Germanium-doped charge trapping layers, related devices, related systems, and related methods

Abstract

The techniques of the present disclosure generally relate to the field of semiconductor devices. More specifically, the invention relates to a memory element including a charge trapping layer, and a system and method for manufacturing the same. A method for forming a charge trapping layer of a storage element, comprising the steps of: providing a substrate into a reaction chamber; performing one or more cycles, the cycles including the hafnium precursor pulses; optionally, a zirconium precursor pulse; an oxygen reactant pulse; a germanium dopant pulse; and wherein, as a result of the one or more cycles, a charge trapping layer comprising one or more germanium-doped hafnium oxide (HfO2) films and / or one or more germanium-doped hafnium zirconium oxide (HZO) films is formed on the substrate.

Description

Technical Field

[0001] The present disclosure generally relates to the field of semiconductor devices, and more particularly to a germanium-doped charge trapping layer of a storage element and a method and system for manufacturing the same. Background Art

[0002] Charge trapping layers included within memory elements are essential components for data storage and retrieval, but also present different challenges that affect device performance and reliability. These issues stem from a complex interaction of material properties, electrical characteristics, and operating conditions. Some of the issues associated with charge trapping layers include inherent manufacturing variations, gradual degradation during use, and charge leakage. In particular, the continued shrinking of semiconductor devices (such as memory elements) has increased the problem of charge leakage, where the trapped charge escapes the insulating layer over time. Inefficient charge capture and release has a significant impact on the write and erase efficiency of memory devices (such as flash memory). In addition, for tightly packed high-density memory arrays, crosstalk and interference effects can be observed due to the undesired charge transfer from the operating memory cell to the adjacent memory cell, resulting in erroneous data reading or data modification. Therefore, there is a need to improve the manufacturing of memory elements including charge trapping layers to avoid the above-mentioned problems, such as charge leakage, and to obtain consistent and reliable semiconductor devices. Summary of the invention

[0003] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0004] Generally speaking, the technology disclosed in this article relates to the field of semiconductor devices, and more specifically, to methods for forming charge retention or capture media for storage elements, which are used to produce several electronic components, such as non-volatile memory technology and memory chips including NAND flash drives and solid-state drives (SSDs).

[0005] One aspect of the present invention relates to a method for forming a charge trapping layer of a storage element, comprising the following steps:

[0006] a) providing a substrate into a reaction chamber;

[0007] b) Execute multiple loops, the loops include:

[0008] i. a hafnium precursor pulse, wherein at least a portion of the substrate is contacted with one or more hafnium precursors by introducing the one or more hafnium precursors into the reaction chamber;

[0009] ii. Optionally, a zirconium precursor pulse, wherein at least a portion of the substrate is contacted with one or more zirconium precursors by introducing one or more zirconium precursors into the reaction chamber;

[0010] iii. an oxygen reactant pulse, wherein at least a portion of the substrate is contacted with one or more oxygen reactants by introducing one or more oxygen reactants into the reaction chamber;

[0011] iv. a germanium dopant pulse, wherein at least a portion of the substrate is contacted with one or more germanium dopants by introducing one or more germanium dopants into the reaction chamber; and

[0012] Wherein, as a result of the plurality of cycles, a charge trapping layer including one or more germanium-doped hafnium zirconium oxide (HZO) films is formed on the substrate.

[0013] The method disclosed herein relates to a deposition process in which one or more layers of metal oxide films are grown by exposing the substrate surface to a series of alternating precursors, reactants and dopants. One or more doped metal oxide films can then be used to capture or store charge, which corresponds to stored data in an electronic device. Advantageously, the inventors have found that the methods and devices disclosed herein can allow the formation of a charge trapping film or layer with reduced layer thickness variation and defects, resulting in improved memory devices. In detail, the method disclosed herein operates by controlled deposition pulses of precursors, reactants and other ingredients to control the growth rate and composition of the formed metal oxide layer. In addition, a dopant pulse is one of the pulses, which can induce controlled doping of the formed metal oxide layer, resulting in good electrical properties while promoting stable and reliable memory element operation. Specifically, one advantage of the present invention is that even when the device size is significantly reduced, the charge leakage of the charge trapping layer is reduced, thereby enabling more reliable data storage.

[0014] In a particular embodiment, the methods disclosed herein provide that the method is an atomic layer deposition (ALD) method. It has been found that when it comes to thin film deposition, ALD provides multiple advantages over traditional sputtering techniques, such as precise layer thickness control, uniform deposition, and controlled film composition, allowing the formation of alloys and oxides with high material purity. In particular, for structures with high aspect ratios (such as deep trenches or high porosity materials), it has been found that ALD can achieve uniform and conformal film deposition, which is challenging for other deposition techniques disclosed in the prior art.

[0015] In certain embodiments, the methods disclosed herein provide for forming the charge trapping layer without any intermediate vacuum interruption. It has been found that the methods disclosed herein allow for continuous or in-situ deposition of materials to grow thin films, resulting in improved film quality, higher efficiency and reduced risk of contamination.

[0016] The following provides an overview of various aspects of the technology of the present disclosure, followed by a detailed description of specific embodiments. It should be understood that the above-mentioned objects and advantages also apply to various aspects and features disclosed herein.

[0017] Another aspect of the present disclosure relates to a system comprising:

[0018] a reaction chamber constructed and arranged to hold a substrate;

[0019] a hafnium precursor container constructed and arranged to contain and evaporate one or more hafnium precursors;

[0020] a zirconium precursor vessel constructed and arranged to contain and vaporize one or more zirconium precursors;

[0021] an oxygen reactant vessel constructed and arranged to contain and vaporize one or more oxygen reactants;

[0022] a germanium dopant vessel constructed and arranged to contain and evaporate one or more germanium dopants;

[0023] a controller operably connected to the hafnium precursor container, the zirconium precursor container, the oxygen reactant container, and the germanium dopant container;

[0024] The controller is configured to control the introduction of the one or more hafnium precursors, the one or more zirconium precursors, the one or more oxygen reactants, and the one or more germanium dopants into the reaction chamber during a plurality of cycles, wherein as a result of the plurality of cycles, a charge trapping layer comprising one or more germanium-doped HZO films is formed on the substrate.

[0025] In certain embodiments, the systems disclosed herein are configured to form a charge-trapping layer of a storage element by the methods disclosed herein.

[0026] Another aspect of the present disclosure relates to a storage element, comprising:

[0027] Gate electrode;

[0028] a blocking dielectric, the blocking dielectric being adjacent to the gate electrode;

[0029] Tunnel dielectrics;

[0030] a charge-trapping layer located between the blocking dielectric and the tunnel dielectric;

[0031] an n-type layer adjacent to the tunnel dielectric; and

[0032] A p-type layer, which is adjacent to the n-type layer;

[0033] Wherein, the charge trapping layer is obtained by the method disclosed in this article.

[0034] Another aspect of the present disclosure relates to a storage element, comprising:

[0035] Gate electrode;

[0036] a blocking dielectric, the blocking dielectric being adjacent to the gate electrode;

[0037] Tunnel dielectrics;

[0038] a charge-trapping layer located between the blocking dielectric and the tunnel dielectric;

[0039] an n-type layer adjacent to the tunnel dielectric; and

[0040] A p-type layer, which is adjacent to the n-type layer;

[0041] Wherein, the charge trapping layer includes one or more germanium-hafnium-doped HZO layers.

[0042] Another aspect of the present disclosure relates to a gate stack 3D NAND memory, comprising:

[0043] A vertical channel and a plurality of floating gate stacks, each floating gate stack comprising a tunnel dielectric adjacent to the vertical channel, a charge trapping layer adjacent to the tunnel dielectric, a blocking dielectric adjacent to the charge trapping layer and a gate electrode adjacent to the blocking dielectric; wherein the charge trapping layer comprises one or more germanium-doped HZO layers.

[0044] In a specific embodiment, the gate stack 3D NAND memory disclosed herein provides that the charge trapping layer is obtained by the method disclosed herein.

[0045] In a particular embodiment, the gate stack 3D NAND memory disclosed herein further includes a storage element as disclosed herein.

[0046] In another aspect, the present invention relates to using germanium precursors to increase charge trapping in semiconductor structures and reduce the rate of charge loss from the charge trapping layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the size of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure.

[0048] Figure 1 An exemplary embodiment of a method for forming a charge trapping layer of a memory element including a doped HfO2 layer disclosed herein is schematically illustrated.

[0049] Figure 2 Another exemplary embodiment of a method for forming a charge trapping layer of a memory element including a doped HfO2 layer disclosed herein is schematically illustrated.

[0050] Figure 3 Another exemplary embodiment of a method for forming a charge trapping layer of a memory element including a doped HZO layer disclosed herein is schematically illustrated.

[0051] Figure 4 Another exemplary embodiment of a method for forming a charge trapping layer of a memory element including a doped HZO layer disclosed herein is schematically illustrated.

[0052] Figure 5 Another exemplary embodiment of a method for forming a charge trapping layer of a storage element comprising a doped HZO layer and a doped HfO 2 layer is schematically illustrated.

[0053] Figure 6 A system 600 according to yet another exemplary embodiment of the present disclosure is schematically shown. DETAILED DESCRIPTION

[0054] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the disclosure extends beyond the specifically disclosed embodiments and / or uses of the disclosure and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosure disclosed should not be limited by the specifically disclosed embodiments described below.

[0055] In the following detailed description, the underlying technology of the present disclosure will be described through different aspects of the present disclosure. It will be readily understood that the various aspects of the present disclosure, as generally described herein and shown in the accompanying drawings, may be arranged, replaced, combined and designed in a variety of different configurations, all of which are expressly intended and form part of the present disclosure. This description is intended to help the reader more easily understand the technical concepts, but is not meant to limit the scope of the present disclosure, which is limited only by the claims.

[0056] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present disclosure. Therefore, the phrases "in one embodiment" or "in an embodiment" appearing in various places in this specification do not necessarily all refer to the same embodiment.

[0057] As used herein, the term "includes" and its variations are synonymous with "comprises" and its variations or "contains" and its variations, and are inclusive or open-ended and do not exclude additional, unlisted components, elements, or method steps. The term "includes" and its variations, when referring to the components, elements, or method steps, also include embodiments consisting of the components, elements, or method steps. The singular forms "a", "an", and "the" include singular and plural referents unless the context clearly dictates otherwise.

[0058] The objects described herein as "connected" or "coupled" reflect a functional relationship between the objects being described, that is, the term indicates that the objects being described must be connected in a manner to perform the specified function, which may be direct or indirect connection, in an electrical or non-electrical (i.e., physical) manner, as appropriate to the context in which the term is used.

[0059] As used herein, the term "substantially" refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result. For example, a "substantially" closed object means that the object is completely closed or nearly completely closed. In some cases, the exact degree of deviation from absolute completeness that is permitted may depend on the circumstances. Generally speaking, however, near completion will have the same overall result as if absolute and complete completion were obtained. When used in a negative sense, the use of "substantially" also applies to referring to the complete or nearly complete absence of an action, characteristic, property, state, structure, item, or result.

[0060] As used herein, the term "about" is used to provide flexibility to a numerical value or a range endpoint, and a given value can be "slightly above" or "slightly below" the value or endpoint, depending on the specific circumstances. Unless otherwise specified, the term "about" used in accordance with a specific numerical value or numerical range should also be understood to support such numerical terms or ranges without the term "about". For example, the expression "about 30" should be interpreted as supporting not only values ​​slightly above and slightly below 30, but also the actual numerical value of 30.

[0061] Numerical ranges listed by endpoints include all integers, and where appropriate, include fractions within the range (e.g., 1 to 5 may include 1, 2, 3, 4 when involving, for example, multiple elements, and may also include 1.5, 2, 2.75, and 3.80 when involving, for example, measured values). The description of endpoints also includes the endpoint values ​​themselves (e.g., 1.0 to 5.0 includes 1.0 and 5.0). Any numerical range listed herein is intended to include all subranges contained therein. In addition, the terms first, second, third, etc. in the specification and claims are used to distinguish similar elements, and are not necessarily used to describe continuous or chronological order, unless otherwise specified. It should be understood that the terms used in this manner are interchangeable where appropriate, and the embodiments of the present disclosure described herein can operate in other sequences different from those described or shown herein.

[0062] In this specification, reference may be made to devices, structures, systems, or methods that provide "improved" performance (e.g., increased or decreased results, as the case may be). It should be understood that, unless otherwise stated, such "improvement" is a measure of the benefit obtained based on a comparison with a device, structure, system, or method in the prior art. In addition, it should be understood that the degree of improved performance may vary between the disclosed embodiments, and equality or consistency in the amount, degree, or implementation of improved performance should not be assumed to be universally applicable.

[0063] In addition, embodiments of the present disclosure may include hardware, software, and electronic components or modules, which, for purposes of discussion, may be illustrated and described as if most of the components were implemented only in hardware. However, those skilled in the art will recognize, based on a reading of this detailed description, that in at least one embodiment, the electronic-based aspects of the present invention may be implemented in software (e.g., instructions stored on a non-transitory computer-readable medium) that may be executed by one or more processing units (e.g., microprocessors and / or application-specific integrated circuits). Therefore, it should be noted that the technology of the present disclosure may be implemented using multiple hardware- and software-based devices and multiple different structural components. For example, the "server" and "computing device" described in the specification may include one or more processing units, one or more computer-readable media modules, one or more input / output interfaces, and various connections of connecting components.

[0064] Reference to substituents throughout this specification means that one or more hydrogen atoms on the atom designated in the expression "substituted" are replaced with a group selected from the designated group as detailed below, provided that the normal valence of the designated atom is not exceeded and that the substitution results in a chemically stable compound, i.e., a compound that is sufficiently stable to survive isolation from a reaction mixture.

[0065] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may be composed of a single gas or a gas mixture depending on the circumstances. Gases other than process gases, i.e., gases that are not introduced through gas distribution components, other gas distribution devices, etc., may be used, for example, to seal reaction spaces, and may include sealing gases, such as rare gases. In some cases, the term "precursor" may refer to a compound that participates in a chemical reaction to produce another compound, particularly a compound that constitutes a membrane matrix or a main skeleton of a membrane; the term "reactant" may be used interchangeably with the term precursor.

[0066] In the present disclosure, the following abbreviations of chemical structures are used: Cp represents cyclopentadienyl, Me represents methyl; Et represents ethyl; n-Pr represents n-propyl; i-Pr represents isopropyl or isopropyl, n-Bu represents n-butyl; t-Bu represents tert-butyl or tert-butyl.

[0067] In this specification, a technique is described by which a charge trapping or charge holding material suitable for manufacturing a memory element or device can be manufactured. More specifically, various embodiments of the present disclosure relate to a thin film deposition method for forming a charge trapping layer of a memory element, comprising the following steps:

[0068] a) providing a substrate into a reaction chamber;

[0069] b) executing one or more loops, the loops comprising:

[0070] i. a hafnium precursor pulse, wherein at least a portion of the substrate is contacted with one or more hafnium precursors by introducing the one or more hafnium precursors into the reaction chamber;

[0071] ii. Optionally, a zirconium precursor pulse, wherein at least a portion of the substrate is contacted with one or more zirconium precursors by introducing one or more zirconium precursors into the reaction chamber;

[0072] iii. an oxygen reactant pulse, wherein at least a portion of the substrate is contacted with one or more oxygen reactants by introducing one or more oxygen reactants into the reaction chamber;

[0073] iv. a germanium dopant pulse, wherein at least a portion of the substrate is contacted with one or more germanium dopants by introducing one or more germanium dopants into the reaction chamber; and

[0074] As a result of the one or more cycles, a charge trapping layer including one or more germanium-doped hafnium oxide (HfO2) films and / or one or more germanium-doped hafnium zirconium oxide (HZO) films is formed on the substrate.

[0075] In certain embodiments, the methods disclosed herein provide for forming a charge trapping layer comprising one or more germanium-doped hafnium oxide (HfO 2 ) films and one or more germanium-doped hafnium zirconium oxide (HZO) films on the substrate as a result of the one or more cycles.

[0076] In certain embodiments, the methods disclosed herein provide that the one or more cycles is a plurality of cycles.

[0077] The "storage element" referred to herein includes an electronic component or device that is capable of storing, maintaining and retrieving digital information or data. It is usually composed of one or more memory cells, each of which can represent a discrete unit of data, usually in the form of a binary state (0 or 1). In a storage element, data storage and retrieval are facilitated by controlled manipulation of the physical state of the storage cell. These states are usually defined by different electrical, optical or magnetic properties, which can be changed by appropriate input signals. In a storage element utilizing charge trapping, the core concept includes manipulating the charge state of a specific area within the device structure called a "charge trapping layer". The term "charge trapping layer" as used herein may refer to a film or layer arranged or located between an insulating material and a semiconductor material as defined below, resulting in a structure that can capture and maintain charges for a long time. Once the charges are trapped in the charge trapping layer, they remain stored in the trap until a specific operation (such as erasing or reading) is performed.

[0078] Thus, the methods disclosed herein include growing a film or layer having specific charge retention properties. The "film" or "layer" referred to herein can be any continuous or discontinuous structure and material, such as a material deposited according to the present technology. For example, the film and / or layer can include a two-dimensional material, a three-dimensional material, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or a cluster of atoms and / or molecules, or a layer composed of isolated atoms and / or molecules. The film or layer can include a material or layer having pinholes, which can be continuous or discontinuous.

[0079] In the methods disclosed herein, a substrate surface is exposed to various precursors, reactants, and germanium dopants to form a charge trapping layer including one or more germanium-doped metal oxide films. As used herein, the term "substrate" may refer to any one or more underlying materials that can be used to form or on which a device, circuit, or film can be formed. A "substrate" may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. A substrate may be in any form, such as a powder, a plate, or a workpiece. Plate-like substrates may include wafers of various shapes and sizes. A substrate may include a bulk material, such as silicon (e.g., single crystal silicon), other Group IV materials, such as germanium, or other semiconductor materials, such as Group II-VI or Group III-V semiconductor materials, and may include one or more layers covering or located below the bulk material. In addition, the substrate may include various features, such as depressions, protrusions, etc. formed in or on at least a portion of the substrate layer. For example, a substrate may include a bulk semiconductor material and an insulating or (high-k) dielectric material layer covering at least a portion of the bulk semiconductor material. In certain embodiments, the substrate may include silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, or silicon carbide. The continuous substrate may extend beyond the boundaries of the processing / reaction chamber where the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber so that the process continues until the end of the substrate is reached. The continuous substrate may be provided from a continuous substrate feed system to allow the continuous substrate to be manufactured and output in any suitable form. Non-limiting examples of continuous substrates may include thin sheets or flexible materials. The continuous substrate may also include a carrier or thin sheet on which a non-continuous substrate is mounted.

[0080] In certain embodiments, the charge trapping layer comprises one or more germanium-doped HfO2 films. In certain embodiments, the charge trapping layer comprises one or more germanium-doped HZO films. In some embodiments, the charge trapping layer comprises one or more germanium-doped HfO2 films and one or more germanium-doped HZO films. Advantageously, the methods disclosed herein can allow controlled deposition, structuring, and formation of a charge trapping layer with a reduced number of defects, uniform layer thickness, and targeted doping, resulting in increased charge trapping efficiency and reduced charge loss rates.

[0081] Specifically, as described herein, forming a charge trapping layer including one or more germanium-doped HfO2 films and / or one or more germanium-doped HZO films on a substrate can involve a cyclic deposition process, such as an atomic layer deposition (ALD) process or a cyclic chemical vapor deposition (CVD) process. The cyclic deposition process can include one or more cycles. In a specific embodiment, the method disclosed herein is an ALD method. Compared to the sputtering technology commonly used in the prior art for depositing thin films and layers in various semiconductor and memory element processes, it is found that a cyclic deposition process such as ALD provides a more uniform deposition on the substrate surface.

[0082] As used herein, the synonymous terms "deposition" or "cyclic deposition" or "cyclic deposition process" or "cyclic deposition process" refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer or film on a substrate, and include processing techniques such as ALD, CVD, and hybrid cyclic deposition processes including an ALD component and a CVD component. Typically, one deposition cycle can form a film or layer of about 0.10 nm. However, the experimental thickness can vary depending on the amount and type of cycles and the available reaction sites on the substrate.

[0083] The term "atomic layer deposition" or "ALD" refers to a vapor deposition process in which a deposition cycle (usually multiple consecutive deposition cycles) is performed in a process chamber. The term atomic layer deposition as used herein is also meant to include processes designated by related terms such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of precursor / reactive gas and purge gas (e.g., inert carrier gas).

[0084] Typically, for an ALD process, during each cycle, a precursor (e.g., a hafnium precursor and / or a zirconium precursor) is introduced into a reaction chamber and chemically adsorbed onto a deposition surface (e.g., a substrate surface that may include previously deposited material from a previous ALD cycle or other material) and forms a material, such as approximately a monolayer or sub-monolayer of material, or several monolayers of material, or multiple monolayers of material that is not readily reactive with additional precursors (i.e., a self-limiting reaction). Thereafter, in some cases, a reactant (e.g., another precursor or reactive gas, such as an oxygen reactant) may subsequently be introduced into the process chamber to convert the chemically adsorbed precursor into the desired material on the deposition surface. The reactant is capable of further reacting with the precursor. During one or more repetitions, such as during each deposition step, a purge step may be utilized to remove any excess precursor from the process chamber and / or to remove any excess reactant and / or reaction byproducts from the reaction chamber. Note that in the various embodiments described herein, the ALD process does not necessarily consist of a series of self-limiting surface reactions.

[0085] As used herein, the term "purge" may refer to the process of providing an inert or substantially inert gas to a reaction chamber between two gas pulses that react with each other. For example, a purge may be provided between a precursor pulse and a reactant pulse, for example using an inert gas such as a noble gas, to avoid or at least minimize gas phase interactions between the precursor and the reactant.

[0086] Advantageously, the cyclic deposition process disclosed herein can be a thermal deposition process. In other words, in some embodiments, no plasma is used for either the pulsing or the purging in the cyclic deposition process. In the case of a thermal cyclic deposition process, the duration of the step of providing the hafnium precursor and / or the zirconium precursor to the reaction chamber, the duration of the step of providing the reactant to the reaction chamber, and / or the duration of the step of providing the germanium dopant to the reaction chamber can be relatively long to allow the precursor, reactant, and / or dopant-containing gas to react with the substrate surface. For example, the duration can be greater than or equal to 5 seconds, or greater than or equal to 10 seconds, or between about 5 and 10 seconds.

[0087] In some embodiments, the cyclic deposition process uses a plasma enhanced deposition technique. For example, the cyclic deposition process may include a plasma enhanced atomic layer deposition process and / or a plasma enhanced chemical vapor deposition process. In this case, any pulse in the cyclic deposition process may include generating a plasma in the reaction chamber.

[0088] In some embodiments, the methods disclosed herein can be a continuous vacuum deposition process. In the case of a continuous vacuum deposition process, the material is deposited onto a substrate in a reaction chamber without introducing atmosphere or any interruption that would destroy the controlled vacuum environment. The process includes maintaining a consistent vacuum pressure within the reaction chamber. In a particular embodiment, the methods disclosed herein provide for forming a charge trapping layer without any intermediate vacuum interruptions. This has the advantage that the present disclosure avoids the need for repeated evacuation and purging of the reaction chamber, which is common in conventional batch deposition methods.

[0089] In certain embodiments, the methods disclosed herein include at least 1 cycle, at least 2 cycles, at least 5 cycles, at least 10 cycles, at least 20 cycles, at least 40 cycles, at least 100 cycles, at least 200 cycles, at least 400 cycles, at least 600 cycles, at least 1000 cycles. In some embodiments, these steps can be repeated for at least 1 cycle to at most 1000 cycles, or at least 2 cycles to at most 100 cycles, or at least 5 cycles to at most 50 cycles.

[0090] In certain embodiments, the methods disclosed herein provide that the formed one or more germanium-doped HfO2 films and / or one or more germanium-doped HZO films may have an average thickness of between 0.10 nm and 30.0 nm, or between 0.10 nm and 20.0 nm, preferably between 0.50 nm and 20.0 nm, or between 1.0 nm and 20.0 nm, or between 1.0 nm and 15.0 nm, or more preferably between 1.0 nm and 10.0 nm, even more preferably between 1.0 nm and 5.0 nm. In some embodiments, the one or more germanium-doped HfO2 films and / or one or more germanium-doped HZO films may have an average thickness of less than 1.0 nm, such as less than 0.50 nm, such as about 0.10 nm.

[0091] It should be understood that when the HfO2 film and / or the HZO film are deposited on a substrate, a certain degree of mixing of the constituent components of these layers may occur. For example, when the HZO layer is deposited on the HfO2 layer, at least one of hafnium, zirconium, or oxygen can be incorporated into the hafnium oxide-containing layer, for example, by diffusion, surface isolation, or another process. For example, when the HZO layer is deposited on a substrate containing silicon oxide, at least one of silicon or oxide can be incorporated into the hafnium zirconium oxide-containing layer. In some embodiments, such mixing can result in the formation of a sandwich containing two components of each layer. In addition, the extremely thin HfO2 film and / or HZO film can further contain hydrogen and / or carbon in the resulting charge trapping layer.

[0092] In some embodiments, one or more Ge-doped HfO2 films and / or one or more Ge-doped HZO films may have a growth rate of 0.10 nm or less / cycle for precursor / reactive gas and purge gas (e.g., inert carrier gas). For many electronic applications, including memory elements for high-density data storage, lower thickness layers may be desirable.

[0093] The methods disclosed herein rely on the execution of one or more cycles to grow thin film charge trapping. The cycles referred to herein include three or more pulses. In some embodiments, at least one pulse involves a self-limiting surface reaction. In some embodiments, all pulses involve a self-limiting surface reaction. In some embodiments, the cycle may include the following pulse sequence: a hafnium precursor pulse, an oxygen reactant pulse, and a germanium dopant pulse. In some embodiments, the cycle may include the following pulse sequence: a hafnium precursor pulse, a zirconium precursor pulse, an oxygen reactant pulse, and a germanium dopant pulse. In the hafnium precursor pulse, one or more hafnium precursors are provided to the reaction chamber and can be chemically adsorbed onto the substrate (i.e., attached to atoms or molecules on the surface of the substrate and form chemical bonds therewith). In the zirconium precursor pulse, one or more zirconium precursors are provided to the reaction chamber and can be chemically adsorbed onto the substrate. In an oxygen reactant pulse, one or more oxygen reactants are provided to a reaction chamber and may react with chemically adsorbed hafnium metal and / or zirconium metal to form a metal oxide film or layer (e.g., hafnium oxide (HfO2) and / or hafnium zirconium oxide (HfZrO2)) on at least a portion of a substrate. In a germanium dopant pulse, one or more germanium dopants are provided to a reaction chamber and may adhere to the surface of the deposited metal oxide film or layer and may react to incorporate germanium dopant atoms or molecules into the growing layer. The number of cycles of the method disclosed herein determines the total thickness of the deposited HfO2 film and / or HZO film and the concentration of germanium dopants therein. An advantage of the currently disclosed cyclic deposition process is the precise control of the total layer thickness and dopant incorporation.

[0094] Figure 1 An exemplary embodiment of a method for forming a charge trapping layer as described herein, the charge trapping layer comprising one or more germanium-doped HfO2 films as disclosed herein, is described. The method begins after a substrate has been provided to a reaction chamber 111. The cyclic deposition process includes contacting one or more hafnium precursors with at least a portion of the substrate in a hafnium precursor pulse 112. Optionally, after the hafnium precursor pulse 112, the reaction chamber is purged 113. Then, one or more oxygen reactants are provided to the reaction chamber in an oxygen reactant pulse 114. Optionally, after the oxygen reactant pulse, the reaction chamber may be purged 115. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 116. Optionally, after the germanium dopant pulse, the reaction chamber may be purged 117.

[0095] The hafnium precursor pulse 112, the oxygen reactant pulse 114, the germanium dopant pulse 116, and the optional purges 113, 115, 117 may be repeated 118 any number of times to obtain a charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness. When the charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness has been deposited, the method ends 119. Once the method ends, the substrate may, for example, be subjected to additional processes to form a device structure and / or device.

[0096] Figure 2 Another exemplary embodiment of a method for forming a charge trapping layer as described herein, the charge trapping layer comprising one or more germanium-doped HfO2 films disclosed herein, is described. The method begins 211 after a substrate has been provided to a reaction chamber. The cyclic deposition process includes providing one or more oxygen reactants to the reaction chamber in an oxygen reactant pulse 212. Optionally, after the oxygen reactant pulse 212, the reaction chamber is purged 213. Then, at least a portion of the substrate is contacted with one or more hafnium precursors in a hafnium precursor pulse 214. Optionally, after the hafnium precursor pulse, the reaction chamber is purged 215. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 216. Optionally, after the germanium dopant pulse, the reaction chamber may be purged 217. The oxygen reactant pulse 212, the hafnium precursor pulse 214, the germanium dopant pulse 216, and the optional purges 213, 215, 217 may be repeated 218 any number of times to obtain a charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness. When the charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness has been deposited, the method ends 219. Once the method ends, the substrate may, for example, be subjected to additional processes to form a device structure and / or device.

[0097] Figure 3Another exemplary embodiment of a method for forming a charge trapping layer as described herein, the charge trapping layer comprising one or more germanium-doped HZO films disclosed herein, is described. The method begins after a substrate has been provided to a reaction chamber 311. The cyclic deposition process includes contacting one or more hafnium precursors with at least a portion of the substrate in a hafnium precursor pulse 312. Optionally, after the hafnium precursor pulse 312, the reaction chamber is purged 313. Then, at least a portion of the substrate is contacted with one or more zirconium precursors in a zirconium precursor pulse 314. Optionally, after the zirconium precursor pulse, the reaction chamber is purged 315. Then, one or more oxygen reactants are provided to the reaction chamber in an oxygen reactant pulse 316. Optionally, the reaction chamber may be purged after the oxygen reactant pulse 317. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 318. Optionally, the reaction chamber may be purged after the germanium dopant pulse 319. The hafnium precursor pulse 312, the zirconium precursor pulse 314, the oxygen reactant pulse 316, the germanium dopant pulse 318, and the optional purges 313, 315, 317, 319 may be repeated 320 any number of times to obtain a charge trapping layer including one or more germanium-doped HZO films having a desired thickness. When the charge trapping layer including one or more germanium-doped HZO films having a desired thickness has been deposited, the method ends 321. Once the method ends, the substrate may, for example, be subjected to additional processes to form a device structure and / or device.

[0098] Figure 4 Another exemplary embodiment of a method for forming a charge trapping layer as described herein, the charge trapping layer comprising one or more germanium-doped HZO films disclosed herein, is described. The method begins after a substrate has been provided to a reaction chamber 411. The cyclic deposition process includes providing one or more oxygen reactants to the reaction chamber in an oxygen reactant pulse 412. Optionally, after the oxygen reactant pulse 412, the reaction chamber may be purged 413. Then, at least a portion of the substrate is contacted with one or more hafnium precursors in a hafnium precursor pulse 414. Optionally, the reaction chamber is purged after the hafnium precursor pulse 415. Then, at least a portion of the substrate is contacted with one or more zirconium precursors in a zirconium precursor pulse 416. Optionally, the reaction chamber is purged after the zirconium precursor pulse 417. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 418. Optionally, the reaction chamber may be purged after the germanium dopant pulse 419. The oxygen reactant pulse 412, the hafnium precursor pulse 414, the zirconium precursor pulse 416, the germanium dopant pulse 418, and the optional purges 413, 415, 417, 419 can be repeated 420 any number of times to obtain a charge trapping layer including one or more germanium-doped HZO films having a desired thickness. When the charge trapping layer including one or more germanium-doped HZO films having a desired thickness has been deposited, the method ends 421. Once the method ends, the substrate can, for example, be subjected to additional processes to form a device structure and / or device.

[0099] Figure 5 Another exemplary embodiment of a method for forming a charge trapping layer as described herein, the charge trapping layer comprising one or more germanium-doped HZO films and one or more germanium-doped HfO2 films disclosed herein, is described. The method begins after a substrate has been provided to a reaction chamber 511. The cyclic deposition process includes contacting one or more hafnium precursors with at least a portion of the substrate in a hafnium precursor pulse 512. Optionally, after the hafnium precursor pulse 512, the reaction chamber is purged 513. Then, at least a portion of the substrate is contacted with one or more zirconium precursors in a zirconium precursor pulse 514. Optionally, after the zirconium precursor pulse, the reaction chamber is purged 515. Then, one or more oxygen reactants are provided to the reaction chamber in an oxygen reactant pulse 516. Optionally, the reaction chamber may be purged after the oxygen reactant pulse 517. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 518. Optionally, after the germanium dopant pulse, the reaction chamber may be purged 519.

[0100] The hafnium precursor pulse 512, the zirconium precursor pulse 514, the oxygen reactant pulse 516, the germanium dopant pulse 518, and the optional purges 513, 515, 517, 519 may be repeated 520 any number of times to obtain a charge trapping layer including one or more germanium doped HZO films having a desired thickness. When the charge trapping layer 521 including one or more germanium doped HZO films having a desired thickness has been deposited, the method proceeds to form one or more germanium doped HfO2 films disclosed herein. After the substrate has been provided to the same reaction chamber or a different reaction chamber, the second portion of the method begins 522. The cyclic deposition process includes contacting one or more hafnium precursors with at least a portion of the substrate in a hafnium precursor pulse 523. Optionally, after the hafnium precursor pulse 523, the reaction chamber is purged 524. Then, one or more oxygen reactants are provided to the reaction chamber in an oxygen reactant pulse 525. Optionally, the reaction chamber may be purged 526 after the oxygen reactant pulse. Then, one or more germanium dopants are provided to the reaction chamber in a germanium dopant pulse 527. Optionally, the reaction chamber may be purged 528 after the germanium dopant pulse.

[0101] The hafnium precursor pulse 523, the oxygen reactant pulse 525, the germanium dopant pulse 527, and the optional purges 524, 526, 528 may be repeated 529 any number of times to obtain a charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness. When the charge trapping layer comprising one or more germanium-doped HfO2 films having a desired thickness has been deposited, the method ends 530. Once the method ends, the substrate may, for example, be subjected to additional processes to form a device structure and / or device.

[0102] like Figures 1 to 5As shown, in some embodiments, the cycle includes a sequence of a hafnium precursor pulse, an optional zirconium precursor pulse, an oxygen reactant pulse, and a germanium dopant pulse. In some embodiments, the method disclosed herein includes multiple cycles, wherein the sequence of consecutive pulses within each cycle can vary. For example, the oxygen reactant pulse can precede the hafnium precursor pulse and / or the zirconium precursor pulse. In a specific embodiment, the method disclosed herein provides for performing an oxygen reactant pulse after each hafnium precursor pulse and / or after each zirconium precursor pulse. In a specific embodiment, the method disclosed herein provides for performing a germanium dopant pulse after the hafnium precursor pulse without any intermediate oxygen reactant pulse. In a specific embodiment, the method disclosed herein provides for performing a germanium dopant pulse after the zirconium precursor pulse without any intermediate oxygen reactant pulse.

[0103] In certain embodiments, the methods disclosed herein provide that the hafnium precursor pulse, the optional zirconium precursor pulse, the oxygen reactant pulse, and / or the germanium dopant pulse include a plurality of micropulses. As used herein, a "micropulse" is a short period during which one or more hafnium precursors, one or more zirconium precursors, one or more oxygen reactants, and / or one or more germanium dopants may be introduced into the reaction chamber. Thus, the methods disclosed herein provide high flexibility in pulse sequence and length, thereby providing a more cost-effective and efficient method than the methods disclosed in the prior art.

[0104] In some embodiments, the hafnium precursor pulse and / or the zirconium precursor pulse lasts at least 0.01 second to at most 120 seconds, or at least 0.01 second to at most 0.1 second, or at least 0.01 second to at most 0.02 seconds, or at least 0.02 seconds to at most 0.05 seconds, or at least 0.05 seconds to at most 0.1 second, or at least 0.1 second to at most 20 seconds, or at least 0.1 second to at most 0.2 seconds, or at least 0.2 seconds to at most 0.5 seconds, or at least 0.5 seconds to at most 1.0 second, or at least 1.0 second to at most 2.0 seconds, or at least 2.0 seconds to at most 5.0 seconds, or at least 5.0 seconds to at most 10.0 seconds, or at least 10.0 seconds to at most 20.0 seconds. In some embodiments, the oxygen reactant pulse lasts from at least 0.1 second to at most 20 seconds, or from at least 0.1 second to at most 0.2 seconds, or from at least 0.2 seconds to at most 0.5 seconds, or from at least 0.5 seconds to at most 1.0 seconds, or from at least 1.0 seconds to at most 2.0 seconds, or from at least 2.0 seconds to at most 5.0 seconds, or from at least 5.0 seconds to at most 10.0 seconds, or from at least 10.0 seconds to at most 20.0 seconds, or from at least 20.0 seconds to at most 120.0 seconds, or from at least 20.0 seconds to at most 50.0 seconds, or from at least 50.0 seconds to at most 80.0 seconds, or from at least 80.0 seconds to at most 120.0 seconds. In some embodiments, the germanium dopant pulse lasts at least 0.1 second to at most 20 seconds, or at least 0.1 second to at most 0.2 seconds, or at least 0.2 seconds to at most 0.5 seconds, or at least 0.5 seconds to at most 1.0 seconds, or at least 1.0 seconds to at most 2.0 seconds, or at least 2.0 seconds to at most 5.0 seconds, or at least 5.0 seconds to at most 10.0 seconds, or at least 10.0 seconds to at most 20.0 seconds, or at least 20.0 seconds to at most 120.0 seconds, or at least 20.0 seconds to at most 50.0 seconds, or at least 50.0 seconds to at most 80.0 seconds, or at least 80.0 seconds to at most 120.0 seconds.

[0105] It should be understood that any two steps and / or pulses and / or micropulses may be separated by a purge. Thus, in some embodiments, the hafnium precursor pulse and / or zirconium precursor pulse and the oxygen reactant pulse may be separated by a purge. In some embodiments, the germanium dopant pulse is preceded by a purge. In some embodiments, subsequent cycles are separated by a purge. In a particular embodiment, the reaction chamber is purged before and / or after each hafnium precursor pulse, optional zirconium precursor pulse, oxygen reactant pulse and / or germanium dopant pulse. The advantage of purging the reaction chamber before and / or after each precursor pulse, reactant pulse and / or dopant pulse is that any residual precursors, reactants, dopants and / or reaction byproducts are removed, thereby avoiding cross contamination between pulses and producing a film or layer with high purity and fewer defects.

[0106] In some embodiments, the plurality of deposition cycles may include a plurality of main cycles. The main cycle may include a germanium dopant pulse and one or more sub-cycles. The sub-cycles may include a hafnium precursor pulse and / or a zirconium precursor pulse and an oxygen reactant pulse. Thus, in some embodiments, the plurality of deposition cycles may be represented by formula i):

[0107] [(Hf precursor + oxygen reactant) x sub-cycle + germanium dopant] x main cycle i)

[0108] Additionally or alternatively, in some embodiments, the plurality of deposition cycles may be represented by equation ii):

[0109] [(Hf precursor + zirconium precursor + oxygen reactant) x sub-cycle + germanium dopant] x main cycle ii)

[0110] Additionally or alternatively, in some embodiments, the plurality of deposition cycles may be represented by equation iii):

[0111] [(oxygen reactant + hafnium precursor) x sub-cycle + germanium dopant] x main cycle iii)

[0112] Additionally or alternatively, in some embodiments, the plurality of deposition cycles may be represented by equation iv):

[0113] [(oxygen reactant + hafnium precursor + zirconium precursor) x sub-cycle + germanium dopant] x main cycle iv)

[0114] Additionally or alternatively, in some embodiments, the plurality of deposition cycles may be represented by equation v):

[0115] [(oxygen reactant + zirconium precursor + hafnium precursor) x sub-cycle + germanium dopant] x main cycle v)

[0116] Among them, "Hf precursor" represents the hafnium precursor pulse, "Zr precursor" represents the zirconium precursor pulse, "Oxygen reactant" represents the oxygen reactant pulse, "x sub-cycle" represents the number of sub-cycles per main cycle, "Ge dopant" represents the germanium dopant pulse, "x main cycle" represents the main cycle number, and "+" represents that one pulse occurs after another pulse.

[0117] In some embodiments, the method comprises from at least 2 sub-cycles to at most 5 sub-cycles, or from at least 5 sub-cycles to at most 10 sub-cycles, or from at least 10 sub-cycles to at most 20 sub-cycles, or from at least 20 sub-cycles to at most 50 sub-cycles, or from at least 50 sub-cycles to at most 100 sub-cycles, or from at least 100 sub-cycles to at most 200 sub-cycles, or from at least 200 sub-cycles to at most 500 sub-cycles, or from at least 500 sub-cycles to at most 1000 sub-cycles, or from at least 1000 sub-cycles to at most 2000 sub-cycles.

[0118] In the present invention, germanium dopants may be strategically introduced to create "charge storage sites" or "charge traps" within the charge trapping layer. Charge storage sites control the capture and release of charge carriers such as electrons or holes, which may represent the data state of a memory cell. The inventors have found that germanium dopants are particularly useful for improving the efficiency of charge trapping in charge retention structures. Without wishing to be bound by theory, it is believed that according to the present disclosure, germanium doping of HfO2 films and / or HZO films may improve the charge retention characteristics of the charge trapping layer by creating deep charge traps (i.e., having a high barrier to the release of charge carriers). This may enhance the ability of the charge trapping layer to capture and retain charge during programming and erasing operations of the storage element, resulting in reliable and consistent data storage. In some embodiments, germanium dopants may be introduced into the growing HfO2 film and / or HZO film (i.e., during film deposition). In some embodiments, germanium dopants may be introduced after the HfO2 film and / or HZO film is formed (i.e., after the film is deposited in one or more sub-cycles).

[0119] In certain embodiments, the methods disclosed herein provide that one or more germanium dopants are represented by the following general formula (I) or (II),

[0120]

[0121] Among them, Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q 10 are each independently selected from hydrogen, halogen, alkyl, alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 )2, alkoxy, heteroalkyl, cycloalkyloxy, cycloalkyl, aryl and (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, alkyl, alkenyl or Si(R 5 )3; where each R 3 is an alkyl group; and wherein each R 5 are independently hydrogen or alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

[0122] The term "halo" or "halogen" as a group or part of a group is a generic term for fluorine (F), chlorine (Cl), bromine (Br), iodine (I).

[0123] The term "alkyl" as a group or part of a group refers to a group of formula C n H 2n+1 wherein n is a number greater than or equal to 1. The alkyl group may be straight or branched and may be substituted as indicated herein. Typically, the alkyl groups disclosed herein contain 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. When a subscript is used after a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C 1-20 "Alkyl" as a group or part of a group refers to a group of the formula -C n H 2n+1 wherein n is a number from 1 to 20. Thus, for example, "C 1-8 "Alkyl" includes all straight or branched chain alkyl groups having between 1 and 8 carbon atoms, thus including methyl, ethyl, n-propyl, isopropyl, butyl and isomers thereof (e.g., n-butyl, isobutyl and tert-butyl); pentyl and isomers thereof, hexyl and isomers thereof, etc. "Substituted alkyl" refers to an alkyl group substituted with one or more substituents (e.g., 1 to 3 substituents, e.g., 1, 2 or 3 substituents) at any available point of attachment.

[0124] When the suffix "ene" is used in conjunction with an alkyl group, i.e., "alkylene", this refers to an alkyl group as defined herein having two single bonds as points of attachment to other groups. As used herein, the term "alkylene" is also known as "alkanediyl" and, by itself or as part of another substituent, refers to a divalent alkyl group, i.e., having two single bonds for attachment to two other groups. Alkylene groups may be straight or branched and may be substituted as indicated herein. Non-limiting examples of alkylene groups include methylene (-CH2-), ethylene (-CH2-CH2-), methylmethylene (-CH(CH3)-), 1-methylethylene (-CH(CH3)-CH2-), n-propylene (-CH2-CH2-CH2-), 2-methylpropylene (-CH2-CH(CH3)-CH2-), 3-methylpropylene (-CH2-CH2-CH(CH3)-), n-butene (-CH2-CH2-CH2-CH2-), 2-methylbutylene (-CH2-CH(CH3)-CH2-CH2-), 4-methylbutene (-CH2-CH2-CH2-CH(CH3)-), pentyl and its chain isomers, hexyl and its chain isomers.

[0125] The term "alkenyl" as a group or part of a group refers to an unsaturated hydrocarbon group, which may be straight or branched, containing one or more carbon-carbon double bonds. Typically, the alkenyl groups disclosed herein contain 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. When a subscript is used after a carbon atom, the subscript refers to the number of carbon atoms that the named group may contain. 3-20 Examples of alkenyl groups are ethenyl, 2-propenyl, 2-butenyl, 3-butenyl, 2-pentenyl and isomers thereof, 2-hexenyl and isomers thereof, 2,4-pentadienyl and the like.

[0126] The term "alkoxy" or "alkyloxy" as a group or part of a group refers to a radical having the formula -OR b A group in which R b is an alkyl group as defined above. Non-limiting examples of suitable alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and hexyloxy.

[0127] The term "cycloalkyl" as a group or part of a group refers to a cyclic alkyl group, i.e., a monovalent saturated hydrocarbon group having one or more ring structures, containing 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms; more preferably 3 to 6 carbon atoms. Cycloalkyl includes all saturated hydrocarbon groups containing one or more rings, including monocyclic, bicyclic or tricyclic rings. The other rings of a polycyclic cycloalkyl group may be fused, bridged and / or connected by one or more spiro atoms. When a subscript is used after a carbon atom in this document, the subscript refers to the number of carbon atoms that the named group may contain. For example, the term "C 3-20 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 20 carbon atoms. For example, the term “C 3-10 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 10 carbon atoms. For example, the term “C 3-8 Cycloalkyl” refers to a cyclic alkyl group containing 3 to 8 carbon atoms. For example, the term “C 3-6 Cycloalkyl" is a cyclic alkyl group containing 3 to 6 carbon atoms. 3-12 Examples of cycloalkyl include, but are not limited to, adamantyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]hept-2-yl, (1S,4R)-norbornan-2-yl, (1R,4R)-norbornan-2-yl, (1S,4S)-norbornan-2-yl, (1R,4S)-norbornan-2-yl.

[0128] When the suffix "" is used in conjunction with a cycloalkyl group, i.e., cycloalkylene, this refers to a cycloalkyl group as defined herein having two single bonds as points of attachment to other groups. Non-limiting examples of "cycloalkylene" include 1,2-cyclopropylene, 1,1-cyclopropylene, 1,1-cyclobutene, 1,2-cyclobutene, 1,3-cyclopentylene, 1,1-cyclopentylene, and 1,4-cyclohexylene.

[0129] When an alkylene or cycloalkylene group is present, the connection to the molecular structure forming part thereof may be through a common carbon atom or different carbon atoms. To illustrate this, using the asterisk nomenclature of the present disclosure, a C3 alkylene group may be, for example, *-CH2CH2CH2-*, *-CH(-CH2CH3)-*, or *-CH2CH(-CH3)-*. Similarly, a C3 cycloalkylene group may be:

[0130]

[0131] The term "aryl" as a group or part of a group refers to a polyunsaturated aromatic hydrocarbon radical having a single ring (i.e., phenyl) or multiple aromatic rings fused together (e.g., naphthyl), or covalently linked, typically containing 6 to 20 atoms; preferably 6 to 10, wherein at least one ring is aromatic. The aromatic ring may optionally include one or two additional rings (cycloalkyl, heterocyclyl, or heteroaryl) fused thereto. Examples of suitable aryl groups include C 6-20 Aryl, preferably C 6-10 Aryl, more preferably C 6-8 Aryl. Non-limiting examples of aryl groups include phenyl, biphenyl, biphenyl or 1- or 2-naphthyl; 1-, 2-, 3-, 4-, 5- or 6-tetrahydronaphthyl (also known as "1,2,3,4-tetrahydronaphthalene"); 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-azulyl, 4-, 5-, 6 or 7-indenyl; 4- or 5-indanyl; 5-, 6-, 7- or 8-tetrahydronaphthyl; 1,2,3,4-tetrahydronaphthyl; and 1,4-dihydronaphthyl; 1-, 2-, 3-, 4- or 5-pyrenyl. "Substituted aryl" refers to an aryl group having one or more substituents (e.g., 1, 2 or 3 substituents, or 1 to 2 substituents) at any available attachment point.

[0132] The term "cycloalkoxy" as a group or part of a group refers to a cycloalkoxy radical having the formula -OR c A group in which R c is a cycloalkyl group as defined above.

[0133] The term "heteroalkyl" as a group or part of a group refers to an acyclic alkyl group in which one or more carbon atoms are replaced by at least one heteroatom selected from O, Si, S, B and P, with the proviso that the chain cannot contain two adjacent heteroatoms. This means that one or more -CH3 of the acyclic alkyl group may be replaced by, for example, -OH, and / or one or more -CR2- of the acyclic alkyl group may be replaced by O, Si, S, B and P.

[0134] In some embodiments, the present disclosure provides that Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q 10 are each independently selected from hydrogen, halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, C 1-8 Alkyl, C 2-8 Alkenyl or Si(R 5 )3; where each R 3 It is C 1-8 Alkyl; wherein each R 5 are independently hydrogen or C 1-8 Alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

[0135] In some embodiments, the present disclosure provides that Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q10 are each independently selected from hydrogen, halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 2. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl or Si(R 5 )3; where each R 3 It is C 1-4 Alkyl; wherein each R 5 are independently hydrogen or C 1-4 Alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

[0136] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the alkyl group is C 1-8 Alkyl, more specifically C 1-4 More particularly, the alkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 alkyl group.

[0137] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the alkenyl group is C 2-8 Alkenyl, more specifically C 2-4 More particularly, alkenyl is C2, C3, C4, C5, C6, C7 and / or C8 alkenyl.

[0138] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the alkoxy group is C 1-8 Alkoxy, more specifically C 1-4 Alkoxy. More particularly, alkoxy is C1, C2, C3, C4, C5, C6, C7 and / or C8 alkoxy.

[0139] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the heteroalkyl group is a heteroC 1-8 Alkyl, more specifically heteroC 1-4 More particularly, the heteroalkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 heteroalkyl group.

[0140] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the cycloalkoxy group is C 3-8 Cycloalkoxy. More particularly, cycloalkoxy is C3, C4, C5, C6, C7 and / or C8 cycloalkoxy.

[0141] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the cycloalkyl group is C 3-8 Cycloalkyl. More particularly, cycloalkyl is C3, C4, C5, C6, C7 and / or C8 cycloalkyl.

[0142] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by formula (I) or (II), the aryl group is C 6-10 More particularly, aryl is C6, C7, C8, C9 and / or C 10 Aryl.

[0143] In certain embodiments, the methods disclosed herein provide that one or more germanium dopants are selected from the group consisting of Ge2H6, GeH4, GeF4, GeHF3, GeH2F2, GeH3F1, GeCl4, GeHCl3, GeH2Cl2, GeH3Cl1, GeBr4, GeHBr3, GeH2Br2, GeH3Br1, GeI4, GeHI3, GeH2I2, GeH3I1, GeF2(C4H8O2), GeCl2(C4H8O2), GeBr2(C4H8O2), GeI2(C4H8O2), GeH2Me2, GeH2Et2, GeH2(i-Pr)2, GeH(n-Bu)3, Ge(NMe2)4, Ge(NMeEt)4, Ge(NEt2)4 ,Ge[N(SiMe3)2]4,Ge(NMe2)2[N(SiMe3)2]2,Ge(NMe2)2[NHt-Bu(CH2)2NHt-Bu],Ge[NHt-Bu(CH2)2NHt-Bu]2,Ge(NMe2)2[NHi-Pr(CH2)2NHi-Pr],Ge[NHi-Pr(CH2 )2NHi-Pr]2,Ge(OMe)4,Ge(OEt)4,Ge(Oi-Pr)4,Ge(Ot-Bu)4, or Ge(On-Bu)4,GeN( CH3)2[(Ni-Pr)2C=N-(CH3)2] and GeN(CH3)2[1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine]. Extensive experiments have shown that the germanium dopants disclosed herein provide a good balance between volatility and reactivity, resulting in efficient transfer of the germanium dopant to the substrate.

[0144] In certain embodiments, the methods disclosed herein provide that the one or more germanium dopants are Ge(NMe2)4.

[0145] In some embodiments, the implanted dose or molar atomic percentage of germanium dopant in one or more deposited HfO2 films and / or one or more deposited HZO films is in the range of 0.10 atomic % to 15.0 atomic %, or 0.50 atomic % to 15.0 atomic %, or 1.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 10.0 atomic %. Preferably, the implanted dose or molar atomic percentage of germanium dopant in one or more deposited HfO2 films and / or one or more deposited HZO films is less than 10.0 atomic %, such as less than 9.0 atomic %, or less than 8.0 atomic %, or less than 7.0 atomic %, or less than 6.0 atomic %, or less than 5.0 atomic %, or less than 4.0 atomic %, or less than 3.0 atomic %, or less than 2.0 atomic %, or less than 1.0 atomic %, or less than 0.50 atomic %. Advantageously, the present method allows the introduction of germanium dopant at a specific location and at a defined concentration in the charge trapping layer. The specific location may include the bulk material of the charge trapping layer and / or the surface of the charge trapping layer. In some embodiments, only a small amount of germanium dopant (at the specific location) is required to provide strong charge retention of the charge trapping layer, thus providing a cost effective and efficient doping method.

[0146] Compared to existing charge trapping layers including SiN, the present invention relies on the formation of a doped metal oxide film or layer. The inventors have found that a hafnium oxide layer and / or a hafnium zirconium oxide layer can provide a particularly improved charge trapping efficiency relative to SiN. In addition, by doping the formed hafnium oxide layer and / or hafnium zirconium oxide layer with a germanium dopant, the charge loss rate can be reduced.

[0147] In the present disclosure, one or more metal precursors (e.g., hafnium and / or zirconium) may adhere and bond to a substrate. It has been found that, in particular, metallic hafnium and / or metallic zirconium provide strong chemical adsorption to the deposition surface, resulting in a thin film or layer with high integrity and functionality.

[0148] In certain embodiments, the methods disclosed herein provide that one or more hafnium precursors are represented by the following general formula (III),

[0149]

[0150] Among them, Q 11 ,Q 12 ,Q 13 ,Q 14 Each is independently selected from halogen, alkyl, alkenyl, N(R 1 )2, alkoxy, heteroalkyl, cycloalkyl, aryl and cyclopentadienyl; wherein each R 1 is independently hydrogen, alkyl or alkenyl.

[0151] The term "cyclopentadienyl" as a group or part of a group refers to a group having the formula (V):

[0152]

[0153] Among them, R d ,R e ,R f ,R g ,R h Each independently selected from hydrogen, alkyl, alkenyl, alkoxy or heteroalkyl as defined above. As disclosed herein, cyclopentadienyl is a 5-membered carbocyclic ring that is combined with a metal such as hafnium and / or zirconium by a covalent η5-bond. Therefore, for example, "cyclopentadienyl" refers to hydrogenated cyclopentadiene-2,4-Dean-1-base (Cp) and substituted cyclopentadiene-2,4-Dean-1-base, such as methyl-cyclopentadiene-2,4-Dean-1-base (MeCp), ethyl-cyclopentadiene-2,4-Dean-1-base (EtCp) and n-propyl-cyclopentadiene-2,4-Dean-1-base (n-PrCp).

[0154] In some embodiments, the present disclosure provides that Q 11 ,Q 12 ,Q 13 ,Q 14 are each independently selected from halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl.

[0155] In some embodiments, the present disclosure provides that Q 11 ,Q 12 ,Q 13 ,Q 14 are each independently selected from halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 2. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-4 Alkyl or C 2-4 Alkenyl.

[0156] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the alkyl group is C 1-8 Alkyl, more specifically C 1-4 More particularly, the alkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 alkyl group.

[0157] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the alkenyl group is C 2-8 Alkenyl, more specifically C 2-4 More particularly, alkenyl is C2, C3, C4, C5, C6, C7 and / or C8 alkenyl.

[0158] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the alkoxy group is C 1-8 Alkoxy, more specifically C 1-4 Alkoxy. More particularly, alkoxy is C1, C2, C3, C4, C5, C6, C7 and / or C8 alkoxy.

[0159] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the heteroalkyl group is a heteroC 1-8 Alkyl, more specifically heteroC 1-4 More particularly, the heteroalkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 heteroalkyl group.

[0160] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the cycloalkoxy group is C 3-8 Cycloalkoxy. More particularly, cycloalkoxy is C3, C4, C5, C6, C7 and / or C8 cycloalkoxy.

[0161] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the cycloalkyl group is C 3-8 Cycloalkyl. More particularly, cycloalkyl is C3, C4, C5, C6, C7 and / or C8 cycloalkyl.

[0162] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (III), the aryl group is C 6-10 More particularly, aryl is C6, C7, C8, C9 and / or C 10 Aryl.

[0163] In certain embodiments, the methods disclosed herein provide that one or more hafnium precursors are selected from HfCl4, HfBr4, HfI4, HfMe4, HfEt4, Hf(nPr)4, Hf(iPr)4, Hf(nBu)4, Hf(tBu)4, Hf(NMe2)4, Hf(NEt2)4, Hf[MeEtN]4, HfCp[(NMe2)3], Hf(OMe)4, Hf(OEt)4, Hf(OnPr)4, Hf(OiPr)4, Hf(OnBu)4, Hf(OtBu)4, Hf[(CpMe)2][OMe][Me], Hf[(CpMe)2][(Me)2], tetrakis(1-methoxy-2-methyl-2-propoxy)hafnium (Hf(mmp)4).

[0164] In certain embodiments, the methods disclosed herein provide that one or more zirconium precursors are represented by the following general formula (IV),

[0165]

[0166] Among them, Q 15 ,Q 16 ,Q 17 ,Q 18 Each is independently selected from halogen, alkyl, alkenyl, N(R 1 )2, alkoxy, heteroalkyl, cycloalkyl, aryl and cyclopentadienyl; wherein each R 1 is independently hydrogen, alkyl or alkenyl.

[0167] In some embodiments, the present disclosure provides that Q 15 ,Q 16 ,Q 17 ,Q 18 are each independently selected from halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl.

[0168] In some embodiments, the present disclosure provides that Q 15 ,Q 16 ,Q 17 ,Q 18 are each independently selected from halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 12. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-4 Alkyl or C 2-4 Alkenyl.

[0169] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the alkyl group is C 1-8 Alkyl, more specifically C 1-4 More particularly, the alkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 alkyl group.

[0170] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the alkenyl group is C 2-8 Alkenyl, more specifically C 2-4 More particularly, alkenyl is C2, C3, C4, C5, C6, C7 and / or C8 alkenyl.

[0171] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the alkoxy group is C 1-8 Alkoxy, more specifically C 1-4 Alkoxy. More particularly, alkoxy is C1, C2, C3, C4, C5, C6, C7 and / or C8 alkoxy.

[0172] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the heteroalkyl group is a heteroC 1-8 Alkyl, more specifically heteroC 1-4 More particularly, the heteroalkyl group is a C1, C2, C3, C4, C5, C6, C7 and / or C8 heteroalkyl group.

[0173] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the cycloalkoxy group is C 3-8 Cycloalkoxy. More particularly, cycloalkoxy is C3, C4, C5, C6, C7 and / or C8 cycloalkoxy.

[0174] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the cycloalkyl group is C 3-8 Cycloalkyl. More particularly, cycloalkyl is C3, C4, C5, C6, C7 and / or C8 cycloalkyl.

[0175] According to certain embodiments, the methods disclosed herein provide that, for one or more germanium dopants represented by the general formula (V), the aryl group is C 6-10 More particularly, aryl is C6, C7, C8, C9 and / or C 10 Aryl.

[0176] In certain embodiments, the methods disclosed herein provide that one or more zirconium precursors are selected from ZrCl4, ZrBr4, ZrI4, ZrMe4, ZrEt4, Zr(nPr)4, Zr(iPr)4, Zr(nBu)4, Zr(tBu)4, Zr(NMe2)4, Zr(NEt2)4, Zr[MeEtN]4, ZrCp[(NMe2)3], Zr(OMe)4, Zr(OEt)4, Zr(OnPr)4, Zr(OiPr)4, Zr(OnBu)4, Zr(OtBu)4, Zr[(CpMe)2][OMe][Me], Zr[(CpMe)2][(Me)2], tetrakis(1-methoxy-2-methyl-2-propoxy)zirconium (Zr(mmp)4). Advantageously, the hafnium precursor and / or zirconium precursor disclosed herein is specifically selected to have low volatility so as to evaporate easily.

[0177] In the present disclosure, one or more oxygen reactants may react with the chemically adsorbed hafnium and / or zirconium. In certain embodiments, the one or more oxygen reactants are selected from H2O, H2O2, O3, O2, O-containing plasma, N2O, NO, N2O5, and oxygen radicals.

[0178] The methods disclosed herein can be performed at different temperatures and / or pressures. In certain embodiments, the methods disclosed herein provide that the substrate can be heated to a temperature of about 80°C to about 400°C, or about 100°C to about 400°C, or about 125°C to about 400°C, preferably about 150°C to about 400°C, or about 175°C to about 400°C, preferably about 200°C to about 400°C, or about 250°C to about 400°C, or about 300°C to about 400°C. The listed temperatures can reduce the time required for material deposition, although lower or higher temperatures are also contemplated.

[0179] In certain embodiments, the methods disclosed herein provide for a pressure in the reaction chamber of between about 0.1 Torr and about 100.0 Torr, or between about 0.5 Torr and about 100.0 Torr, or between about 1.0 Torr and about 100.0 Torr, or between about 2.0 Torr and about 100.0 Torr, or between about 5.0 Torr and about 100.0 Torr, or between about 5.0 Torr and about 80.0 Torr, or preferably between about 5.0 Torr and about 50.0 Torr, or between about 10.0 Torr and about 50.0 Torr. The listed pressures can reduce the time required for material deposition, although lower or higher pressures are also contemplated.

[0180] The germanium-doped HfO2 film and / or the germanium-doped HZO film can be formed in any suitable reactor. Therefore, in some embodiments, the germanium-doped HfO2 film and / or the germanium-doped HZO film is deposited in a cross-flow reactor. In some embodiments, the germanium-doped HfO2 film and / or the germanium-doped HZO film is deposited in a showerhead reactor. In some embodiments, the germanium-doped HfO2 film and / or the germanium-doped HZO film is deposited in a hot wall reactor. In some embodiments, the germanium-doped HfO2 film and / or the germanium-doped HZO film is deposited in a cold wall reactor. Doing so can advantageously improve the uniformity and / or repeatability of the germanium-doped HfO2 film and / or the germanium-doped HZO film deposition process.

[0181] In some embodiments, after the cyclic deposition process, the substrate is subjected to an annealing step in an environment containing hydrogen and nitrogen. Suitably, the annealing step may be performed at a temperature of at least 300° C. to at most 600° C. Alternatively, the annealing step may be performed at a temperature of at least 300° C. to at most 1000° C.

[0182] In some embodiments, the hafnium precursor, zirconium precursor and / or oxygen reactant are provided to the reaction chamber via a carrier gas. Exemplary carrier gases include nitrogen (N2) and a noble gas such as He, Ne, Ar, Xe or Kr.

[0183] Another aspect of the present disclosure relates to a system comprising:

[0184] a reaction chamber constructed and arranged to hold a substrate;

[0185] a hafnium precursor container constructed and arranged to contain and evaporate one or more hafnium precursors;

[0186] a zirconium precursor vessel constructed and arranged to contain and vaporize one or more zirconium precursors;

[0187] an oxygen reactant vessel constructed and arranged to contain and vaporize one or more oxygen reactants;

[0188] a germanium dopant vessel constructed and arranged to contain and evaporate one or more germanium dopants;

[0189] a controller operably connected to the hafnium precursor container, the zirconium precursor container, the oxygen reactant container, and the germanium dopant container;

[0190] The controller is configured to control the introduction of one or more hafnium precursors, one or more zirconium precursors, one or more oxygen reactants, and one or more germanium dopants into the reaction chamber during one or more cycles, wherein as a result of the cycles, a charge trapping layer including one or more germanium-doped HfO2 films and / or one or more germanium-doped HZO films is formed on the substrate.

[0191] In certain embodiments, the systems disclosed herein provide that, as a result of the cycling, a charge trapping layer including one or more germanium-doped HfO 2 films and one or more germanium-doped HZO films is formed on the substrate.

[0192] In certain embodiments, the systems disclosed herein provide that the one or more cycles is a plurality of cycles.

[0193] It has been found that a controller configured to precisely control the introduction of precursor gases, reactive gases, and dopant gases is particularly advantageous for performing well-controlled chemical reactions that can produce more uniform and reproducible thin films or layers. In addition, the controller can adjust the flow rates and timing to optimize the reaction kinetics to produce desired film properties, such as reduced charge leakage, uniform layer thickness, and controlled composition of the formed charge trapping layer. In particular, the system can be configured to form a charge trapping layer with reduced layer thickness variation and defects, resulting in an improved memory device.

[0194] In certain embodiments, the systems disclosed herein are configured to form a charge-trapping layer of a storage element by the methods disclosed herein.

[0195] In some embodiments, the hafnium precursor, zirconium precursor, oxygen reactant, and / or germanium dopant are provided to the reaction chamber from a temperature-controlled container. In some embodiments, the temperature-controlled container is configured to cool the precursors, reactants, and / or dopants. In some embodiments, the temperature-controlled container is configured to heat the precursors, reactants, and / or dopants. In some embodiments, the temperature-controlled container is maintained at a temperature of at least -50°C to at most 20°C, or at a temperature of at least 20°C to at most 250°C, or at a temperature of at least 100°C to at most 200°C.

[0196] Figure 6 A system 600 according to another exemplary embodiment of the present disclosure is schematically shown. The system 600 can be used to perform the methods described herein and / or form a portion of a structure or device described herein.

[0197] In the illustrated example, the system 600 includes one or more reaction chambers 602, a hafnium precursor gas source 604, an oxygen reactant gas source 606, a germanium dopant source 608, a purge gas source 610, an exhaust 612, and a controller 614. The reaction chamber 602 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. Optionally, the system 600 includes additional gas sources, such as a gas source 607 containing a zirconium precursor.

[0198] The hafnium precursor gas source 604 may include a container and one or more hafnium precursors as described herein, either alone or mixed with one or more carrier gases (e.g., inert gases). The oxygen reactant gas source 606 may include a container and one or more nitrogen reactants as described herein, either alone or mixed with one or more carrier gases. The germanium dopant gas source 608 may include a container and one or more germanium dopants as described herein, either alone or mixed with one or more carrier gases. As described herein, the purge gas source (610) may include one or more inert gases, such as N2 or a rare gas. The system 600 may include any suitable number of gas sources. The gas sources 604-610 may be coupled to the reaction chamber 602 via lines 616-622, which may each include a flow controller, a valve, a heater, etc. The exhaust device 612 may include one or more vacuum pumps.

[0199] The controller 614 includes electronic circuits and software to selectively operate valves, manifolds, heaters, pumps and other components included in the system 600. Such circuits and components are used to introduce precursors, reactants and purge gases from the corresponding sources 604-610. The controller 614 can control the timing of gas pulse sequences, the temperature of the substrate and / or the reaction chamber, the pressure in the reaction chamber, and various other operations to provide the correct operation of the system 600. The controller 614 may include control software to control the flow of precursors, reactants (i.e., nitrogen reactants and / or oxygen reactants) and purge gases into and out of the reaction chamber 602 by electrically or pneumatically controlling valves. The controller 614 may include modules that perform certain tasks, such as software or hardware components, such as FPGAs or ASICs. The modules may be advantageously configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0200] Other configurations of the system 600 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the goal of selectively supplying gases into the reaction chamber 602. In addition, as a schematic representation of the system, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0201] During operation of reactor system 600, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to reaction chamber 602. Once the substrate is transferred to reaction chamber 602, one or more gases, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into reaction chamber 602 from gas sources 604-610.

[0202] Another aspect of the present disclosure relates to a storage element, comprising:

[0203] Gate electrode;

[0204] a blocking dielectric, the blocking dielectric being adjacent to the gate electrode;

[0205] Tunnel dielectrics;

[0206] a charge-trapping layer located between the blocking dielectric and the tunnel dielectric;

[0207] an n-type layer adjacent to the tunnel dielectric; and

[0208] A p-type layer, which is adjacent to the n-type layer;

[0209] Wherein, the charge trapping layer is obtained by the method disclosed in this article.

[0210] Another aspect of the present disclosure relates to a storage element, comprising:

[0211] Gate electrode;

[0212] a blocking dielectric, the blocking dielectric being adjacent to the gate electrode;

[0213] Tunnel dielectrics;

[0214] a charge-trapping layer located between the blocking dielectric and the tunnel dielectric;

[0215] an n-type layer adjacent to the tunnel dielectric; and

[0216] A p-type layer, which is adjacent to the n-type layer;

[0217] Wherein, the charge trapping layer includes one or more germanium-doped HZO films.

[0218] Advantageously, the memory element disclosed herein can be considered a general purpose technology because it can be readily adapted to various electronic devices and systems, including but not limited to computers, consumer electronics, communications equipment, automotive systems, and industrial control systems. In addition, one or more germanium-doped HZO films are characterized by deep charge traps, resulting in improved charge retention of the charge trapping layer and allowing the memory element to more accurately write, erase, and read data. In some embodiments, the memory element can be used in a solid-state drive or a memory card.

[0219] In certain embodiments, the memory elements disclosed herein provide that the charge trapping layer further includes one or more germanium-doped hafnium oxide films and / or one or more hafnium oxide films.

[0220] In a specific embodiment, the memory element disclosed herein provides that the germanium-doped HZO layer includes a Hf / Zr molar atomic ratio of 0.1 to 0.9, or 0.2 to 0.8, or 0.3 to 0.7, or 0.4 to 0.7, or 0.5 to 0.7, or 0.3 to 0.6, and preferably a Hf / Zr molar atomic ratio of about 0.5. This has the advantage of adjusting the capacitance of the charge trapping layer without increasing or substantially increasing the charge leakage or charge loss of the charge trapping layer. Outside this range, the charge trapping stability may be affected and / or a thicker charge trapping layer may be required.

[0221] In a specific embodiment, the memory element disclosed herein provides that the germanium-doped HZO layer includes the following molar atomic percentages: 0.10 atomic % to 15.0 atomic %, or 0.50 atomic % to 15.0 atomic %, or 1.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 10.0 atomic %. Preferably, the germanium dopant in the germanium-doped HZO layer includes a molar atomic percentage of less than 10.0 atomic %, for example, less than 9.0 atomic %, or less than 8.0 atomic %, or less than 7.0 atomic %, or less than 6.0 atomic %, or less than 5.0 atomic %, or less than 4.0 atomic %, or less than 3.0 atomic %, or less than 2.0 atomic %, or less than 1.0 atomic %, or less than 0.5 atomic %.

[0222] In a preferred embodiment, the memory element disclosed herein provides that the charge trapping layer is obtained by the method disclosed herein.

[0223] Another aspect of the present disclosure relates to a gate stack 3D NAND memory, including a vertical channel and a plurality of floating gate stacks, each floating gate stack including a tunnel dielectric adjacent to the vertical channel, a charge trapping layer adjacent to the tunnel dielectric, a blocking dielectric adjacent to the charge trapping layer, and a gate electrode adjacent to the blocking dielectric; wherein the charge trapping layer includes one or more germanium-doped HZO films.

[0224] Generally speaking, 3D NAND (non-and) memory refers to a non-volatile memory technology that enhances data storage capacity and performance by vertically stacking memory cells into multiple layers (e.g., floating gate stacks). Unlike conventional 2D NAND memory devices, the gate stack 3D NAND memory disclosed herein is suitable for applications that require large data storage in a compact form, such as solid-state drives and memory cards. The advantage of a gate stack 3D NAND memory including a charge trapping layer is that performance is improved due to increased charge retention of the charge traps, the charge trapping layer including one or more germanium-doped HZO films.

[0225] In certain embodiments, the gate stack 3D NAND memory disclosed herein provides that the charge trapping layer further includes one or more germanium-doped hafnium oxide films and / or one or more hafnium oxide films.

[0226] In a specific embodiment, the gate stack 3D NAND memory disclosed herein provides that the germanium-doped HZO layer includes a Hf / Zr molar atomic ratio of 0.3 to 0.7, and preferably a Hf / Zr molar atomic ratio of about 0.5. This has the advantage of adjusting the capacitance of the charge trapping layer without increasing or substantially increasing the charge leakage or charge loss of the charge trapping layer. Outside this range, the charge trapping stability may be affected and / or a thicker charge trapping layer may be required.

[0227] In a specific embodiment, the gate stack 3D NAND memory disclosed herein provides that the germanium-doped HZO layer includes the following molar atomic percentages: 0.10 atomic % to 15.0 atomic %, or 0.50 atomic % to 15.0 atomic %, or 1.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 15.0 atomic %, or 5.0 atomic % to 10.0 atomic %. Preferably, the germanium dopant in the germanium-doped HZO layer includes a molar atomic percentage of less than 10.0 atomic %, for example, less than 9.0 atomic %, or less than 8.0 atomic %, or less than 7.0 atomic %, or less than 6.0 atomic %, or less than 5.0 atomic %, or less than 4.0 atomic %, or less than 3.0 atomic %, or less than 2.0 atomic %, or less than 1.0 atomic %, or less than 0.50 atomic %.

[0228] In a preferred embodiment, the gate stack 3D NAND memory disclosed herein provides that the charge trapping layer is obtained by the method disclosed herein.

[0229] In a preferred embodiment, the gate stack 3D NAND memory disclosed herein further comprises a storage element according to the storage element disclosed herein.

[0230] Another aspect of the present disclosure relates to the use of germanium precursors to increase charge traps in semiconductor structures and reduce the charge loss rate of charge trapping layers.

[0231] In certain embodiments, the uses disclosed herein provide that the germanium precursor is represented by the general formula (I) or (II),

[0232]

[0233] Among them, Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q8 ,Q 9 and Q 10 has the meaning as defined above.

[0234] In some embodiments, the uses disclosed herein provide that the germanium precursor is selected from the group consisting of Ge2H6, GeH4, GeF4, GeHF3, GeH2F2, GeH3F1, GeCl4, GeHCl3, GeH2Cl2, GeH3Cl1, GeBr4, GeHBr3, GeH2Br2, GeH3Br1, GeI4, GeHI3, GeH2I2, GeH3I1, GeF2(C4H8O2), GeCl2(C4H8O2), GeBr2(C4H8O2), GeI2(C4H8O2), GeH2Me2, GeH2Et2, GeH2(i-Pr)2, GeH(n-Bu)3, Ge(NMe2)4, Ge(NMeEt)4, Ge(NEt2)4, Ge[N(SiMe3 )2]4,Ge(NMe2)2[N(SiMe3)2]2,Ge(NMe2)2[NHt-Bu(CH2)2NHt-Bu],Ge[NHt-Bu(CH 2)2NHt-Bu]2,Ge(NMe2)2[NHi-Pr(CH2)2NHi-Pr],Ge[NHi-Pr(CH2)2NHi-Pr]2,Ge( OMe)4,Ge(OEt)4,Ge(Oi-Pr)4,Ge(Ot-Bu)4, or Ge(On-Bu)4,GeN(CH3)2[(Ni-Pr)2C= N-(CH3)2], GeN(CH3)2[1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine]; and the preferred germanium precursor is Ge(NMe2)4.

[0235] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

[0236] The illustrations presented herein are not meant to be actual views of any particular material, structure, or device but are merely idealized representations used to describe embodiments of the present disclosure.

[0237] The specific embodiments shown and described are illustrative of the present disclosure and its best mode and are not intended to limit the scope of these aspects and embodiments in any way. In fact, for the sake of brevity, the traditional manufacturing, connection, preparation and other functional aspects of the system may not be described in detail. In addition, the connecting lines shown in the various figures are intended to represent exemplary functional relationships and / or physical connections between various elements. In actual systems, there may be many alternative or additional functional relationships or physical connections, and / or may not exist in some embodiments.

[0238] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

Claims

1. A method for forming a charge trapping layer of a storage element, comprising the following steps: a) providing a substrate into a reaction chamber; b) Execute multiple loops, the loops include: i. a hafnium precursor pulse, wherein at least a portion of the substrate is contacted with one or more hafnium precursors by introducing the one or more hafnium precursors into the reaction chamber; ii. Optionally, a zirconium precursor pulse, wherein at least a portion of the substrate is contacted with one or more zirconium precursors by introducing one or more zirconium precursors into the reaction chamber; iii. an oxygen reactant pulse, wherein at least a portion of the substrate is contacted with one or more oxygen reactants by introducing one or more oxygen reactants into the reaction chamber; iv. a germanium dopant pulse, wherein at least a portion of the substrate is contacted with one or more germanium dopants by introducing one or more germanium dopants into the reaction chamber; and Wherein, as a result of the plurality of cycles, a charge trapping layer including one or more germanium-doped hafnium zirconium oxide (HZO) films is formed on the substrate.

2. The method according to claim 1, wherein: The one or more germanium dopants are represented by the following general formula (I) or (II), Among them, Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q 10 are each independently selected from hydrogen, halogen, alkyl, alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 )2, alkoxy, heteroalkyl, cycloalkyloxy, cycloalkyl, aryl and (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, alkyl, alkenyl or Si(R 5 )3; where each R 3 is an alkyl group; and wherein each R 5 are independently hydrogen or alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

3. The method according to claim 2, wherein: Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q 10 are each independently selected from hydrogen, halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, C 1-8 Alkyl, C 2-8 Alkenyl or Si(R 5 )3; where each R 3 It is C 1-8 Alkyl; wherein each R 5 are independently hydrogen or C 1-8 Alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

4. The method according to claim 2, wherein: Q 1 ,Q 2 ,Q 3 ,Q 4 ,Q 5 ,Q 6 ,Q 7 ,Q 8 ,Q 9 ,Q 10 are each independently selected from hydrogen, halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 )2、(R 2 )2NR 3 N(R 4 2. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkoxy, C 3-8 Cycloalkyl, C 6-10 Aryl, (R6R7N)(R8R9N)C=NR 10 ; where each R 1 , R 2 and R 4 are independently hydrogen, C 1-4 Alkyl, C 2-4 Alkenyl or Si(R 5 )3; where each R 3 It is C 1-4 Alkyl; wherein each R 5 are independently hydrogen or C 1-4 Alkyl; and wherein (R6R7N)(R8R9N)C=NR 10 It is 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine.

5. The method according to claim 1, wherein: The one or more germanium dopants are selected from Ge2H6, GeH4, GeF4, GeHF3, GeH2F2, GeH3F1, GeCl4, GeHCl3, GeH2Cl2, GeH3Cl1, GeBr4, GeHBr3, GeH2Br2, GeH3Br1, GeI4, GeHI3, GeH2I2, GeH3I1, GeF2(C4H8O2), GeCl2(C4H8O2), GeBr2(C4H8O2), GeI2(C4H8O2), GeH2Me2, GeH2Et2, GeH2(i-Pr)2, GeH(n-Bu)3, Ge(NMe2)4, Ge(NMeEt)4, Ge(NEt2)4, Ge[N(S iMe3)2]4,Ge(NMe2)2[N(SiMe3)2]2,Ge(NMe2)2[NHt-Bu(CH2)2NHt-Bu],Ge[NHt-Bu(CH2)2NHt-Bu]2,Ge(NMe2)2[NHi-Pr(CH2)2NHi-Pr],Ge[NHi-Pr(CH2)2N Hi-Pr]2,Ge(OMe)4,Ge(OEt)4,Ge(Oi-Pr)4,Ge(Ot-Bu)4, or Ge(On-Bu)4,GeN(CH 3) 2[(Ni-Pr)2C=N-(CH3)2] and GeN(CH3)2[1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine].

6. The method according to claim 1, wherein: The one or more germanium dopants are Ge(NMe2)4.

7. The method according to claim 1, wherein: The one or more hafnium precursors are represented by the following general formula (III), Among them, Q 11 ,Q 12 ,Q 13 ,Q 14 are independently selected from halogen, alkyl, alkenyl, N(R 1 )2, alkoxy, heteroalkyl, cycloalkyl, aryl and cyclopentadienyl; wherein each R 1 is independently hydrogen, alkyl or alkenyl.

8. The method according to claim 7, wherein: Q 11 ,Q 12 ,Q 13 ,Q 14 are each independently selected from halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl.

9. The method according to claim 7, wherein: Q 11 ,Q 12 ,Q 13 ,Q 14 are each independently selected from halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 2. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-4 Alkyl or C 2-4 Alkenyl.

10. The method according to claim 1, wherein: The one or more hafnium precursors are selected from HfCl4, HfBr4, HfI4, HfMe4, HfEt4, Hf(nPr)4, Hf(iPr)4, Hf(nBu)4, Hf(tBu)4, Hf(NMe2)4, Hf(NEt2)4, Hf[MeEtN]4, HfCp[(NMe2)3], Hf(OMe)4, Hf(OEt)4, Hf(OnPr)4, Hf(OiPr)4, Hf(OnBu)4, Hf(OtBu)4, Hf[(CpMe)2][OMe][Me], Hf[(CpMe)2][(Me)2], tetrakis(1-methoxy-2-methyl-2-propoxy)hafnium (Hf(mmp)4).

11. The method according to claim 1, wherein: The one or more zirconium precursors are represented by the following general formula (IV), Among them, Q 15 ,Q 16 ,Q 17 ,Q 18 Each is independently selected from halogen, alkyl, alkenyl, N(R 1 )2, alkoxy, heteroalkyl, cycloalkyl, aryl and cyclopentadienyl; wherein each R 1 is independently hydrogen, alkyl or alkenyl.

12. The method according to claim 11, wherein: Q 15 ,Q 16 ,Q 17 ,Q 18 are each independently selected from halogen, C 1-8 Alkyl, C 2-8 Alkenyl, N(R 1 2. C 1-8 Alkoxy, heterocyclic C 1-8 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-8 Alkyl or C 2-8 Alkenyl.

13. The method according to claim 11, wherein: Q 15 ,Q 16 ,Q 17 ,Q 18 are each independently selected from halogen, C 1-4 Alkyl, C 2-4 Alkenyl, N(R 1 2. C 1-4 Alkoxy, heterocyclic C 1-4 Alkyl, C 3-8 Cycloalkyl, C 6-10 aryl and cyclopentadienyl; wherein each R 1 are independently hydrogen, C 1-4 Alkyl or C 2-4 Alkenyl.

14. The method according to claim 1, wherein: The one or more zirconium precursors are selected from ZrCl4, ZrBr4, ZrI4, ZrMe4, ZrEt4, Zr(nPr)4, Zr(iPr)4, Zr(nBu)4, Zr(tBu)4, Zr(NMe2)4, Zr(NEt2)4, Zr[MeEtN]4, ZrCp[(NMe2)3], Zr(OMe)4, Zr(OEt)4, Zr(OnPr)4, Zr(OiPr)4, Zr(OnBu)4, Zr(OtBu)4, Zr[(CpMe)2][OMe][Me], Zr[(CpMe)2][(Me)2], tetrakis(1-methoxy-2-methyl-2-propoxy)zirconium (Zr(mmp)4).

15. The method according to claim 1, wherein: The one or more oxygen reactants are selected from H2O, H2O2, O3, O2, O-containing plasma, N2O, NO, N2O5 and oxygen radicals.

16. The method according to claim 1, wherein: The substrate includes silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride or silicon carbide.

17. The method according to claim 1, wherein: The substrate is heated to a temperature of about 80°C to about 400°C.

18. The method according to claim 1, wherein: The pressure in the reaction chamber is between about 0.1 Torr and about 100.0 Torr.

19. The method according to claim 1, wherein: An oxygen reactant pulse is performed after each hafnium precursor pulse and / or after each zirconium precursor pulse.

20. The method according to claim 19, wherein: The germanium dopant pulse is performed after the hafnium precursor pulse without any intermediate oxygen reactant pulse.

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