include a first vaporization device 216 downstream of the first precursor source 202 and a second vaporization device 218 downstream of the second precursor source 204. The first vaporization device 216 may be configured and operated to receive a first fluid flow containing the first precursor in liquid form from the first precursor source 202 and vaporize the first precursor in liquid form to form the first precursor in gaseous form, which may then be directed toward the time-sharing ALD device 208. The second vaporization device 218 may be configured and operated to receive a second fluid flow from the second precursor source 204 containing a liquid material to be used to form the second precursor, and to vaporize the liquid material to form a gaseous material, which may then be directed toward the time-sharing ALD device 208. In an additional embodiment, the time-sharing ALD system 200 may include a single (e.g., only one) vaporization device in selective (e.g., controlled by an operator or system) fluid communication with each of the first precursor source 202 and the second precursor source 204. The single vaporization device may, for example, be configured and operated to vaporize material received from each of the first precursor source 202 and the second precursor source 204 (e.g., the first precursor in liquid form, the liquid material for forming the second precursor) at different times during the time-sharing ALD process of this disclosure.

[0081] Optionally, the time-sharing ALD system 200 may further include one or more radical generating devices (e.g., remote plasma sources, laser energy sources, microwave energy sources) operatively associated with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and other material sources 210. By way of non-limiting example, the time-sharing ALD system 200 may include a first radical generating device 220 downstream of the second precursor source 204 (and a second vaporization device 218 if present) and a second radical generating device 222 downstream of the third precursor source 206. In some embodiments, one or more of the first radical generating device 220 and the second radical generating device 222 are also downstream of other material sources 210. The first radical generating device 220 may be configured and operated to receive a material in gaseous form (e.g., a Si-containing compound) contained in the second precursor source 204 (e.g., from the second vaporization device 218) and generate a second precursor (e.g., a Si-centered radical) previously described herein. Next, the second precursor can be directed toward the time-sharing ALD device 208. The second radical generating device 222 can be configured and operated to receive a material in gaseous form (e.g., containing N molecules) contained in the third precursor source 206 and generate the third precursor (e.g., an N-centered radical) previously described herein. The third precursor can then be directed toward the time-sharing ALD device 208. In additional embodiments (e.g., embodiments where one or more of the second and third precursors (e.g., each) are formed within the time-sharing ALD device 208 (e.g., relative to a location remote from the time-sharing ALD device 208), one or more of the first radical generating device 220 and the second radical generating device 222 are omitted (e.g., missing) from the time-sharing ALD system 200.

[0082] like Figure 4 As shown, the time-sharing ALD system 200 may further include various valves 224 operatively associated with one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, and other material sources 210. Some valves 224 may, for example, be configured and positioned to selectively (e.g., under operator or system control) establish (and, as needed, terminate) fluid communication between the other material sources 210 and one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, the first radical generating device 220 (if any), the second radical generating device 222 (if any), and the time-sharing ALD device 208. For clarity and ease of understanding of the figures and associated descriptions, Figure 4The configuration and location of all potential valves (and therefore, pipes) that can be used to selectively establish (and, if necessary, terminate) fluid communication between other material sources 210 and one or more of the first precursor source 202, the second precursor source 204, the third precursor source 206, the first free radical generating device 220 (if any), the second free radical generating device 222 (if any), and the time-sharing ALD device 208 are not depicted.

[0083] Continue to refer to Figure 4 The time-sharing ALD device 208 is located downstream of a first precursor source 202 (and a first vaporization device 216 (if any)), a second precursor source 204 (and a second vaporization device 218 (if any); a first radical generating device 220 (if any)), a third precursor source 206 (and a second radical generating device 222 (if any)), and other material sources 210. The time-sharing ALD device 208 includes a housing structure 226, and each of at least one dispensing assembly 228 (e.g., a dispensing manifold) and at least one substrate support 230 within the housing structure 226. The dispensing assembly 228 and the substrate support 230 may be spaced apart from each other within the housing structure 226 (e.g., separated, isolated). The time-sharing ALD device 208 may further include additional features (e.g., additional structures, additional devices), as described in further detail below.

[0084] The housing structure 226 of the time-sharing ALD device 208 exhibits: multiple inlets fluidly connected to and configured and positioned with respect to a first precursor source 202, a second precursor source 204, a third precursor source 206, and other material sources 210 to receive multiple gaseous feed (e.g., inflow) streams; and at least one outlet positioned to guide at least one discharge (e.g., outflow) fluid stream comprising reaction byproducts and unreacted materials from the time-sharing ALD device 208. The gaseous feed streams may, for example, comprise at least: a first gaseous feed stream containing a first precursor previously described herein (e.g., an hydrazine compound containing Si-N-Si bonds); a second gaseous feed stream containing a second precursor previously described herein (e.g., a Si-centered radical), and / or materials for forming the second precursor (e.g., a Si-containing compound); and a third gaseous feed stream containing a third precursor previously described herein (e.g., an N-centered radical), and / or materials for forming the third precursor (e.g., N-containing molecules). The housing structure 226 may at least partially define at least one internal chamber 232 of the time-sharing ALD device 208. The internal chamber 232 may surround and hold the dispensing assembly 228 and substrate support 230 of the time-sharing ALD device 208. The housing structure 226 may further include one or more sealable structures (e.g., covers, doors, windows) that facilitate access to the internal chamber 232 to allow insertion and removal of structures (e.g., substrates) into and from the internal chamber 232. The housing structure 226 may be formed of and comprise any material (e.g., metals, alloys, glass, polymers, ceramics, composites, or combinations thereof) compatible with the operating conditions of the time-sharing ALD device 208 (e.g., temperature, pressure, material exposure, generated electric fields, generated magnetic fields). In some embodiments, the housing structure 226 is formed of and comprises stainless steel.

[0085] The substrate support 230 is configured and positioned to support and temporarily hold at least one substrate 236. For example... Figure 4As shown, a substrate support 230 can be mounted on at least one rod structure 238 operatively associated with a motor assembly 240. The rod structure 238 and the motor assembly 240 can, for example, be configured and operated to adjust the position of the substrate support 230 (and therefore the substrate 236 thereon) between a relatively low position (e.g., for loading and unloading the substrate 236) and a relatively high position (e.g., for handling the substrate 236). Optionally, the substrate support 230 can be electrically connected to at least one signal generator 242 of the time-sharing ALD system 200. The signal generator 242 may include at least one power supply (e.g., DC power, RF power, AC power). The signal generator 242 may also include additional components, such as at least one waveform modulator having a circuitry configured to modulate the waveform, frequency, and amplitude of the output signal. In an additional embodiment, the signal generator 242 is omitted (e.g., missing) from the time-sharing ALD system 200.

[0086] The dispensing assembly 228 is configured and positioned to guide the material of the gaseous feed stream received by the time-sharing ALD device 208 into the internal chamber 232 of the time-sharing ALD device 208. For example... Figure 4 As shown, the dispensing assembly 228 may include multiple ports 244 (e.g., vents) configured and positioned to introduce material from a gaseous feed stream into an internal chamber 232. Ports 244 may be in fluid communication with a first precursor source 202 (and a first vaporization device 216, if any), a second precursor source 204 (and a second vaporization device 218, if any; and a first radical generation device 220, if any), a third precursor source 206 (and a second radical generation device 222, if any)), and other material sources 210, if any. Ports 244 may introduce different materials from different gaseous feed streams into the internal chamber 232 at different times by controlling at least some valves 224 of the time-sharing ALD system 200. For example, as described further below, for each action of a given deposition cycle of a time-sharing ALD process employing the time-sharing ALD system 200 (e.g., previously referenced herein), Figure 2 The first, second, third, and fourth actions described herein involve one or more of the valves 224 upstream of the time-sharing ALD device 208 selectively opening (controlled by the operator or system), while one or more other valves 224 upstream of the time-sharing ALD device 208 are selectively closed. The valves 224 of the time-sharing ALD system 200 at least partially control the flow rate and duration of the different gaseous feed streams directed toward the time-sharing ALD device 208, and thus at least partially control the material deposition sequence of each deposition cycle employing the time-sharing ALD process of the time-sharing ALD system 200.

[0087] Still referencing Figure 4Optionally, the time-sharing ALD device 208 may further include at least one coil structure 252 positioned between a dispensing assembly 228 and a substrate support 230 within an internal chamber 232 of the time-sharing ALD device 208. The coil structure 252 may be configured and operated to assist in generating and / or maintaining plasma between the dispensing assembly 228 and the substrate 236. As described in further detail below, the coil structure 252 may be configured and operated to inductively couple energy into the plasma generated within the internal chamber 232 to induce an electromagnetic current in the plasma. The electromagnetic current can heat the plasma through ohmic heating to maintain the plasma in a stable state. Figure 4 As shown, if present, coil structure 252 may be electrically connected to at least one further signal generator 254 of the time-sharing ALD system 200. Further signal generator 254 may include at least one additional power supply (e.g., RF power supply, DC power supply). Further signal generator 254 may also include additional components, such as impedance matching networks. Coil structure 252 may act as the first winding of a transformer. In an additional embodiment, coil structure 252 is omitted (e.g., missing) from the time-sharing ALD device 208.

[0088] Continue to refer to Figure 4 The time-sharing ALD device 208 may optionally further include at least one heating device 256 operatively associated with its internal chamber 232. The heating device 256 (if present) may include at least one means (e.g., a radiation heater; a combustion heater; a nuclear heater; an ultrasonic heater; a resistance heater; an inductive heater; an electromagnetic heater, such as an infrared heater and / or a microwave heater) configured and operated to heat at least a portion of the internal chamber 232 during use and operation of the time-sharing ALD device 208. The heating device 256 may be used to heat or maintain one or more portions of the internal chamber 232 at a desired temperature, for example, to promote the temperature at which a sealing material is formed through the time-sharing ALD process of this disclosure. In some embodiments, the heating device 256 is configured and positioned to promote a temperature within the internal chamber 232 greater than or equal to about 200°C (e.g., in the range from about 200°C to about 550°C). In additional embodiments (such as some embodiments in which the material guided into the internal chamber 232 does not require additional heating to form the sealing material to be sealed by time-sharing ALD), the heating device 256 is omitted (e.g., missing) from the time-sharing ALD device 208.

[0089] Still referencing Figure 4Optionally, the time-sharing ALD system 200 may further include at least one vacuum device 258 (e.g., a negative pressure device) operatively associated with at least one outlet of the housing structure 226 of the time-sharing ALD device 208. If present, the vacuum device 258 may be configured and operated to assist in controlling the pressure within the internal chamber 232 of the time-sharing ALD device 208 and in removing reaction byproducts and / or unreacted materials (e.g., unreacted precursor materials, their unreacted derivatives, unreacted additional materials) from the internal chamber 232 of the time-sharing ALD device 208. The vacuum device 258 may be configured and operated to apply negative pressure to the internal chamber 232 of the time-sharing ALD device 208. In an additional embodiment, the vacuum device 258 is omitted (e.g., absent) from the time-sharing ALD system 200.

[0090] During the use and operation of the time-sharing ALD system 200, the substrate 236 may be delivered to the time-sharing ALD device 208. The substrate 236 may be provided to the internal chamber 232 of the time-sharing ALD device 208 by any desired means. In some embodiments, one or more conventional robotic devices (e.g., robotic arms, robots) are used to deliver the substrate 236 to the time-sharing ALD device 208.

[0091] After the substrate 236 is delivered into the time-division ALD apparatus 208, different gaseous feed streams can be sequentially introduced into the internal chamber 232 through port 244 to form the sealing material of this disclosure. The sequence of introducing different gaseous feed streams corresponds to the desired material deposition sequence of an individual deposition cycle in the time-division ALD process of this disclosure. In some embodiments, at least one individual deposition cycle follows the sequence previously referenced herein. Figure 2 The material deposition sequence is described. For example, in the first action of the deposition cycle, a first precursor P1 may be introduced into the internal chamber 232 through port 244. Subsequently, in the second action, the flow of the first precursor P1 into the internal chamber 232 may be stopped, and one or more of the second precursor P2 and the materials used to form the second precursor P2 may be introduced into the internal chamber 232 through port 244. Next, in the third action, the flow of the second precursor P2 into the internal chamber 232 may be stopped, and one or more of the third precursor P3 and the materials used to form the third precursor P3 may be introduced into the internal chamber 232 through port 244. Next, in the fourth action, the flow of the third precursor P3 into the internal chamber 232 may be stopped, and other materials X (if any) may be introduced into the internal chamber 232 through port 244 to complete one deposition cycle of the time-division ALD process of this disclosure. Previous Reference Figure 2 The described deposition cycle can be repeated a desired number of times to form the sealing material of this disclosure. Additional non-limiting details of the time-sharing ALD process of this disclosure facilitated by the time-sharing ALD system 200 are provided below.

[0092] In some embodiments, during the first action of the deposition cycle of the time-division ALD process of this disclosure, the first precursor P1 in gaseous form (e.g., an hydrazine compound containing Si-N-Si bonds, such as those previously referenced herein) Figure 1 The described compound flows through port 244 of dispensing assembly 228 into internal chamber 232 of time-sharing ALD device 208. The first precursor P1 may then react with uncoordinated sites at the surface of substrate 236 to adsorb (e.g., chemisorb) the first precursor P1 onto the surface of substrate 236. The surface of substrate 236 may include the surface of a material (e.g., a chalcogenide material) formed separately with the time-sharing ALD process for forming the sealing material of this disclosure, or may include a temporary surface of the sealing material formed by an earlier deposition cycle of the time-sharing ALD process.

[0093] Next, in the second action of the deposition cycle, the flow of the first precursor P1 in gaseous form can be stopped (e.g., via one or more of valves 224), and one or more of the second precursor P2 in gaseous form (e.g., a Si-centered radical) and the material used to form the second precursor P2 (e.g., a Si-containing compound) flow through port 244 of the dispensing assembly 228 into the internal chamber 232 of the time-sharing ALD device 208. Thereafter, the second precursor P2 can react with the adsorbed first precursor to form a Si-containing secondary intermediate material from the second precursor P2.

[0094] In some embodiments, the second precursor P2 is introduced (e.g., guided, delivered) into the internal chamber 232 of the time-sharing ALD device 208 via a port 244 of the dispensing assembly 228 of the time-sharing ALD device 208, located remotely from the internal chamber 232. In additional embodiments, at least some of the second precursor P2 are introduced into the internal chamber 232 via at least one of the ports 244 of the dispensing assembly 228, where at least one Si-containing compound is directly formed within (e.g., formed inside) the internal chamber 232 of the time-sharing ALD device 208. For example, one or more of the signal generators (e.g., one or more of signal generator 242, additional signal generator 250, and further signal generator 254) can apply voltage to one or more components of the time-sharing ALD device 208 to generate plasma within the internal chamber 232, and the plasma can interact with and excite the Si-containing compound to form the second precursor P2.

[0095] Next, in the third action of the deposition cycle, the flow of the gaseous second precursor P2 and one or more of the materials used to form the second precursor P2 can be stopped (e.g., via one or more of valves 224), and one or more of the gaseous third precursor P3 (e.g., N-centered radicals) and the materials used to form the third precursor P3 (e.g., N-containing molecules) flow through port 244 of the dispensing assembly 228 into the internal chamber 232 of the time-sharing ALD device 208. Thereafter, the third precursor P3 can react with secondary intermediate materials to form at least partially an N-containing sealing material from the third precursor P3.

[0096] In some embodiments, the third precursor P3 is introduced into the internal chamber 232 (e.g., formed outside) of the time-division ALD device 208 (e.g., formed within the first radical generation device 220) via a port 244 of the dispensing assembly 228 of the time-division ALD device 208. In an additional embodiment, at least some of the third precursor P3 are directly formed within the internal chamber 232 (e.g., formed inside) by at least one N-containing molecule introduced into the internal chamber 232 via the port 244 of the dispensing assembly 228. For example, one or more of the signal generators (e.g., one or more of signal generator 242, additional signal generator 250, and further signal generator 254) may apply voltage to one or more components of the time-division ALD device 208 to generate plasma within the internal chamber 232, and the plasma may interact with and excite the N-containing molecules to form the third precursor P3.

[0097] If the generated plasma is used to form a third precursor P3 within the internal chamber 232 of the time-division ALD device 208, then a relatively high frequency can be used to drive the plasma, for example, a frequency greater than or equal to about 20 MHz (e.g., in the range from about 20 MHz to about 2.45 GHz (e.g., from about 27 MHz to about 2.45 GHz, or from about 60 MHz to about 2.45 GHz)). Such a relatively high frequency can limit IEDF and promote radical reactions.

[0098] Additionally, if the generated plasma is used to form a third precursor P3 within the internal chamber 232 of the time-sharing ALD device 208, the continuity (or discontinuity) of the bias applied to a given component of the time-sharing ALD device 208 during a given time period can also be used to control the properties of the sealing material formed on or above the substrate 236. Pulsed signals (e.g., PRF signals, PDC signals) can be used to bias different components of the time-sharing ALD device 208, and / or non-pulsed signals (e.g., continuous signals, such as continuous RF signals, continuous DC signals) can be used to bias different components of the time-sharing ALD device 208. In some embodiments, a pulsed signal comprising current bursts (e.g., RF current, DC) is used to bias one or more components of the time-sharing ALD device 208. Pulsing the applied current can, for example, facilitate heat dissipation during no-signal periods. If a pulsed signal is used, the duration of the applied bias waveform (t1 / T1, where t1 is the pulse width and T1 is the frequency of the pulsed or modulated signal) can be controlled to promote desired characteristics in the sealing material formed on or above the substrate 236. For example, increasing the duration of the bias waveform applied to the substrate support 230 can reduce (or even eliminate) unwanted impurities and / or void spaces (e.g., generated by at least some impurities after annealing) within the sealing material.

[0099] Furthermore, if the generated plasma is used to form a third precursor P3 within the internal chamber 232 of the time-division ALD device 208, one or more ion filter structures may be included in the internal chamber 232 to at least partially separate the formed ions (e.g., nitrogen ions, other formed ions) from the third precursor P3 (e.g., N-centered radicals). The third precursor P3 may continue to move toward and interact with the secondary intermediate material (e.g., react), while preventing at least some ions from continuing to move toward and interact with the secondary intermediate material. Therefore, the ion filter structures reduce the exposure of the secondary intermediate material to ions formed within the internal chamber 232 compared to the third precursor P3 formed within the internal chamber 232.

[0100] Still referencing Figure 4In the fourth action of the deposition cycle, the flow of the gaseous third precursor P3 and one or more of the materials used to form the third precursor P3 can be stopped (e.g., via one or more of valves 224), and other materials X (if any) can flow through port 244 of the dispensing assembly 228 into the internal chamber 232 of the time-sharing ALD device 208. Thereafter, the sealing material formed on or above the substrate 236 can be treated with the other materials X. In some embodiments, the other materials X are used as a flushing material to remove unwanted materials (e.g., reaction byproducts, residual precursors) from the internal chamber 232 of the time-sharing ALD device 208. As a non-limiting example, the other materials X may include N2 gas and / or an inert gas. In additional embodiments, the sealing material is further treated with the other materials X to modify one or more of its properties (e.g., physical properties). As a non-limiting example, the other materials X may include plasma (e.g., N-containing plasma). In such embodiments, if the other material X comprises plasma, the plasma may be formed away from the internal chamber 232 (e.g., formed outside it) or may be formed directly within the internal chamber 232 (e.g., formed inside it).

[0101] In some embodiments, due to the use of at least a first precursor (e.g., an hydrazine compound containing Si-N-Si bonds, such as those previously referenced herein) in the time-division ALD process of this disclosure, Figure 1 The operating temperature of the time-sharing ALD device 208 during the formation of the sealing material described herein (of the compound) may be less than or equal to about 550°C, for example, in the range from about 200°C to about 550°C. The operating temperature of the time-sharing ALD device 208 may be significantly lower than the operating temperature required by many conventional ALD devices and conventional ALD processes used to form sealing materials on or over a substrate.

[0102] Although this article has referenced Figure 4 Describes the use and operation of the time-sharing ALD system 200 (including the use and operation of its time-sharing ALD devices 208) for implementation. Figure 2 The material deposition sequence of the deposition cycle described herein is not limited thereto. Rather, the time-sharing ALD system 200 (including its time-sharing ALD device 208) is operable to implement different material deposition sequences of different deposition cycles (e.g., different sequences of first precursor P1, second precursor P2, third precursor P3, and other materials X (if any)), and may include, as needed (but not limited to), other material deposition sequences of other potential deposition cycles previously described herein.

[0103] Therefore, according to embodiments of this disclosure, a method of forming a microelectronic device includes treating a substrate structure with a first precursor to adsorb the first precursor onto the surface of the substrate structure and form a first material. The first precursor includes an hydrazine compound comprising Si-N-Si bonds. The first material is treated with a second precursor to convert the first material into a second material. The second precursor includes a Si-centered radical. The second material is treated with a third precursor to convert the second material into a third material comprising Si and N. The third precursor includes an N-centered radical.

[0104] Furthermore, the ALD system according to embodiments of this disclosure includes a first source, a second source, a third source, and an ALD device downstream of and in fluid communication with each of the first, second, and third sources. The first source is configured to contain a hydrazine compound comprising Si-N-Si bonds. The third source is configured to contain N-containing molecules. The ALD device includes a housing structure, a dispensing assembly, and a substrate support. The housing structure defines an internal chamber. The dispensing assembly is configured to receive and guide each of the gaseous hydrazine compound, the Si-containing compound, and the N-containing molecules into the internal chamber. The substrate support is located within the internal chamber and configured to hold a substrate structure thereon.

[0105] Furthermore, according to embodiments of this disclosure, a method for forming a sealing material via an ALD includes directing a first gas flow comprising a hydrazine compound containing Si-N-Si bonds into an internal chamber of an ALD device to chemically adsorb the hydrazine compound onto a substrate structure immobilized within the internal chamber. A second gas flow comprising one or more of a Si-containing compound and Si-central radicals is directed into the internal chamber to react with the chemically adsorbed hydrazine compound and form an intermediate material. A third gas flow comprising one or more of an N-containing compound and N-central radicals is directed into the internal chamber to react with the intermediate material and form at least a portion of the sealing material.

[0106] Compared to conventional material deposition systems (e.g., conventional ALD systems) and conventional methods (e.g., conventional ALD processes), the ALD system disclosed herein (e.g., space ALD system 100) offers advantages over conventional methods. Figure 3A ), Time-sharing ALD system 200 ( Figure 4 The methods (e.g., spatial ALD processes, time-division ALD processes) facilitate cost reduction (e.g., manufacturing costs, material costs), increase component miniaturization, improve performance, and increase packaging density. Compared to conventional material deposition systems and methods, the ALD systems and methods disclosed herein offer improved scalability, quality, efficiency, and simplicity.

[0107] Additional non-limiting exemplary embodiments of this disclosure include:

[0108] Example 1: A method for forming a microelectronic device, comprising: treating a substrate structure with a first precursor to adsorb the first precursor onto the surface of the substrate structure and form a first material, the first precursor comprising an hydrazine compound containing Si-N-Si bonds; treating the first material with a second precursor to convert the first material into a second material, the second precursor comprising a Si-centered free radical; and treating the second material with a third precursor to convert the second material into a third material comprising Si and N, the third precursor comprising an N-centered free radical.

[0109] Example 2: According to the method described in Example 1, the first precursor has the following structure:

[0110]

[0111] Each of the Rs is individually hydrogen, unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl.

[0112] Example 3: The method according to Example 2, wherein each R is a methyl group.

[0113] Example 4: The method according to any one of Examples 1 to 3 further includes performing each of the following in an ALD device via an atomic layer deposition (ALD) process: treating the substrate structure with the first precursor, treating the first material with the second precursor, and treating the second material with the third precursor.

[0114] Example 5: According to the method of Example 4, the treatment of the first material with the second precursor includes: forming the second precursor from a Si-containing compound in a free radical generation device upstream of the ALD device; and guiding the second precursor into the ALD device.

[0115] Example 6: According to the method of Example 4, the treatment of the first material with the second precursor includes: guiding a gaseous Si-containing compound into the ALD device; and forming the second precursor from the Si-containing compound within the ALD device.

[0116] Example 7: According to the method of Example 4, the treatment of the second material using the third precursor includes: forming the third precursor from an N-containing compound in a free radical generation device upstream of the ALD device; and guiding the third precursor into the ALD device.

[0117] Example 8: According to the method of Example 4, the treatment of the second material using the third precursor includes: guiding gaseous N-containing molecules into the ALD device; and forming the third precursor from the N-containing molecules within the ALD device.

[0118] Example 9: According to the method of Example 8, the formation of the third precursor from the N-containing molecules within the ALD device includes interacting the N-containing molecules with plasma generated within the ALD device to excite the N-containing molecules and thereby form the third precursor.

[0119] Example 10: The method according to Example 9 further includes driving the plasma at a frequency greater than or equal to about 20 MHz.

[0120] Example 11: The method according to Example 9 further includes separating the ions generated by the plasma from the third precursor before treating the second material with the third precursor.

[0121] Example 12: The method according to any one of Examples 4 to 11 further includes selecting the ALD device to include a spatial ALD device.

[0122] Example 13: The method according to any one of Examples 4 to 11 further includes selecting the ALD device to include a time-sharing ALD device.

[0123] Example 14: The method according to any one of Examples 4 to 11 further includes performing the ALD process at a temperature ranging from about 200°C to about 550°C.

[0124] Example 15: An atomic layer deposition (ALD) system comprising: a first source configured to contain an hydrazine compound comprising Si-N-Si bonds; a second source configured to contain a Si-containing compound; a third source configured to contain N-containing molecules; and an ALD device downstream of and in fluid communication with each of the first, second, and third sources, the ALD device comprising: a housing structure defining an internal chamber; a dispensing assembly configured to receive and direct each of the gaseous hydrazine compound, the Si-containing compound, and the N-containing molecules into the internal chamber; and a substrate support within the internal chamber and configured to hold a substrate structure thereon.

[0125] Example 16: The ALD system according to Example 15 further includes at least one vaporization device in fluid communication with the first source, the second source and the ALD device, the at least one vaporization device being configured to receive one or more of the hydrazine compound in liquid form and the Si-containing compound in liquid form, and to form one or more of the hydrazine compound in gaseous form and the Si-containing compound in gaseous form from the hydrazine compound in liquid form.

[0126] Example 17: An ALD system according to one of Examples 15 and 16, further comprising at least one radical generating device in fluid communication with the second source, the third source and the ALD device, the at least one radical generating device being configured to receive one or more of the Si-containing compound and the N-containing molecule and to form one or more of the Si-centered radicals from the Si-containing compound and the N-centered radicals from the N-containing molecule.

[0127] Example 18: An ALD system according to any of Examples 15 to 17, wherein the ALD device includes a spatial ALD device, the spatial ALD device further including a separator within the internal chamber and dividing the internal chamber into a plurality of processing zones comprising: a first processing zone configured to receive the hydrazine compound in gaseous form from a first port of the dispensing assembly; a second processing zone adjacent to the first processing zone and configured to receive one or more of the Si-containing compound and Si-centered radicals in gaseous form from a second port of the dispensing assembly; and a third processing zone adjacent to the second processing zone and configured to receive one or more of the N-containing molecules and N-centered radicals in gaseous form from a third port of the dispensing assembly.

[0128] Example 19: The ALD system according to Example 18, wherein the plurality of processing zones further includes a fourth processing zone adjacent to the third processing zone and configured therein to receive or generate plasma.

[0129] Example 20: An ALD system according to one of Examples 18 and 19, wherein: the dispensing assembly is configured to simultaneously receive one or more of the hydrazine compound, the Si-containing compound and the Si-centered radical, and one or more of the N-containing molecule and the N-centered radical; the dispensing assembly is configured to simultaneously guide the hydrazine compound into the first processing region through the first port, guide one or more of the Si-containing compound and the Si-centered radical into the second processing region through the second port, and guide one or more of the N-containing molecule and the N-centered radical into the third processing region through the third port; and the substrate support is configured to rotate through the first processing region, the second processing region, and the third processing region.

[0130] Example 21: An ALD system according to any of Examples 18 to 20, further comprising at least one signal generator electrically connected to the space ALD device and configured to generate plasma within at least the third processing zone to form the N-centered free radical from the N-containing molecules.

[0131] Example 22: The ALD system according to Example 15, wherein the ALD device includes a time-division ALD device configured to direct two or more of the gaseous form of the hydrazine compound, the Si-containing compound, and the N-containing molecule into the internal chamber at different times.

[0132] Example 23: The ALD system according to Example 22 further includes at least one signal generator electrically connected to the time-division ALD device and configured to generate plasma in the internal chamber.

[0133] Example 24: A method for forming a sealing material by atomic layer deposition (ALD), comprising: directing a first gas flow including a hydrazine compound containing Si-N-Si bonds into an internal chamber of an ALD device to chemisorb the hydrazine compound onto a substrate structure held within the internal chamber; directing a second gas flow including one or more of a Si-containing compound and Si-centered radicals into the internal chamber to react with the chemisorbed hydrazine compound and form an intermediate material; and directing a third gas flow including one or more of an N-containing compound and N-centered radicals into the internal chamber to react with the intermediate material and form at least a portion of the sealing material.

[0134] Example 25: The method according to Example 24, wherein the ALD device includes a spatial ALD device.

[0135] Example 26: The method according to Example 24, wherein the ALD device includes a time-sharing ALD device.

[0136] Example 27: The method according to any of Examples 24 to 26 further includes directing a fourth gas flow comprising one or more of N2 gas and N-containing plasma into the internal chamber to interact with the at least portion of the sealing material.

[0137] While this disclosure is readily presented in various modifications and alternatives, specific embodiments have been shown by way of example in the drawings and described in detail herein. However, this disclosure is not limited to the specific forms disclosed. Rather, this disclosure is intended to cover all modifications, equivalents, and alternatives falling within the scope of the appended claims and their legal equivalents. For example, elements and features disclosed with respect to one embodiment may be combined with elements and features disclosed with respect to other embodiments of this disclosure.

Claims

1. A method for forming a microelectronic device, comprising: A first precursor is used to treat a substrate structure to adsorb the first precursor onto the surface of the substrate structure and form a first material, wherein the first precursor comprises an hydrazine compound containing Si-N-Si bonds. The first material is processed using a second precursor to convert the first material into a second material, the second precursor comprising a Si-centered free radical; and The second material is treated with a third precursor to convert it into a third material comprising Si and N, the third precursor comprising an N-centered free radical.

2. The method according to claim 1, wherein the first precursor has the following structure: ， Each of the Rs is individually hydrogen, unsubstituted alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, or substituted heteroaryl.

3. The method of claim 2, wherein each R is a methyl group.

4. The method of claim 1, further comprising performing each of the following within an ALD apparatus via an atomic layer deposition (ALD) process: treating the substrate structure with the first precursor, treating the first material with the second precursor, and treating the second material with the third precursor.

5. The method of claim 4, wherein treating the first material with the second precursor comprises: The second precursor is formed from a Si-containing compound within a free radical generation device upstream of the ALD device; and The second precursor is guided into the ALD device.

6. The method of claim 4, wherein treating the first material with the second precursor comprises: The gaseous form of the Si-containing compound is directed into the ALD device; and The second precursor is formed from the Si-containing compound within the ALD device.

7. The method of claim 4, wherein treating the second material with the third precursor comprises: The third precursor is formed from an N-containing compound within a free radical generation device upstream of the ALD device; and The third precursor is guided into the ALD device.

8. The method of claim 4, wherein treating the second material with the third precursor comprises: Guide gaseous N-containing molecules into the ALD device; and The third precursor is formed from the N-containing molecules within the ALD device.

9. The method of claim 8, wherein forming the third precursor from the N-containing molecules within the ALD device comprises interacting the N-containing molecules with plasma generated within the ALD device to excite the N-containing molecules and thereby form the third precursor.

10. The method of claim 9, further comprising driving the plasma at a frequency greater than or equal to 20 MHz.

11. The method of claim 9, further comprising separating the ions generated by the plasma from the third precursor before treating the second material with the third precursor.

12. The method according to any one of claims 4 to 11, further comprising selecting the ALD device to include a spatial ALD device.

13. The method according to any one of claims 4 to 11, further comprising selecting the ALD device to include a time-sharing ALD device.

14. The method according to any one of claims 4 to 11, further comprising performing the atomic layer deposition (ALD) process at a temperature ranging from 200°C to 550°C.

15. An atomic layer deposition (ALD) system, comprising: The first source is configured to contain an hydrazine compound comprising Si-N-Si bonds; The second source is configured to contain Si-containing compounds; The third source is configured to contain N-containing molecules; and An ALD device, which is downstream of and in fluid communication with each of the first, second, and third sources, the ALD device comprising: The outer shell structure defines the internal chambers; A dispensing assembly configured to receive each of the gaseous hydrazine compound, the Si-containing compound, and the N-containing molecule and guide them into the internal chamber; and A substrate support frame is located within the internal cavity and configured thereon to hold the substrate structure.

16. The atomic layer deposition (ALD) system of claim 15, further comprising at least one vaporization device in fluid communication with the first source, the second source, and the ALD device, the at least one vaporization device being configured to receive one or more of the hydrazine compound in liquid form and the Si-containing compound in liquid form, and to form one or more of the hydrazine compound in gaseous form and the Si-containing compound in gaseous form from the hydrazine compound in liquid form.

17. The atomic layer deposition (ALD) system of claim 15, further comprising at least one radical generating device in fluid communication with the second source, the third source, and the ALD device, the at least one radical generating device being configured to receive one or more of the Si-containing compound and the N-containing molecule, and to form one or more of the Si-centered radicals from the Si-containing compound and the N-centered radicals from the N-containing molecule.

18. The atomic layer deposition (ALD) system according to any one of claims 15 to 17, wherein the ALD device comprises a spatial ALD device, the spatial ALD device further comprising a partition within the internal chamber and dividing the internal chamber into a plurality of processing zones comprising: A first processing zone is configured to receive the hydrazine compound in gaseous form from a first port of the dispensing assembly; A second processing zone, adjacent to the first processing zone and configured to receive one or more of the gaseous Si-containing compound and Si-central radicals from a second port of the dispensing assembly; and A third processing zone, adjacent to the second processing zone and configured to receive one or more of the gaseous N-containing molecules and N-centered free radicals from the third port of the dispensing assembly.

19. The atomic layer deposition (ALD) system of claim 18, wherein the plurality of processing regions further includes a fourth processing region adjacent to the third processing region and configured therein to receive or generate plasma.

20. The atomic layer deposition (ALD) system according to claim 18, wherein: The dispensing assembly is configured to simultaneously receive one or more of the hydrazine compound, the Si-containing compound and the Si-centered free radical, and one or more of the N-containing molecule and the N-centered free radical. The dispensing assembly is configured to simultaneously guide the hydrazine compound into the first processing region through the first port, guide one or more of the Si-containing compound and Si-centered radicals into the second processing region through the second port, and guide one or more of the N-containing molecule and N-centered radicals into the third processing region through the third port; and The substrate support is configured to rotate through the first processing area, the second processing area, and the third processing area.

21. The atomic layer deposition (ALD) system of claim 18, further comprising at least one signal generator electrically connected to the space ALD device and configured to generate plasma within at least the third processing zone to form the N-centered radical from the N-containing molecules.

22. The atomic layer deposition (ALD) system according to any one of claims 15 to 17, wherein the ALD device comprises a time-division ALD device configured to direct two or more of the gaseous form of the hydrazine compound, the Si-containing compound, and the N-containing molecule into the internal chamber at different times.

23. The atomic layer deposition (ALD) system of claim 22, further comprising at least one signal generator electrically connected to the time-division ALD device and configured to generate plasma within the internal chamber.

24. A method for forming a sealing material by atomic layer deposition (ALD), comprising: A first gas flow, comprising a diamine compound containing Si-N-Si bonds, is directed into the internal chamber of the ALD device to chemically adsorb the diamine compound onto a substrate structure immobilized within the internal chamber. A second gas flow, comprising one or more of a Si-containing compound and a Si-centered free radical, is directed into the internal chamber to react with the chemisorbed hydrazine compound and form an intermediate material; and A third gas flow, comprising one or more of N-containing compounds and N-centered free radicals, is directed into the internal chamber to react with the intermediate material and form at least a portion of the sealing material.

25. The method of claim 24, wherein the ALD device comprises a spatial ALD device.

26. The method of claim 24, wherein the ALD device comprises a time-sharing ALD device.

27. The method according to any one of claims 24 to 26, further comprising directing a fourth gas flow comprising one or more of N2 gas and N-containing plasma into the internal chamber to interact with said at least a portion of the sealing material.

Images