Enhanced ald film growth in dual-chamber

Abstract

A method for forming a film on a surface of a substrate is provided. The method includes introducing the substrate into a lower chamber of a reaction chamber, wherein the reaction chamber is divided into an upper chamber and the lower chamber using an ion trap; introducing a first plasma into the upper chamber; introducing a precursor into the reaction chamber and radicalizing the precursor using the first plasma; introducing a reactant into the reaction chamber; introducing a second plasma into the upper chamber to radicalize the reactant.

Description

Technical Field

[0001] The present invention relates to a method and system for enhanced ALD film growth in a deposition chamber having two plasma zones, and more particularly, to a method and system for partially decomposing precursors for enhanced ALD film growth in the two zones. Background Technology

[0002] Fabricating modern semiconductor devices requires the precise deposition of materials with carefully controlled thickness and composition. Ideally, the desired material composition could be deposited directly in a single-step process, but this is often impractical, necessitating the deposition of a material layer and then its transformation into a layer with the desired elemental composition and properties. For example, SiON can be fabricated by exposing a SiO2 layer to N2 plasma, as the reactivity of nitrogen ions and radicals is insufficient to remove all oxygen from the film. However, carbonitride films such as SiCN or SiOCN present further challenges, as any carbon present in the precursor molecules or grown film is readily removed by nitrogen or oxygen plasma. Using a CVD process with precursor chemicals containing the desired elements would be an option, but this introduces issues with film conformability and compositional control. Alternative processing options exist to enhance the usability of CVD precursors, where the precursor is exposed to a low-power plasma that partially breaks down the molecules to produce more reactive material more likely to adhere to the substrate surface. This so-called precursor radicalization method makes CVD precursors usable for ALD processing, and it requires exposing the precursor stream to direct plasma without affecting the substrate.

[0003] Plasma-enhanced atomic layer deposition (PEALD) is a widely used deposition method in which plasma is used to generate high-energy ions and reactive radicals, which can greatly benefit the deposition process. However, due to the inherent anisotropic nature of ion flux on the substrate, PEALD processes often suffer from conformal issues in the deposited film. To combat this, radical-enhanced ALD (REALD) was developed as a variant of PEALD, in which ions formed in the plasma sheath are not allowed to reach the substrate, and film growth depends solely on reactive radicals in the plasma. This approach results in a process with properties between PEALD and thermal ALD, and it can be very useful, especially for applications requiring high levels of conformal performance. However, some applications will benefit from the possibility of using both direct plasma treatment and radical exposure in the same process. Summary of the Invention

[0004] Embodiments of the present invention provide a method for forming a film on the surface of a substrate. The method includes introducing the substrate into a lower chamber of a reaction chamber, wherein the reaction chamber is divided into an upper chamber and a lower chamber using an ion trap. The method includes introducing a first plasma into the upper chamber. The method includes introducing a precursor into the reaction chamber and radicalizing the precursor using the first plasma. The method includes introducing a reactant into the reaction chamber. The method includes introducing a second plasma into the upper chamber to radicalize the reactant.

[0005] In some embodiments, the precursor comprises a silazane. In some embodiments, the ion trap is grounded. In some embodiments, the precursor and reactants are introduced into the reaction chamber via a spray head. The spray head is connected to an RF generator to generate a first plasma and a second plasma. In some embodiments, the first and second plasmas induce self-confined thin film growth. In some embodiments, the method further includes a purging step after introducing the precursor into the reaction chamber and after introducing the second plasma into the upper chamber. In some embodiments, the RF power of the first plasma is lower than the RF power of the second plasma. In some embodiments, the RF power of the first plasma is less than 100 W, and the RF power of the second plasma is greater than 50 W.

[0006] Embodiments of the present invention provide a method for forming a film on the surface of a substrate. The method includes providing a reaction chamber having an upper chamber and a lower chamber separated by an ion trap. The method includes introducing a substrate into the lower chamber. The method includes introducing a precursor into the reaction chamber and using a first plasma in the upper chamber to radicalize the precursor to form a radicalized precursor. The method includes introducing reactants into the reaction chamber and generating a second plasma in the lower chamber to decompose the reactants and expose the substrate to ions and other plasma material. The RF power of the second plasma is higher than that of the first plasma.

[0007] In some embodiments, the precursor comprises a silazane. In some embodiments, the method further includes purging the reaction chamber between the steps of introducing the precursor and introducing the reactant. In some embodiments, the method further includes repeating the steps of providing the precursor and providing the reactant. In some embodiments, the precursor and reactant are introduced into the reaction chamber via a spray head, and the spray head is connected to a first RF generator to generate a first plasma. A substrate is placed on a base, and the base is connected to a second RF generator to generate a second plasma. In some embodiments, the RF power of the first plasma is less than 100 W, and the RF power of the second plasma is less than 1500 W. In some embodiments, the reactant comprises at least one of hydrogen, nitrogen, and oxygen. In some embodiments, the RF power of the second plasma is higher than the RF power of the first plasma.

[0008] Embodiments of the present invention provide a semiconductor processing apparatus, including a reaction chamber, a spray head, a base, an ion trap, a precursor source, a reactant source, and a first RF generator. The spray head is located at the upper part of the reaction chamber. The base is located at the lower part of the reaction chamber and supports a substrate. The ion trap is disposed between the spray head and the base. The precursor source introduces a precursor into the reaction chamber via the spray head. The reactant source introduces a reactant into the reaction chamber via the spray head. The first RF generator is connected to the spray head and generates a first plasma between the spray head and the ion trap via the spray head.

[0009] In some embodiments, the ion trap is a mesh plate, and the mesh plate is grounded. In some embodiments, the semiconductor processing apparatus further includes a controller. The controller is configured to ignite a first plasma between the spray head and the ion trap. The controller is configured to introduce a precursor into the reaction chamber. The controller is configured to purge the reaction chamber. The controller is configured to introduce reactants into the reaction chamber. The controller is configured to ignite a second plasma between the ion trap and the base. The controller is configured to purge the reaction chamber. In some embodiments, a second RF generator is connected to the base and generates a second plasma between the ion trap and the base via the base. In some embodiments, the first RF generator and the second RF generator are separate RF generators. Attached Figure Description

[0010] A more complete understanding of the invention can be obtained by referring to the following detailed description and examples, in which:

[0011] Figure 1 This is a schematic diagram of a method for forming a film on the surface of a substrate according to some embodiments of the present disclosure;

[0012] Figure 2 This is a timing diagram according to some embodiments of the present disclosure;

[0013] Figure 3 This is a schematic diagram of a method for forming a film on the surface of a substrate according to some embodiments of the present disclosure;

[0014] Figure 4 This is a schematic diagram of a semiconductor processing apparatus according to some embodiments of the present disclosure;

[0015] Figure 5 This is a schematic diagram of a semiconductor processing apparatus according to some embodiments of the present disclosure. Detailed Implementation

[0016] This disclosure will now be described more fully below with reference to the accompanying drawings. However, this disclosure may be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0017] It should be understood that although the terms “first,” “second,” etc., may be used herein to describe various components, regions, layers, and / or parts, these components, regions, layers, and / or parts should not be limited by these terms. These terms do not refer to a particular order, vertical relationship, or preference, and are used only to distinguish one component, region, or part from another. Therefore, without departing from the teachings of this disclosure, the first component, region, or part described below may refer to the second component, region, or part.

[0018] As used herein, "basic" or "approximately equivalent" means ±5%, ±2%, ±1%, or ±0.5% of another value or shape (e.g., one or more cross-sectional dimensions of a shape). Percentages can be absolute or relative.

[0019] In the accompanying drawings, variations in the illustrated shapes can be anticipated due to factors such as manufacturing techniques and / or tolerances. Therefore, embodiments should not be construed as limited to a specific shape within the areas shown herein, but may include shape deviations, for example, due to manufacturing processes. Furthermore, the drawings may be used to illustrate various features that may not be drawn to scale.

[0020] When phrases like "at least one of..." precede a list of components, they modify the entire list of components, but not the individual components in the list.

[0021] As used herein, the abbreviation "ALD" for "atomic layer deposition" refers to a method of depositing a film on a substrate by sequentially exposing the surface of the substrate to alternating gaseous reactants. Unlike chemical vapor deposition, the different reactants are not present simultaneously in the reactor, but are introduced as a series of sequential, non-overlapping pulses. In each of these pulses, the reactant reacts with the surface in a self-limiting or substantially self-limiting manner. Furthermore, as used herein, ALD can also refer to processes specified by related terms such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas-source MBE or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of reactants.

[0022] As used in this article, "boron carbide" or "B" x C y "Borne carbide" refers to a material containing boron and carbon. In some embodiments, boron carbide may not include a significant proportion of elements other than boron and carbon. In some embodiments, boron carbide comprises B4C. In some embodiments, boron carbide may consist essentially of B4C. In some embodiments, boron carbide may not include stoichiometric amounts of boron carbide. In some cases, boron carbide may contain other elements, such as hydrogen.

[0023] As used in this article, "boron carbonitride" or "B"x C y N z "" refers to materials containing boron, carbon, and nitrogen. Boron carbonitride can be produced by formula B x C y N z This indicates that the sum of x, y, and z equals 3. In some cases, boron carbonitride can include other elements, such as hydrogen. Boron carbonitride can include both boron carbide and boron nitride.

[0024] As used in this article, "boron nitride" or "B" x N y "Boron nitride" refers to a material containing boron and nitrogen. In some embodiments, boron nitride may not include elements other than boron and nitrogen in significant proportions. In some embodiments, boron nitride includes BN. In some embodiments, boron nitride may consist essentially of BN. In some cases, boron nitride may not include stoichiometric amounts of boron nitride. In some cases, boron nitride may include other elements, such as hydrogen.

[0025] As used in this article, "boron oxide" or "B" x O y "" refers to a material containing boron and oxygen. In some embodiments, boron oxide may not include a significant proportion of elements other than boron and oxygen. Boron oxide can be produced by formula B x O y The expression indicates that x can be from about 0 to about 6, and y can be from about 0 to about 3. In some embodiments, boron oxide comprises B₂O₃. In some embodiments, boron oxide may consist essentially of B₂O₃. In some cases, boron oxide may not include stoichiometric amounts of boron oxide. In some cases, boron oxide may include other elements, such as carbon and / or hydrogen.

[0026] As used herein, the abbreviation "CVD" for "chemical vapor deposition" refers to a method of depositing a film on a substrate by exposing the substrate surface to one or more gaseous reactants, which react and / or decompose on the substrate surface to produce the desired film. Typically, CVD is performed by co-introducing the reactants into a reactor.

[0027] As used herein, “chemisorption” refers to an adsorption process caused by a reaction on an exposed surface, which creates, for example, covalent or ionic bonds between the surface and the adsorbate.

[0028] As used herein, a “membrane” refers to a continuous, substantially continuous, or discontinuous material that extends in a direction perpendicular to its thickness to cover at least a portion of a surface. Membranes can include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers, partial or complete atomic layers, or atomic and / or molecular clusters. Membranes can be constructed from one or more indistinguishable layers (e.g., monolayers or submonolayers) to produce a homogeneous or substantially homogeneous material, wherein the number of layers affects the thickness of the material.

[0029] As used herein, “gas” refers to a state of matter consisting of atoms or molecules that have neither a defined volume nor a defined shape. Gases include evaporated solids and / or liquids, and may, depending on the circumstances, consist of a single gas or a mixture of gases.

[0030] As used herein, “plasma” refers to an ionized gas containing approximately equal amounts of negatively and positively charged matter (typically electrons and ions). Plasma also contains excited and reactive matter, such as atoms and free radicals, metastable atoms and molecules, and photons. Plasma discharge requires an externally applied electric or magnetic field to ionize the gas. Plasma generation schemes and geometries include, but are not limited to, capacitively coupled plasma (CCP), inductively coupled plasma (ICP), and RF hollow cathode (HC) plasma, which differ in the generation of excited and reactive matter and therefore can provide very different fluxes of various substances.

[0031] As used herein, a "precursor" refers to a compound that participates in a chemical reaction to form another compound or element, wherein a portion of the precursor (an element or group within the precursor) is incorporated into the compound or element produced by the chemical reaction. The compound or element produced by the chemical reaction may be a layer and / or film formed on a substrate surface.

[0032] As used herein, "reactant" refers to a compound that participates in a chemical reaction to form another compound or element. In some cases, a reactant is a precursor. In other cases, the compound or element produced by a chemical reaction does not contain any part of the reactant (the element or group within the reactant), and therefore the reactant is not a precursor.

[0033] As used herein, "self-limiting" refers to a process that proceeds through a finite process and terminates once that finite process is complete. For example, a self-limiting surface reaction terminates when the surface becomes saturated and all available and / or accessible surface reactive sites are exhausted. At most, a single monolayer can form on the surface.

[0034] As used herein, “silicon carbide” or “SiC” refers to a material comprising silicon and carbon. In some embodiments, silicon carbide may not include a significant proportion of elements other than silicon and carbon. Silicon carbide may be represented by the formula SiC. In some embodiments, silicon carbide comprises SiC. In some embodiments, silicon carbide may consist essentially of SiC. Silicon carbide is not necessarily a stoichiometric composition. The amount of silicon may range from 5% to 50%; the amount of carbon may range from about 50% to about 95%. In some embodiments, the SiC film may include one or more elements other than silicon and carbon, such as hydrogen and / or nitrogen.

[0035] As used in this article, "silicon carbonitride" or "Si" x C y N z "Silicon carbonitride" or "SiCN" refers to a material comprising silicon, carbon, and nitrogen. Silicon carbonitride can be produced by the formula Si x C y N z In some embodiments, silicon carbonitride may contain more Si-N bonds than Si-C bonds, for example, the ratio of Si-N bonds to Si-C bonds may be from about 1:10 to about 10:1. In some embodiments, the silicon carbonitride film may contain about 0% to about 50% carbon on an atomic basis. In some embodiments, silicon carbonitride may contain about 0.1% to about 40%, about 0.5% to about 30%, about 1% to about 30%, or about 5% to about 20% carbon on an atomic basis. In some embodiments, silicon carbonitride may contain about 0% to about 70% nitrogen on an atomic basis. In some embodiments, silicon carbonitride may contain about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% nitrogen on an atomic basis. In some embodiments, silicon carbonitride may contain about 0% to about 50% silicon on an atomic basis. In some embodiments, silicon carbonitride may contain about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon on an atomic basis. In some cases, silicon carbonitride may include other elements, such as hydrogen. Silicon carbonitride may include both silicon carbide and silicon nitride.

[0036] As used in this article, "silicon nitride" or "Si" x N y "Silicon nitride" refers to a material comprising silicon and nitrogen. In some embodiments, silicon nitride may not include a significant proportion of elements other than silicon and nitrogen. Silicon nitride may be represented by the formula Si3N4. In some embodiments, silicon nitride comprises Si3N4. In some embodiments, silicon nitride may consist essentially of Si3N4. In some cases, silicon nitride may not include stoichiometric amounts of silicon nitride. In some cases, silicon nitride may include other elements, such as carbon, oxygen, and / or hydrogen.

[0037] As used in this article, "silicon oxide" or "SiO" x"Silicon oxide" refers to materials containing both silicon and oxygen. Silicon oxide can be produced by the formula SiO2. x The expression indicates that x can be between 0 and 2. In some embodiments, silicon oxide may not include elements other than silicon and oxygen in significant proportions. Silicon oxide may be represented by the formula SiO2. In some embodiments, silicon oxide comprises SiO2. In some embodiments, silicon oxide may consist essentially of SiO2. In some cases, silicon oxide may not include stoichiometric amounts of silicon oxide. In some cases, silicon oxide may include other elements, such as carbon, nitrogen, and / or hydrogen.

[0038] As used in this article, "silicon oxide" or "SiO2" x C y "SiOC" or "SiO2O3" refers to a material comprising silicon, oxygen, and carbon. As used herein, unless otherwise stated, SiOC is not intended to limit, constrain, or define the bonding or chemical state, such as oxidation state, of any of the Si, O, C, and / or any other elements in the film. In some embodiments, SiO2O3... z O x C y It may contain Si-C bonds and / or Si-O bonds. In some embodiments, SiOC may contain Si-C bonds and Si-O bonds, and may not contain Si-N bonds. In some embodiments, in addition to Si-C and / or Si-O bonds, SiOC may also contain Si-H bonds. In some embodiments, SiOC may contain more Si-O bonds than Si-C bonds, for example, the ratio of Si-O bonds to Si-C bonds may be from about 1:10 to about 10:1. In some embodiments, SiOC may contain about 0% to about 50% carbon on an atomic basis. In some embodiments, SiOC may contain about 0.1% to about 40%, about 0.5% to about 30%, about 1% to about 30%, or about 5% to about 20% carbon on an atomic basis. In some embodiments, SiOC may contain about 0% to about 70% oxygen on an atomic basis. In some embodiments, SiOC may contain about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen on an atomic basis. In some embodiments, SiOC may contain about 0% to about 50% silicon on an atomic basis. In some embodiments, the SiOC film may comprise about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% on an atomic basis. In some embodiments, silicon oxide may be derived from silicon oxide with the chemical formula SiOxC. y It is indicated that z can be in the range of about 0 to about 2, x can be in the range of about 0 to about 2, and y can be in the range of about 0 to about 5.

[0039] As used in this article, "silicon, oxygen, carbon, nitrogen" or "Si" z O x C y N w"SiOCN" or "SiOCN" refers to a material comprising silicon, oxygen, nitrogen, and carbon. As used herein, unless otherwise stated, SiOCN is not intended to limit, constrain, or define the bonding or chemical state, such as oxidation state, of any of the Si, O, C, N, and / or any other elements in the material. In some embodiments, SiOCN is a material that can be produced from the chemical formula Si z O x C y N w The material represents the range of z from about 0 to about 2, x from about 0 to about 2, y from about 0 to about 2, and w from about 0 to about 2.

[0040] As used in this article, "silicon oxynitride" or "SiO2" x N y "" refers to materials containing silicon, oxygen, and nitrogen. As used herein, unless otherwise stated, SiO2... x Ny is not intended to limit, constrain, or define the bonding or chemical state, such as the oxidation state of Si, O, N, and / or any other element in the material. In some embodiments, SiO x N y It can be made from the chemical formula SiO x N y The material is indicated by x, which can range from about 0 to about 2, and y, which can range from about 0 to about 2. Silicon oxynitride can include silicon oxide and silicon nitride.

[0041] As used herein, "substrate" refers to one or more underlying materials on which devices, circuits, materials, or material layers can be formed or on which they are formed. Substrate can be continuous or discontinuous; rigid or flexible; solid or porous; and combinations thereof. Substrate can be in any form, such as powder, plate, or workpiece. Plate-type substrates can include wafers of various shapes and sizes. Substrate can be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide. Substrate can include one or more layers covering a bulk material, such as nitrides (e.g., TiN), oxides, insulating materials, dielectric materials, conductive materials, metals (e.g., tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper) or metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or single-crystal materials. Substrate can include various topologies, such as gaps, including recesses, lines, trenches, or spaces between protrusions (e.g., fins) formed within or on at least a portion of the layers of the substrate.

[0042] As used herein, an "ion trap" refers to a structure, region, device, or configuration within a semiconductor processing chamber (such as a plasma-enhanced atomic layer deposition (PE-ALD) chamber or a radical-enhanced atomic layer deposition (RE-ALD) chamber) designed to selectively capture, retain, and control ionic material generated during the deposition process. Ion traps can be integrated into or located adjacent to the inner surface of the chamber, including, for example, chamber walls, gas distribution plates, or other internal components, to manage the energy, directionality, and concentration of ions within the reaction space. By influencing ion trajectories and reducing unwanted ion bombardment or plasma-induced damage to the substrate and underlying device structure, ion traps can help maintain optimal conditions for uniform and conformal film growth. Ion traps can be formed from a variety of conductive, semiconductive, or dielectric materials and can include engineered geometries, patterned surfaces, coatings, or other configurations tailored to specific process chemicals, power levels, and plasma conditions of interest. In some embodiments, ion traps can be dynamically adjusted or tuned to accommodate varying process parameters, thereby improving process stability, film quality, and overall device performance in advanced semiconductor manufacturing environments.

[0043] As used herein, a "substituent" is an atom or group of atoms that replaces one or more atoms (e.g., hydrogen atoms) or groups of atoms in a parent compound to produce a new compound. A substituent replaces an original atom or group of atoms in a parent molecule. For simplicity, a substituent may be represented in a chemical formula as an "R" group, and each "R" group in a compound may be chosen independently unless otherwise specifically stated. Examples of substituents include, but are not limited to: hydrogen atoms (H); "alkyl" groups, such as saturated straight-chain or branched C1 to C2 groups. 10 Hydrocarbons, preferably C1 to C6 hydrocarbons (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 3-pentyl, neopentyl, and hexyl); "cycloalkyl", such as C3 to C6 cyclic hydrocarbons (e.g., cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl); "alkenyl", such as C2 to C6 straight-chain or branched unsaturated hydrocarbons (e.g., vinyl, allyl, propenyl, butenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, ethynyl, propargyl, butynyl, pentynyl, and hexynyl); "aryl", such as phenyl, benzyl, tolyl, xylyl, naphthyl, cyclopentadienyl, and methyl, dimethyl, or ethylcyclopentadienyl; hydroxyl (OH); "alkoxy", such as straight-chain or branched C1 to C6 hydrocarbons. 10 Alkoxy groups, typically C1 to C4 alkoxy groups (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy); hydroxyalkyl groups, such as straight-chain or branched C1 to C4 alkoxy groups. 10Hydroxyalkyl, typically straight-chain or branched C1 to C4 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl); "alkoxycarbonyl", such as straight-chain or branched C1 to C6 carbonyl hydrocarbons (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, and hexoxycarbonyl); thiol group (SH); "alkylthiol group", such as straight-chain or branched C1 to C6 thiols (e.g., thiol methyl, hydroxyethyl, hydroxypropyl ... Thiols (ethyl, propyl, butyl, pentyl, and hexyl); halides (X), such as fluorides (F), chlorides (Cl), bromides (Br), and iodides (I); and "haloalkyl", such as straight-chain or branched C1 to C6 alkyl halides having one or more halogen atoms (e.g., iodomethyl, bromomethyl, chloromethyl, fluoromethyl, trifluoromethyl, 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, and pentafluoroethyl). The substituent itself can be substituted. For example, hydroxyalkyl is a substituted alkyl group in which the H atom on the alkyl group is replaced by an OH group.

[0044] As used herein, “radicalization” refers to the process of converting a stable precursor or reactant gas into radicals (highly reactive neutral substances with unpaired electrons) within a semiconductor deposition chamber environment, such as during plasma-enhanced atomic layer deposition (PE-ALD) or radical-enhanced atomic layer deposition (RE-ALD). These radicals can be generated by introducing an energy source (e.g., plasma, photons, thermal energy) that dissociates gaseous molecules into more reactive fragments. The radicalization process can occur within or near the deposition chamber and can be achieved through dedicated radical generation zones, plasma sources, radical injectors, or other field-generating components. By generating controlled populations of radicals, the radicalization process enhances reaction kinetics, improves overall chemical reactivity at the substrate surface, and enables more uniform, conformal, and efficient film deposition. These radicals can react with a variety of substrate surfaces, including silicon-based materials, metals, nitrides, oxides, and other semiconductor or dielectric materials, thereby promoting customized surface modification or layer formation. The radicalization process can be dynamically adjusted by controlling parameters such as gas flow rate, chamber pressure, plasma power, or residence time of precursor materials, thereby allowing for fine-tuning of film properties, improved process stability, and enhanced device performance in advanced semiconductor manufacturing environments.

[0045] The article “a” or “an” refers to a single substance or a genus comprising multiple substances, depending on the context. Therefore, the terms “a / an,” “one or more,” and “at least one” are used interchangeably herein. It should also be noted that the terms “comprising,” “including,” and “having” are used interchangeably.

[0046] The term "approximately" typically refers to a range of numbers that are considered equivalent to the listed values ​​(e.g., having the same function or result). In some cases, the term "approximately" may include numbers rounded to the nearest significant figure.

[0047] The term “basic” when applied to compositions, methods, or systems generally means that the additional components do not substantially alter the properties and / or functions of the composition, method, or system.

[0048] The term "basic" applied to compositions, methods, or systems generally refers to a proportion of a value, property, characteristic, etc., or conversely, a proportion lacking therein, and is at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, at least about 98%, at least about 99%, at least about 99.5%, at least about 99.9% or more, or any proportion between about 70% and about 100%. In some embodiments, the term "basic" means a proportion of about 90%, about 95%, about 97%, about 98%, about 99%, about 99.5%, or about 99.9%.

[0049] "At least one," "one or more," and "and / or" are open-ended expressions that are both conjunction and disjunctive in operation. For example, each of the expressions "at least one of A, B, and C," "at least one of A, B, or C," "one or more of A, B, and C," "one or more of A, B, or C," and "A, B, and / or C" means a single A, a single B, a single C, A and B together, A and C together, B and C together, or A, B, and C together. When each of A, B, and C in the above expressions refers to elements such as X, Y, and Z, or such as X1-X... n Y1-Y m and Z1-Z o When referring to element categories, this phrase is intended to refer to a single element selected from X, Y, and Z; a combination of elements selected from the same category (e.g., X1 and X2); and a combination of elements selected from two or more categories (e.g., Y1 and Z). o ).

[0050] It should be understood that every numerical range given in this disclosure is considered to include the upper and lower limits, as well as every narrower numerical range falling within such a wider range, as all such narrower numerical ranges are explicitly stated herein. For example, the phrase “about 2 to about 4” or “2 to 4” includes 2 and 4, as well as integer and / or integer ranges of about 2 to about 3, about 3 to about 4, and every possible range based on real numbers (e.g., irrational and / or rational numbers), such as about 2.1 to about 3.9, about 2.1 to about 3.4, etc.

[0051] This disclosure generally relates to methods and systems for forming films on the surface of a substrate using plasma-enhanced atomic layer deposition (PE-ALD), and specifically to using low-power plasma to influence the partial decomposition of chemical precursors to enhance their reactivity. More specifically, this disclosure generally relates to methods and systems for forming films on the surface of a substrate using radical-enhanced atomic layer deposition (RE-ALD), and specifically to using low-power plasma to influence the partial decomposition of chemical precursors to enhance their reactivity. Various aspects of the methods and systems, and the benefits derived therefrom, will now be described.

[0052] The search for improved chemical precursors for ALD processes is an ongoing endeavor, driven by increasingly stringent material and process requirements for improving semiconductor devices. Typically, precursors are sought that readily volatilize and transport to the deposition site at temperatures consistent with the fabrication of the device structure. The desired precursors should produce highly conformal films on the substrate in contact with the precursor vapor without undergoing decomposition reactions that would adversely affect the product device structure. A typical approach to working with relatively unreactive chemicals is to utilize plasma treatment; however, this has its own drawbacks (e.g., plasma-induced damage, anisotropy) and limits options if the precursor is too unreactive to even chemisorb onto the substrate surface. In this regard, methods and systems are disclosed herein for depositing films on the surface of a substrate using low-power plasma to partially decompose precursors and increase their reactivity. The methods and systems disclosed herein advantageously expand the selection of precursors and allow the use of relatively “non-reactive” precursors that may not readily chemisorb onto the substrate surface and / or participate in the thermal ALD reaction. The disclosed method can improve film growth rate, allow for processing at lower temperatures, and improve film uniformity and conformation, while minimizing the negative impacts typically associated with plasma processing. These and other advantages will be apparent from the disclosure of the various aspects, embodiments, and configurations contained herein.

[0053] Please refer to Figure 1 , Figure 1 This is a schematic diagram of a method 100 for forming a film on the surface of a substrate according to some embodiments of the present disclosure. In step 110, the substrate is introduced into the lower chamber of a reaction chamber. An ion trap is used to divide the reaction chamber into an upper chamber and a lower chamber. The ion trap may be a mesh made of metal (e.g., aluminum) and is grounded. Details of the ion trap can be described in... Figure 4 As seen in the relevant paragraphs. Next, step 120 involves introducing a first plasma into the upper chamber. The first plasma is introduced into the upper chamber via a top plate disposed within the reaction chamber. The plasma is a low-power plasma, and the first plasma is confined by the upper chamber (i.e., between the top plate and the ion trap).

[0054] According to some embodiments of this disclosure, the top plate is a spray head that supplies gas (such as a carrier gas, precursor, reactant, or a combination thereof) into the reaction chamber. The spray head is connected to an RF generator to form a first plasma in the upper chamber. In different embodiments of this disclosure, the RF power used to generate the first plasma can be varied. As will be understood, the power used to generate the first plasma, and therefore the ionization energy of the plasma, can vary based on the type of precursor and can be adjusted to affect the degree of dissociation of the precursor and chemisorption onto the substrate surface. The RF power should be set high enough to form precursor-based activated radical material, but low enough that breakdown is insufficient to induce CVD-type film deposition. Typically, the RF power used to generate the first plasma is maintained at about 100 W or less, typically at about 50 W or less, typically at about 25 W or less, or more typically at about 20 W. Typically, the RF power used to generate the first plasma is maintained at about 0.1 W or higher, usually about 1 W or higher, usually about 5 W or higher, or more typically about 20 W (in contrast, the RF power of conventional PE-ALD processes is much higher, typically between 100 and 1500 W). At such low RF power, the first plasma can be characterized as having low ionization and low electron density.

[0055] In some embodiments, the RF power used to generate the first plasma is maintained at about 100 W or less, typically from about 0.1 W to about 100 W, more typically from about 1 W to about 100 W, more typically from about 1 W to about 90 W, more typically from about 1 W to about 80 W, more typically from about 1 W to about 70 W, more typically from about 1 W to about 60 W, more typically from about 1 W to about 50 W, more typically from about 1 W to about 40 W, more typically from about 1 W to about 30 W, more typically from about 1 W to about 20 W, more typically from about 1 W to about 10 W, more typically from about 5 W to about 100 W, more typically from about 5 W to about 90 W, and more typically from about 5 W to about 80 W. W, more typically in the range of about 5W to about 70W, more typically in the range of about 5W to about 60W, more typically in the range of about 5W to about 50W, more typically in the range of about 5W to about 40W, more typically in the range of about 5W to about 30W, more typically in the range of about 5W to about 20W, more typically in the range of about 10W to about 100W, more typically in the range of about 10W to about 90W, more typically in the range of about 10W to about 80W, more typically in the range of about 10W to about 70W, more typically in the range of about 10W to about 60W, more typically in the range of about 10W to about 50W, more typically in the range of about 10W to about 40W, more typically in the range of about 10W to about 30W, or any intermediate range of power between about 0.1W and about 100W. In some embodiments, the RF power may be maintained at approximately 100W or less, approximately 90W or less, approximately 80W or less, approximately 70W or less, approximately 60W or less, approximately 50W or less, approximately 40W or less, approximately 30W or less, approximately 25W or less, approximately 20W or less, approximately 15W or less, or approximately 10W or less. In some embodiments, the RF power may be maintained at approximately 1W, approximately 5W, approximately 10W, approximately 20W, approximately 25W, approximately 30W, approximately 40W, approximately 50W, approximately 60W, approximately 70W, approximately 80W, approximately 90W, or approximately 100W.

[0056] In some embodiments, the duration of the first plasma is about 100 seconds or less, typically from about 0.01 seconds to about 100 seconds, more typically from about 0.01 seconds to about 50 seconds, more typically from about 0.01 seconds to about 10 seconds, more typically from about 0.01 seconds to about 5 seconds, more typically from about 0.01 seconds to about 1 second, more typically from about 0.01 seconds to about 0.5 seconds, more typically from about 0.01 seconds to about 0.1 seconds, more typically from about 0.1 seconds to about 100 seconds, more typically from about 1 second to about 50 seconds, more typically from about 0.1 seconds to about 10 seconds, more typically from about 0.1 seconds to about 5 seconds, more typically from about 0.1 seconds to about 1... The duration is approximately 1 second, more typically about 0.1 seconds to about 0.5 seconds, more typically about 0.5 seconds to about 100 seconds, more typically about 0.5 seconds to about 50 seconds, more typically about 0.5 seconds to about 10 seconds, more typically about 0.5 seconds to about 5 seconds, more typically about 0.5 seconds to about 1 second, more typically about 1 second to about 100 seconds, more typically about 1 second to about 50 seconds, more typically about 1 second to about 10 seconds, more typically about 1 second to about 5 seconds, more typically about 5 seconds to about 100 seconds, more typically about 5 seconds to about 50 seconds, more typically about 5 seconds to about 10 seconds, or any intermediate range between about 0.01 seconds and about 100 seconds. In some embodiments, the RF power may be maintained for about 100 seconds or less, about 50 seconds or less, about 10 seconds or less, about 5 seconds or less, about 1 second or less, about 0.5 seconds or less, or about 0.1 seconds or less. In some embodiments, the RF power may be maintained for about 0.01 seconds, about 0.1 seconds, about 0.5 seconds, about 1 second, about 5 seconds, about 10 seconds, about 50 seconds, or about 100 seconds.

[0057] Next, in step 130, the precursor is introduced into the reaction chamber and radicalized by a first plasma to form a radicalized precursor. The precursor is carried into the reaction chamber by a carrier gas through a spray head. The precursor is metered or pulsed into a continuous stream of carrier gas. In some embodiments, the carrier gas may be a feed gas for plasma discharge. In some embodiments, the precursor comprises a silazane (e.g., hexamethyldisilazane ([(CH3)3Si]2NH), hexamethylcyclotrisilazane (C6H)). 21 N3Si3), all-hydrogenated polysilazane ([SiH2NH) nIn some embodiments, the first plasma is generated by a gas consisting primarily of rare gases. In some embodiments, the first plasma is generated by a rare gas. The rare gas may be selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. When RF power is applied, the carrier gas may contribute to the excitation and partial decomposition of the precursor, but the carrier gas does not chemically react with the precursor. In other embodiments, one or more additives may be introduced together with or separately from the precursor. The low-power plasma is ignited by pulsed RF power. The duration of the RF power pulse should at least partially overlap with the duration of the precursor pulse. The relative timing of the low-power plasma and the precursor pulse can be used to adjust the degree of precursor decomposition and radicalization. In some embodiments, the RF power and the precursor pulse are initiated simultaneously. In some embodiments, the RF power is initiated later than the precursor pulse. In some embodiments, the precursor pulse is initiated later than the RF power. In some embodiments, the precursor is pulsed after the pulsed RF power, such that the durations of the two pulses overlap (see, for example, see...). Figure 2 In other embodiments, the duration of the RF power pulse is longer than the duration of the precursor pulse. Since the chemisorption step is a self-limiting or substantially self-limiting process, the amount of precursor molecules deposited is determined by or substantially by the number of accessible reaction sites on the surface and is independent of the exposure time after surface saturation. Excess precursor can be supplied to the reaction chamber, and the duration of both the precursor and plasma pulses should be long enough to saturate the surface. Typical plasma / precursor pulse times range from about 0.1 seconds to about 10 seconds, preferably from about 1 second to about 5 seconds, after which the reaction chamber can be flushed or purged to remove unreacted precursors, gaseous reaction byproducts, and other substances.

[0058] Next, step 140 involves introducing a reactant (e.g., a reactive gas) into the reaction chamber. In some embodiments, the reactive gas is entrained or pulsed into a continuous stream of carrier gas entering the reaction chamber. In some embodiments, the reactive gas is a precursor (and may be referred to as a second precursor), meaning that a portion of the reactive gas (elements or groups within the reactive gas) is incorporated into the resulting membrane. For example, the reactive substance can react with the chemisorption layer via an exchange reaction or an addition reaction. In other embodiments, the reactive gas can chemically modify the chemisorption layer to form a membrane, for example, by an elimination reaction or by oxidation or reduction, but the elements or groups within the reactive substance are not incorporated into the resulting membrane. The choice of reactive gas will depend on the composition of the chemisorption layer and the desired membrane. In some embodiments, the deposition reaction can be carried out via a thermal process, whereby the reactive gas thermally reacts with the chemisorption layer on the substrate surface. In other embodiments, the deposition reaction can be carried out via a plasma-enhanced process, whereby the reactive gas includes excited material and / or free radicals that react with the chemisorption layer. Similar to the adsorption step, the deposition step is a self-limiting or substantially self-limiting process, determined by the amount of precursor molecules deposited on the surface and independent of the exposure time after saturation. An excess of reactive gas can be provided, and the duration of the reactive gas pulse should be sufficiently long to substantially or completely convert the chemisorbed layer into the target layer. Typical exposure or pulse times are from about 0.1 seconds to about 10 seconds, preferably from about 1 second to about 5 seconds, followed by flushing or purging of the reaction chamber to remove any unreacted reactive gases, gaseous reaction byproducts, and other substances.

[0059] Next, step 150 involves introducing a second plasma into the upper chamber to radicalize the reactants. A spray head is connected to an RF generator to form a second plasma in the upper chamber. The second plasma can be formed using a feed gas comprising a carrier gas (inert gas), a reactive gas, or a mixture of gases. The feed gas is fed into the reaction chamber, and the second plasma is pulsed. In some embodiments, the second plasma is generated by a feed gas containing a reactive gas, which may optionally be mixed with or co-fed with the carrier gas. In other embodiments, the second plasma is generated by a reactive gas. As a non-limiting example, the reactive gas may be oxygen (O2), nitrogen (N2), ammonia (NH3), hydrogen (H2), and mixtures thereof. The carrier gas may be a rare gas selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. The excited material from the rare gas in the second plasma does not necessarily contribute material to the deposited film, but in some cases may contribute to film growth and to the formation and ignition of the second plasma. In some embodiments, the feed gas contains oxygen. In some embodiments, the feed gas contains nitrogen. In some embodiments, the feed gas comprises ammonia. In some embodiments, the feed gas comprises hydrogen. In some embodiments, the feed gas comprises nitrogen and hydrogen. In some embodiments, the feed gas comprises an oxygen-containing compound that forms O* atoms in the second plasma. In some embodiments, the feed gas comprises a nitrogen-containing compound that forms N* atoms in the second plasma. In some embodiments, the feed gas comprises a hydrogen-containing compound that forms H* atoms in the second plasma.

[0060] In some embodiments, the RF power used to generate the second plasma is maintained at about 500 W or less, typically between about 5 W and 500 W, more typically between about 5 W and 400 W, more typically between about 5 W and 300 W, more typically between about 5 W and 250 W, more typically between about 5 W and 200 W, more typically between about 5 W and 150 W, more typically between about 5 W and 100 W, more typically between about 5 W and 50 W, more typically between about 5 W and 10 W, more typically between about 10 W and 500 W, more typically between about 10 W and 400 W, more typically between about 10 W and 300 W, more typically between about 10 W and 250 W, more typically between about 10 W and 200 W, more typically between about 10 W and 150 W, more typically between about 10 W and 100 W, more typically between about 10 W and 50 W, more typically between about 50 W and 500 W. More typically between approximately 50W and 400W, more typically between approximately 50W and 300W, more typically between approximately 50W and 250W, more typically between approximately 50W and 200W, more typically between approximately 50W and 150W, more typically between approximately 50W and 100W, more typically between approximately 100W and 500W, more typically between approximately 100W and 400W, more typically between approximately 100W and 300W, more typically between approximately 100W and 300W. The power ranges from 0W to approximately 250W, more typically from approximately 100W to approximately 200W, more typically from approximately 100W to approximately 150W, more typically from approximately 150W to approximately 500W, more typically from approximately 150W to approximately 400W, more typically from approximately 150W to approximately 300W, more typically from approximately 150W to approximately 250W, more typically from approximately 150W to approximately 200W, or any intermediate range between approximately 5W and approximately 500W. In some embodiments, the RF power may be maintained at approximately 500W or less, approximately 400W or less, approximately 300W or less, approximately 250W or less, approximately 200W or less, approximately 150W or less, approximately 100W or less, approximately 50W or less, or approximately 10W. In some embodiments, the RF power may be maintained at about 5W, about 10W, about 50W, about 100W, about 150W, about 200W, about 250W, about 300W, about 400W, or about 500W. In some embodiments, the RF power of the second plasma is higher than that of the first plasma.

[0061] In some embodiments, the duration of the second plasma may be similar to the duration of the first plasma described above. In some embodiments, the duration of the second plasma is the same as the duration of the first plasma. In some embodiments, the duration of the second plasma is longer than the duration of the first plasma. In some embodiments, the duration of the second plasma is shorter than the duration of the first plasma.

[0062] In some embodiments, method 100 further includes steps 135 and 155. Step 135 is performed between steps 130 and 140, while step 155 is performed after step 150. In steps 135 and 155, the reaction chamber is purged to remove unreacted chemicals (e.g., precursors and reactive gases) and gaseous reaction byproducts from the surface of the substrate. Purging can be achieved, for example, by evacuating the reaction chamber with a vacuum pump and / or by replacing the gases in the reaction chamber with an inert or substantially inert gas such as argon or nitrogen. In some cases, the purging step can be performed between two gas pulses that react with each other, or in other cases, purging can be performed between two gas pulses that do not react with each other. Purging can avoid or at least reduce gaseous interactions between two gases that react with each other. It should be understood that purging can be affected temporally, spatially, or both. For example, in the case of time-purge, the purging step can be used in the order of introducing the precursor into the reaction chamber, introducing the purge gas into the reaction chamber, and then introducing the reactive gas into the reaction chamber, wherein the substrate on which material is deposited does not move.

[0063] In some embodiments, steps 120, 130, and 135 form sub-cycle 125. Sub-cycle 125 may be repeated until the substrate is substantially or completely covered with a chemisorption layer. In some embodiments, steps 140, 150, and 155 form sub-cycle 145. Sub-cycle 145 may be repeated until the chemisorption layer on the substrate is substantially or completely converted into the target layer. In some embodiments, steps 120, 130, 135, 140, 150, and 155 form cycle 160. Cycle 160 may be repeated until a film of the desired thickness is formed on the substrate.

[0064] In some embodiments, loop 160 is repeated at least once or more, typically once to about 10,000 times, more typically once to about 1,000 times, more typically once to about 100 times, more typically once to about 10 times, more typically 10 times to about 10,000 times, more typically 10 times to about 1,000 times, more typically 10 times to about 100 times, more typically 100 times to about 10,000 times, more typically 100 times to about 1,000 times, more typically 1,000 times to about 10,000 times. In some embodiments, loop 160 is repeated at least once, about 10 times, about 100 times, about 1,000 times, or about 10,000 times.

[0065] Please refer to Figure 2 , Figure 2This is a schematic diagram of the timing according to some embodiments of the present disclosure. A first plasma is ignited before the precursor is introduced into the reaction chamber, and the first plasma pulse continues after the precursor pulse ends. A second plasma is ignited after the reactant is introduced into the reaction chamber, and the second plasma pulse ends before the reactant pulse ends. Figure 2 The diagram illustrates cycle 160 repeated once. In some embodiments, the first plasma is ignited simultaneously with the introduction of the precursor into the reaction chamber. In some embodiments, the first plasma is ignited after the introduction of the precursor into the reaction chamber. In some embodiments, the first plasma pulse ends at the end of the reactant pulse. In some embodiments, the first plasma pulse ends before the end of the reactant pulse. In some embodiments, the second plasma is ignited while the reactant is being introduced into the reaction chamber. In some embodiments, the second plasma pulse ends at the end of the reactant pulse. In some embodiments, the second plasma pulse ends after the end of the reactant pulse. In some embodiments, cycle 160 is repeated until a film of the desired thickness is formed.

[0066] Please refer to Figure 3 , Figure 3 This is a schematic diagram of a method 300 for forming a film on the surface of a substrate according to some embodiments of the present disclosure. In step 310, a reaction chamber having an upper chamber and a lower chamber separated by an ion trap is provided. The upper chamber is between a top plate and the ion trap, while the lower chamber is between the ion trap and a base. The ion trap may be a mesh plate made of metal (e.g., aluminum), and the ion trap is grounded. Details of the ion trap can be provided in... Figure 5 As seen in the relevant paragraphs. Next, step 320 involves introducing a substrate into the lower chamber. The substrate is disposed on a pedestal and between the ion trap and the pedestal. Next, step 330 involves introducing a precursor into the reaction chamber and using a first plasma in the upper chamber to radicalize the precursor to form a radicalized precursor. According to some embodiments of this disclosure, the top plate is a spray head that supplies gases (such as carrier gas, precursor, and / or reactants) into the reaction chamber. The spray head is connected to a first RF generator to form a first plasma in the upper chamber. The precursor and first plasma in method 300 are similar to those in method 100, and therefore will not be described again herein.

[0067] Next, step 340 involves introducing reactants (reactive gases) into the reaction chamber and generating a second plasma in the lower chamber to decompose the reactants and expose the substrate to various plasma materials. The reactants in method 300 are similar to those in method 100, and therefore will not be described again herein. A pedestal is connected to a second RF generator to form the second plasma in the lower chamber. The reactants include one or more excited and / or radical materials, which can be formed in situ in the reaction chamber using direct plasma formed near or directly above the substrate. Typically, the use of direct plasma results in a higher density of plasma materials (e.g., ions, electrons, radicals, and other excited materials) near the substrate, and those materials may interact with the substrate and affect film growth and quality.

[0068] A second plasma can be formed using a feed gas comprising a carrier gas (inert gas), a reactive gas, or a mixture of gases. The feed gas is fed into the reaction chamber and the plasma is pulsed. In some embodiments, the plasma is generated by a feed gas containing a reactive gas, which may optionally be mixed with or co-fed with the carrier gas. In other embodiments, the plasma is generated by a reactive gas. As a non-limiting example, the reactive gas may be oxygen (O2), nitrogen (N2), ammonia (NH3), hydrogen (H2), and mixtures thereof. The carrier gas may be a rare gas selected from helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and mixtures thereof. The excited material from the rare gas in the plasma does not necessarily contribute to the material of the deposited film, but in some cases may contribute to film growth and to the formation and excitation of the plasma. In some embodiments, the feed gas contains oxygen. In some embodiments, the feed gas contains nitrogen. In some embodiments, the feed gas contains ammonia. In some embodiments, the feed gas contains hydrogen. In some embodiments, the feed gas contains both nitrogen and hydrogen. In some embodiments, the feed gas contains an oxygen-containing compound that forms O* atoms in the plasma. In some embodiments, the feed gas contains a nitrogen-containing compound that forms N* atoms in the plasma. In some embodiments, the feed gas contains a hydrogen-containing compound that forms H* atoms in the plasma.

[0069] In different embodiments of this disclosure, the RF power used to generate the second plasma can be varied. In some embodiments, the power used to generate the second plasma is typically from about 10 W to about 1500 W, more typically from about 20 W to about 1000 W, more typically from about 20 W to about 900 W, more typically from about 20 W to about 800 W, more typically from about 20 W to about 700 W, more typically from about 20 W to about 600 W, more typically from about 20 W to about 500 W, more typically from about 20 W to about 400 W, more typically from about 20 W to about 300 W, more typically from about 20 W to about 200 W, more typically from about 20 W to about 100 W, or any power in an intermediate range between about 10 W and about 1500 W. In some embodiments, the RF power used to generate the second plasma can be maintained at approximately 20W, approximately 30W, approximately 40W, approximately 50W, approximately 60W, approximately 70W, approximately 80W, approximately 90W, approximately 100W, approximately 120W, approximately 140W, approximately 160W, approximately 180W, approximately 200W, approximately 220W, approximately 240W, approximately 260W, approximately 280W, approximately 300W, approximately 320W, approximately 340W, approximately 360W, approximately 380W, approximately 400W, approximately 420W, approximately 4 40W, approximately 460W, approximately 480W, approximately 500W, approximately 520W, approximately 540W, approximately 560W, approximately 580W, approximately 600W, approximately 620W, approximately 640W, approximately 660W, approximately 680W, approximately 700W, approximately 720W, approximately 740W, approximately 760W, approximately 780W, approximately 800W, approximately 820W, approximately 840W, approximately 860W, approximately 880W, approximately 900W, approximately 920W, approximately 940W, approximately 960W, approximately 980W, or approximately 1000W. Adjusting the power of the plasma generator can affect the amount / density and energy of the reactive substances generated by the plasma. Without limiting the disclosed methods to any particular theory, higher power can lead to the generation of higher-energy ions and free radicals. This may affect the degree of damage that the reactive substances may cause on the surface of the substrate.

[0070] In method 300, the duration of the second plasma may be similar to the duration of the first plasma described above. In some embodiments, the duration of the second plasma is the same as the duration of the first plasma. In some embodiments, the duration of the second plasma is longer than the duration of the first plasma. In some embodiments, the duration of the second plasma is shorter than the duration of the first plasma.

[0071] In some embodiments, method 300 further includes steps 350 and 360. Step 350 is performed between steps 330 and 340, while step 360 is performed after step 340. Steps 350 and 360 are similar to steps 135 and 155, respectively, and therefore will not be described again herein.

[0072] In some embodiments, steps 330 and 350 form sub-cycle 335. Sub-cycle 335 may be repeated until the substrate is substantially or completely covered with a chemisorption layer. In some embodiments, steps 340 and 360 form sub-cycle 345. Sub-cycle 345 may be repeated until the chemisorption layer on the substrate is substantially or completely converted into the target layer. In some embodiments, steps 330, 350, 340, and 360 form cycle 365. Cycle 365 may be repeated until a film of the desired thickness is formed on the substrate.

[0073] The timing of method 300 is similar to that of method 100. Figure 2 Therefore, this article will not repeat the description.

[0074] Please refer to Figure 4 , Figure 4 This is a schematic diagram of a semiconductor processing apparatus 400 according to some embodiments of the present disclosure. The semiconductor processing apparatus 400 is an implementation of method 100. Therefore, the elements and / or components described herein can be connected to method 100.

[0075] A carrier gas is supplied from a carrier gas source 402 to the reaction chamber 420 via a gas manifold 401. The carrier gas flows through a spray head 407 positioned directly above a base 411 on which a substrate (i.e., a wafer) 410 is placed. A precursor is also supplied in gaseous form from a precursor source 403 via a gas manifold 401 and enters the reaction chamber 420 through the spray head 407. The precursor may be evaporated and entrained or pulsed into the carrier gas. A reactant is supplied in gaseous form from a reactant source 404 via a gas manifold 401 and enters the reaction chamber 420 through the spray head 407. The semiconductor processing apparatus 400 is also configured to allow the introduction of other gases (such as other reactants (reactive gases) and other gases (e.g., other carrier gases, precursor or reactive gases, carrier gas, diluent, process gas, feed gas, and / or purge gas)) into the reaction chamber 420 via the spray head 407 or from other ports (not shown). Therefore, the semiconductor processing apparatus 400 may include other sources (not shown). Unreacted gases and gaseous reaction byproducts exit the reaction chamber 420 through an exhaust line 412. The reaction chamber 420 may optionally be equipped with a purge line (not shown) and / or a pump line (not shown) connected to a vacuum pump (not shown), allowing the reaction chamber 420 to be purged between various reaction cycles. An RF generator 413 and a corresponding matching unit (not shown) (electrically) connected to a spray head 407 allow the spray head 407 to be biased relative to the ion trap to form a first plasma and / or a second plasma (refer to the first and second plasmas of method 100, respectively) discharging between the spray head 407 and the ion trap 409. The ion trap 409 is positioned between the spray head 407 and the base 411 to divide the reaction chamber 420 into an upper chamber 421 and a lower chamber 422. An upper chamber 421 is located between the spray head 407 and the ion trap 409, and a lower chamber 422 is located between the ion trap 409 and the base 411. The ion trap 409 confines the first plasma and / or the second plasma to the upper chamber 421 above the ion trap 409. For example, an electrically grounded mesh can be used as the ion trap 409. In some embodiments, the mesh is a metal plate (such as aluminum) comprising hundreds of holes in a spray head-like pattern, allowing free radical material to pass through to the substrate 410 while trapping ions. For example, the mesh may comprise between about 1,000 and about 5,000 holes, each with a diameter between about 0.5 mm and about 2 mm. The addition of the ion trap 409 advantageously reduces or even eliminates the interaction of electrons and ions with the surface of the substrate 410 by confining the first plasma and / or the second plasma to the upper chamber 421. The semiconductor processing apparatus 400 also includes a controller 414, an RF generator 413, and other components (not shown) operably connected to the first valve 415, the second valve 416, and the third valve 417.

[0076] Controller 414 is configured and programmed to independently control (e.g., turn on and off) the supply of various gases (e.g., carrier gas, precursor, reactants and any diluents, processing, feed and / or purge gases, etc.) and RF generator 413 as needed to deposit a film on the surface of substrate 410. In some embodiments, controller 414 is configured to control a first valve 415 to allow carrier gas to flow from carrier gas source 402 into reaction chamber 420. Controller 414 is further configured to open a second valve 416 to allow precursor to flow from precursor source 403 into reaction chamber 420 and to turn on RF generator 413 to form a first plasma. Turning on RF generator 413 and opening second valve 416 can be done sequentially or simultaneously. After a set time period, controller 414 closes the second valve 416 leading to precursor source 403 and turns off RF generator 413. Next, controller 414 opens a third valve 417 to allow reactants to flow from reactant source 404 into reaction chamber 420 and turns on RF generator 413 to form a second plasma. The RF generator 413 and the third valve 417 can be turned on one after the other, or simultaneously. After a set time period, the controller 414 closes the third valve 417 leading to the reactant source 404 and turns off the RF generator 413. The controller 414 is programmed to repeat various process steps to grow a film on the surface of the substrate 410. The controller 414 can be programmed to perform other process steps between these various steps.

[0077] In another embodiment, controller 414 is configured to open a first valve 415 to allow carrier gas to flow from carrier gas source 402 into reaction chamber 420, and then open a second valve 416 to allow precursor to flow from precursor source 403 into reaction chamber 420, while simultaneously activating RF generator 413 to form a first plasma. Activating RF generator 413 and opening second valve 416 can be done sequentially or simultaneously. After a set time period, controller 414 closes second valve 416 leading to precursor source 403 and shuts off RF generator 413. Next, controller 414 opens a third valve 417 to allow reactants to flow from reactant source 404 into reaction chamber 420. After another set time period, controller 414 closes third valve 417 leading to reactant source 404. Controller 414 is programmed to repeat various process steps to grow a film on the surface of substrate 410. Controller 414 can be programmed to perform additional process steps between these various steps.

[0078] Precursors and reactants are deposited on substrate 510 via a RE-ALD process using semiconductor processing equipment 400.

[0079] Please refer to Figure 5 , Figure 5This is a schematic diagram of a semiconductor processing apparatus 500 according to some embodiments of the present disclosure. The semiconductor processing apparatus 500 is an implementation of method 300. Therefore, the elements and / or components described herein can be connected to method 300.

[0080] A carrier gas is supplied from a carrier gas source 502 to the reaction chamber 520 via a gas manifold 501. The carrier gas flows through a spray head 507 positioned directly above a base 511 on which a substrate (i.e., a wafer) 510 is placed. A precursor is also supplied in gaseous form from a precursor source 503 via a gas manifold 501 and enters the reaction chamber 520 through the spray head 507. The precursor may be evaporated and entrained or pulsed into the carrier gas. A reactant is supplied in gaseous form from a reactant source 504 via a gas manifold 501 and enters the reaction chamber 520 through the spray head 507. The semiconductor processing apparatus 500 is also configured to allow the introduction of other gases (e.g., other reactants (reactive gases) and other gases (e.g., other carrier gases, precursor or reactive gases, carrier gas, diluent, process gases, feed gases, and / or purge gases)) into the reaction chamber 520 via the spray head 507 or from other ports (not shown). Therefore, the semiconductor processing apparatus 500 may include other sources (not shown). Unreacted gases and gaseous reaction byproducts exit the reaction chamber 520 through an exhaust line 512. The reaction chamber 520 may optionally be equipped with a purge line (not shown) and / or a pump line (not shown) connected to a vacuum pump (not shown) to allow purging of the reaction chamber 520 between various reaction cycles. A first RF generator 513 and a corresponding matching unit (not shown) (electrically) connected to a spray head 507 allow the spray head 507 to be biased relative to an ion trap 509 to form a first plasma (refer to the first plasma of method 300) discharge between the spray head 507 and the ion trap 509. The ion trap 509 is located between the spray head 507 and the base 511 to divide the reaction chamber 520 into an upper chamber 521 and a lower chamber 522. The upper chamber 521 is between the spray head 507 and the ion trap 509, and the lower chamber 522 is between the ion trap 509 and the base 511. Ion trap 509 confines the first plasma to an upper chamber 521 above the ion trap 509. For example, an electrically grounded mesh plate can be used as the ion trap 509. In some embodiments, the mesh plate is a metal plate (e.g., aluminum) comprising hundreds of holes in a spray head pattern, allowing free radical material to pass through to the substrate 510 while trapping ions. For example, the mesh plate may comprise between about 1,000 and about 5,000 holes, each with a diameter between about 0.5 mm and about 2 mm. The addition of ion trap 509 advantageously reduces or even eliminates the interaction of electrons and ions with the surface of substrate 510 by confining the first plasma to the upper chamber 521. A second RF generator 523, separate from the first RF generator 513, and a corresponding matching unit (not shown) (electrically) connected to a base 511 allow the base 511 to be biased relative to the ion trap 509 to form a second plasma (refer to the second plasma of method 300) discharge between the base 511 and the ion trap 509. Ion trap 509 confines the second plasma to the lower chamber 521 below ion trap 509.The semiconductor processing apparatus 500 also includes a controller 514 operatively connected to the first valve 515, the second valve 516, and the third valve 517, a first RF generator 513, a second RF generator 523, and other components (not shown).

[0081] Controller 514 is configured and programmed to independently control (e.g., open and close) the supply of various gases (e.g., carrier gas, precursor, reactants and any diluents, processing, feed and / or purge gases, etc.), the first RF generator 513, and the second RF generator 523 as needed to deposit a film on the surface of substrate 510. In some embodiments, controller 514 is configured to control a first valve 515 to allow carrier gas to flow from carrier gas source 502 into reaction chamber 520. Controller 514 is further configured to open a second valve 516 to allow precursor to flow from precursor source 503 into reaction chamber 520 and to turn on the first RF generator 513 to form a first plasma. Turning on the first RF generator 513 and opening the second valve 516 can be done sequentially or simultaneously. After a set time period, controller 514 closes the second valve 516 leading to precursor source 503 and turns off the first RF generator 513. Next, controller 514 opens third valve 517 to allow reactants to flow from reactant source 504 into reaction chamber 520 and activates second RF generator 523 to form a second plasma. Activating second RF generator 523 and opening third valve 517 can be done sequentially or simultaneously. After a set time period, controller 514 closes third valve 517 to reactant source 504 and shuts down second RF generator 523. Controller 514 is programmed to repeat various process steps to grow a film on the surface of substrate 510. Controller 514 can be programmed to perform additional process steps between these various steps.

[0082] In the semiconductor processing apparatus 500, the precursor is deposited on the substrate 510 via a RE-ALD process, and the reactant is deposited on the substrate 510 via a PE-ALD process.

[0083] Conformal deposition of SiCN and SiOCN is achieved by activating silazane precursor molecules via partial decomposition using a first plasma, which is challenging for conventional plasma processing. The elemental composition of the film material can be controlled by selecting precursor chemicals and radical treatments during the process. Because there is no ion bombardment on the substrate, it is easier to retain sensitive elements such as carbon in the film.

[0084] The plasma can be ignited in either the upper or lower chamber as needed. This allows for the design of processes utilizing RE-ALD, PE-ALD, or a combination of both. Having two RF generators provides significant process flexibility. The device allows for faster processing, combining pulsed and constant plasmas, and simultaneously igniting two plasma zones to generate a radical-rich plasma flux on the substrate. For example, plasma exposure can be used to suppress growth on the top surface of high aspect ratio structures, or radical treatment can be used to modulate the elemental composition of films deposited with direct plasma. Therefore, having hardware capable of performing this operation in a single deposition chamber is advantageous. The presence of two RF generators and a matching unit ensures stable plasma generation without requiring plasma tuning or adjustment during processing. The spray head and base also have sufficient surface area on their back sides to ensure good, noise-free contact of the RF energy.

[0085] The semiconductor processing apparatus or system disclosed herein may include Figure 4 and Figure 5 Additional sources and components, not shown, such as those commonly found in semiconductor processing equipment. For example, a semiconductor processing equipment may be equipped with one or more heaters and one or more temperature regulators to activate the reaction by raising the temperature of one or more substrates and / or gases (e.g., carrier gas, precursor, reactive gas, etc.) entering the reaction chamber. The semiconductor processing equipment may also be equipped with a pumping system for purging the reaction chamber between various processing steps.

[0086] The reaction chamber may be part of an ALD assembly and may be a single-wafer reactor, or it may comprise one or more multi-station deposition chambers. Alternatively, the reactor may be a batch reactor. The various steps of the method may be performed in a single reaction chamber, or they may be performed in multiple reaction chambers, such as the reaction chamber of a cluster tool. In some embodiments, the method is performed in a single reaction chamber of a cluster tool, but other, prior or subsequent fabrication steps of the structure or device are performed in additional reaction chambers of the same cluster tool. Optionally, the assembly including the reaction chamber may be provided with a heater to activate the reaction by raising the temperature of one or more of the substrate, reactants, precursors, and other gases. Spray-head type reaction chambers or cross-flow reaction chambers, or combinations thereof, may be used to introduce reactants, precursors, and other gases into the chamber.

[0087] The foregoing discussion has been provided for illustrative purposes using sub-cycles and cycles. The sub-cycles and cycles shown are sufficient to explain the disclosed method, but those skilled in the art will understand that the principles and advantages of the embodiments taught herein can be readily extended to more complex ALD processes. Those skilled in the art will readily understand that each cycle may include additional steps (e.g., a second reactant pulse, a third reactant pulse, etc. may be introduced), or the same reactants, and not all cycles need to be the same (e.g., a second reactant may be introduced every five cycles to incorporate a different element in the desired percentage). This flexibility is provided without departing from the spirit of this disclosure and allows for the production of a wide variety of membranes.

[0088] The methods and systems disclosed herein can be used to deposit a variety of films, such as silicon (Si) films and boron (B) films, as well as metal films, metal oxide films, and metal nitride films, including films containing aluminum (Al), molybdenum (Mo), titanium (Ti), hafnium (Hf), tungsten (W), magnesium (Mg), tantalum (Ta), strontium (Sr), etc., as non-limiting examples. The methods and systems disclosed herein can be used to increase the reactivity of certain precursors, such as silicon-containing precursors, boron-containing precursors, and metal-containing precursors, such as those containing aluminum, molybdenum, titanium, hafnium, tungsten, magnesium, tantalum, strontium, etc., as non-limiting examples. Precursors and the radicalized precursors formed therefrom can include silicon, boron, and one or more metals selected from aluminum, molybdenum, titanium, hafnium, tungsten, magnesium, tantalum, and strontium. Suitable precursors can include those known to be usable in CVD processes. In some embodiments, the precursor can be used in CVD-type deposition processes, but it can be non-reactive in ALD-type deposition processes. In this case, the radicalization of the precursor makes it reactive during ALD-type deposition.

[0089] The methods and systems disclosed herein can be used to deposit silicon-containing (Si) films, such as, by way of non-limiting examples, low-dielectric-constant (k) films, high-k gate silicates, low-temperature silicon epitaxial films, and films comprising silicon nitride, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, silicon carbide, silicon carbonitride, and silicon oxide. In some embodiments, the Si-containing film is selected from silicon nitride, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, silicon carbide, silicon carbonitride, silicon oxide, and combinations thereof. In some embodiments, the Si-containing film is selected from silicon oxycarbonitride, silicon carbonitride, and combinations thereof. In these embodiments, the precursor and thus the radicalized precursor formed therefrom comprises silicon. In some embodiments, the precursor comprises silicon and may also comprise one or more of carbon (C), hydrogen (H), nitrogen (N), oxygen (O), and halogen (X, where X may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)). The silicon-containing precursor may comprise one or more Si-C bonds, Si-H bonds, Si-N bonds, Si-O bonds, and Si-X bonds. Suitable silicon-containing precursors may be selected from silanes, halosilanes, aminosilanes, silanodes, siloxanes, and combinations thereof. In some embodiments, the silicon-containing precursor is a silane. Silanes contain silicon and hydrogen, and may optionally also contain one or more carbon, oxygen, nitrogen, and halogen atoms. Examples of silanes include methylsilane (SiH). 4-n (R) n (where n is an integer from 0 to 4), silane (S2H) 6-n (R) n (where n is an integer from 0 to 6) and propane (S3H 8-n (R) nIn some embodiments, the silicon-containing precursor is a silane, where n is an integer from 0 to 8, etc., where each R is an independently chosen substituent, preferably alkyl or aryl. Examples of suitable silane precursors are silanes (SiH4), silanes (Si2H6), and organosilanes such as dimethylsilane (H2Si(CH3)2), diethylsilane (H2Si(C2H5)2), trimethylsilane (HSi(CH3)3), triethylsilane (HSi(C2H5)3), etc. In some embodiments, the silicon-containing precursor is a halosilane. The halosilane contains at least one halogen atom bonded to a silicon atom (Si-X), and may optionally contain one or more hydrogen, carbon, oxygen, and nitrogen atoms. Examples of halosilanes include halosilanes, halodisilanes (Si-Si), halotrisilanes (Si-Si-Si), etc. Examples of suitable halosilane precursors are dichlorosilane (SiH₂Cl₂), dibromosilane (SiH₂Br₂), diiodosilane (SiH₂I₂), hexachlorodisilane (Si₂Cl₆), octachlorotrisilane (Si₃Cl₈), etc. In some embodiments, the silicon-containing precursor is an aminosilane. An aminosilane (or silylamine) comprises at least one nitrogen atom (Si-N) bonded to a silicon atom, as well as carbon and / or hydrogen, and may optionally contain one or more oxygen and halogen atoms. Examples of aminosilanes include monoaminosilanes, diaminosilanes, triaminosilanes, and tetraaminosilanes (e.g., H3Si(NH2), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), silazanes (e.g., NH(SiH3)2), and trimethylsilylamines (e.g., N(SiH3)2) and their substituted linear and cyclic derivatives, wherein one or more hydrogen atoms on the amino and / or silyl groups are independently substituted by a substituent (R), preferably an alkyl or aryl group. An example of an aminosilane precursor is bis(diethylamino)silane (C8H... 20 N2Si), diisopropylaminosilane (C6H) 17 NSi), N-(diethylaminosilyl)-N-ethylethylamine (C8H) 22 N2Si), hexamethyldisilazane ([(CH3)3Si]2NH), hexamethylcyclotrisilazane (C6H) 21 N3Si3), all-hydrogenated polysilazane ([SiH2NH) nIn some embodiments, the silicon-containing precursor is a silanol. The silanol comprises at least one Si-O-Si bond and may optionally contain one or more hydrogen, nitrogen, and halogen atoms. Examples of silanols include monosilanols, disilanols, trisilanols, and tetrasilanols (e.g., H3SiOCH3, H2Si(OCH3)2, HSi(OCH3)3, and Si(OCH3)4, respectively), and their substituted linear and cyclic derivatives, wherein one or more hydrogen atoms on the methyl and / or silyl groups are independently substituted by a substituent (R), preferably alkyl or aryl. Examples of silanol precursors are tetraethyl orthosilicate (TEOS, Si(OC2H5)4), dimethoxydimethylsilane (Si(OCH3)2(CH3)2), trimethoxymethylsilane (Si(OCH3)3CH3), etc. In some embodiments, the silicon-containing precursor is a siloxane. The siloxane comprises at least one Si-O-Si bond and may optionally contain one or more hydrogen, carbon, and halogen atoms. Examples of siloxanes include linear and cyclic siloxanes, such as cyclotrisiloxanes, cyclotetrasiloxanes, and sesquioxanes. Examples of suitable siloxane precursors include octamethylcyclotetrasiloxane (OMCTS, C8H). 24 O4Si4), 1,1,3,5,5,7-hexamethylcyclotetrasiloxane (HMCTS, C8H 24 O3Si4), 1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS, C4H) 16 O4Si4), etc. In some embodiments, the silicon-containing precursor is selected from dimethylsilane, diethylsilane, trimethylsilane, triethylsilane, dichlorosilane, diiodosilane, hexachlorodisilane, octachlorotrisilane, bis(dimethylamino)silane, bis(diethylamino)silane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, hexamethylcyclotrisilazane, tetraethyltrisilicate, dimethoxydimethylsilane, trimethoxymethylsilane, octamethylcyclotetrasiloxane, 1,1,3,5,5,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and combinations thereof.

[0090] The methods and systems disclosed herein can be used to deposit boron-containing (B) films, as non-limiting examples, such as hard masks, low-electricity dielectrics, liner layers, boron-doped films (e.g., borosilicate glasses), and films comprising boron nitride, boron carbide, boron carbonitride, and boron oxide. In some embodiments, the boron-containing film is selected from boron nitride, boron carbide, boron carbonitride, boron oxide, and combinations thereof. In some embodiments, the boron-containing film is amorphous boron nitride. In these embodiments, the precursor and the radicalized precursor formed therefrom comprise boron. In some embodiments, the precursor comprises boron and may also comprise one or more of carbon (C), hydrogen (H), nitrogen (N), and oxygen (O). The boron-containing precursor may include one or more BC bonds, BH bonds, BN bonds, and BO bonds. In some embodiments, the boron-containing precursor consists of boron and a halogen. The halogen may be selected from fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). In some embodiments, the halogen is selected from chlorine (Cl), bromine (Br), and iodine (I). In some embodiments, the halogen is selected from chlorine (Cl) and bromine (Br). In some embodiments, the boron-containing precursor comprises boron and a halogen. In some embodiments, the boron-containing precursor is selected from boron trihalides. In some embodiments, the boron-containing precursor comprises BCl3. In some embodiments, the boron-containing precursor comprises BBr3.

[0091] Other suitable boron-containing precursors may be selected from boranes, alkylboranes, arylboranes, carboranes, amines or aminoboranes, borate esters, cycloboranes, and combinations thereof. In some embodiments, the boron-containing precursor is a borane (B x H Y Suitable examples of borane precursors are diborane (B2H6) and tetraborane (B4H6). 10 ), pentaborane (B5H9), decaborane (B 10 H 14 ), octadecorane (B) 18 H 22 In some embodiments, the borane precursor is substituted with one or more alkyl, aryl, or combinations thereof. For example, one or more hydrogen atoms in the borane may be substituted with alkyl and / or aryl groups. Examples of suitable alkyl and aryl borane precursors include trimethylborane (B(CH3)3), triethylborane (B(C2H5)3), triphenylborane (B(C6H5)3), etc. In some embodiments, the boron-containing precursor is a carborane. Carboranes contain boron, carbon, and hydrogen, and may optionally be substituted with one or more oxygen, nitrogen, and halogen atoms. Examples of suitable carborane precursors are meta-carborane (C2B4H8), ortho-carborane (C2B... 10 H 12 In some embodiments, the boron-containing precursor is an amine or an aminoborane. Examples of aminoboranes include ammoniaborane (NH3BH3) and its substituted derivatives (e.g., NR). n H 3-nBH3, where n is an integer from 1 to 3, and each R is independently a substituent, preferably alkyl or aryl). Examples of aminoboranes include monoaminoboranes, diaminoboranes, triaminoboranes (e.g., H2B(NH2), HB(NH2)2, and B(NH2)3, respectively) and their linear and cyclic substituted derivatives (e.g., H2B(NHR), H2B(NR2), HB(NHR)2, HB(NR2)2, B(NHR)3, and B(NR2)3, wherein each R is independently a substituent, preferably alkyl or aryl). Examples of suitable amine and aminoborane precursors are ammoniaborane (NH3BH3), methylamineborane (CH3NH2BH3), dimethylamineborane ((CH3)2NHBH3), trimethylamineborane ((CH3)3NBH3), tert-butylamineborane ((CH3)3CNH2BH3), tris(dimethylamino)borane (B(N(CH3)2)3), and β-cycloboronylamineborane (B4N4H). 16 In some embodiments, the boron-containing precursor is a borate ester. Examples of borate esters include orthoborates such as borate esters (BR2(OR)), borate esters (BR2(OR)), and borate esters (B(OR)3), as well as metaborates (B3O3(OR)3), wherein each R is independently a substituent, preferably alkyl or aryl. Examples of suitable borate ester precursors are trimethyl borate (B(OCH3)3), triethyl borate (B(OCH2CH3)3), etc. In some embodiments, the boron-containing precursor is a cycloborazane or a substituted cycloborazane. Cycloborazanes have the chemical structure B3H6N3. In substituted cycloborazanes, one or more H atoms are replaced by substituents (R), preferably alkyl or aryl. Additionally or alternatively, one or more boron or nitrogen atoms in the cycloborazane ring may be replaced by carbon atoms. Examples of suitable cycloborazine precursors are cycloborazine (B3H6N3), 2,4,6-trichlorocycloborazine (B3H3Cl3N3), 2,4,6-tribromocycloborazine (B3H3Br3N3), etc. In some embodiments, the boron-containing precursor is selected from meta-carboranes, ortho-carboranes, aminoboranes, dimethylamineboranes, trimethylamineboranes, tert-butylamineboranes, tris(dimethylamino)boranes, β-(cycloborazinyl)amineboranes, trimethyl borate, triethyl borate, cycloborazines, 2,4,6-trichlorocycloborazines, 2,4,6-tribromocycloborazines, dicycloborazines, and combinations thereof.

[0092] In some embodiments, the reactive gas may be an oxygen-containing gas. For example, the oxygen-containing gas may be selected from one or more of the following: oxygen (O2), ozone (O3), water (H2O), hydrogen peroxide (H2O2), alcohols (ROH, where R is alkyl or aryl) such as methanol (CH3OH) and ethanol (C2H5OH), nitrogen dioxide (NO2), nitrous oxide (N2O), and oxygen atoms (O*) generated in the plasma. In some embodiments, the reactive gas may be a nitrogen-containing gas. For example, the nitrogen-containing gas may be selected from one or more of ammonia (NH3), hydrazine (N2H4), nitric oxide (NO) and activated nitrogen (N2), activated ammonia (NH3), and nitrogen atoms (N*) generated in the plasma. In some embodiments, the reactive gas may be selected from one or more of hydrogen (H2) and hydrogen atoms (H*) generated in the plasma. In some embodiments, the reactive gas includes one or more of O2, H2O, NH3, and H2. In some embodiments, the reactive gas may contain O*, N*, H*, and combinations thereof.

[0093] The methods and systems disclosed herein offer several benefits, including enhanced precursor reactivity, which can reduce processing time and / or the number of cycles required to achieve the desired film thickness. It also allows deposition to occur under lower temperature processing conditions. The methods and systems can also improve film uniformity and conformability. Free radicalized precursors are more reactive and can be smaller in size compared to their derived parent precursors, which may lead to a higher degree of surface coverage on the substrate, resulting in faster growth, higher uniformity, and improved consistency, which can occur, for example, on the sidewalls of trench structures.

[0094] Although embodiments of the present disclosure and their advantages have been described in detail, it should be understood that various changes, substitutions, and modifications can be made herein without departing from the spirit and scope of the disclosure as defined by the appended claims. For example, those skilled in the art will readily understand that many features, functions, processes, and materials described herein can vary while still remaining within the scope of the present disclosure. Furthermore, the scope of this application is not intended to be limited to specific embodiments of the processes, machines, manufactures, compositions of matter, apparatuses, methods, and steps described in the specification. As will be readily understood by those skilled in the art from the disclosure of this disclosure, existing or later-developed processes, machines, manufactures, compositions of matter, apparatuses, methods, or steps can be utilized to perform substantially the same functions or achieve substantially the same results as the corresponding embodiments described herein. Therefore, the appended claims are intended to include such processes, machines, manufactures, compositions of matter, apparatuses, methods, or steps within their scope. Moreover, the scope of this disclosure is defined by the scope of the appended claims. Additionally, the scope of each claim is constructed as an individual embodiment, and various combinations of claims and combinations of embodiments are within the scope of this disclosure.

Claims

1. A method for forming a film on the surface of a substrate, comprising: The substrate is introduced into the lower chamber of the reaction chamber, wherein an ion trap is used to divide the reaction chamber into an upper chamber and a lower chamber; The first plasma is introduced into the upper chamber; The precursor is introduced into the reaction chamber and radicalized using a first plasma; The reactants are introduced into the reaction chamber; A second plasma is introduced into the upper chamber to radicalize the reactants.

2. The method as described in claim 1, wherein, The precursor includes silazane.

3. The method as described in claim 1, wherein, The ion trap is grounded.

4. The method of claim 1, wherein, The precursor and the reactant are introduced into the reaction chamber via a spray head, and the spray head is connected to an RF generator to generate the first plasma and the second plasma.

5. The method of claim 1, further comprising a purging step after introducing the precursor into the reaction chamber and after introducing the second plasma into the upper chamber.

6. The method of claim 1, wherein, The RF power of the first plasma is lower than that of the second plasma.

7. The method of claim 1, wherein, The first plasma has an RF power of less than 100W, and the second plasma has an RF power of more than 50W.

8. A method for forming a film on the surface of a substrate, comprising: A reaction chamber is provided, which has an upper chamber and a lower chamber separated by an ion trap; The substrate is introduced into the lower chamber; The precursor is introduced into the reaction chamber and the first plasma is used in the upper chamber to radicalize the precursor to form a radicalized precursor; The reactants are introduced into the reaction chamber and a second plasma is generated in the lower chamber to decompose the reactants and expose the substrate to various plasma materials.

9. The method of claim 8, wherein, The precursor includes silazane.

10. The method of claim 8, further comprising: The reaction chamber is purged between the steps of introducing the precursor and introducing the reactant.

11. The method of claim 8, further comprising: Repeat the steps of introducing the precursor and the reactant.

12. The method as described in claim 8, in, The precursor and the reactant are introduced into the reaction chamber via a spray head, and the spray head is connected to a first RF generator to generate the first plasma. The substrate is placed on a base, and the base is connected to a second RF generator to generate the second plasma.

13. The method of claim 8, wherein, The RF power of the first plasma is less than 100W, and the RF power of the second plasma is less than 1500W.

14. The method of claim 8, wherein, The reactants include at least one of hydrogen, nitrogen, and oxygen.

15. The method of claim 8, wherein, The RF power of the second plasma is higher than that of the first plasma.

16. A semiconductor processing apparatus, comprising: Reaction chamber; The spray head is located at the top of the reaction chamber; The base, located at the bottom of the reaction chamber, supports the substrate; An ion trap is located between the spray head and the base; A precursor source, used to introduce the precursor into the reaction chamber via a spray nozzle; Reactant source, used to introduce reactants into the reaction chamber via spray nozzles; A first RF generator is connected to a spray head and generates a first plasma between the spray head and the ion trap via the spray head.

17. The semiconductor processing apparatus of claim 16, wherein, The ion trap is a mesh plate, and the mesh plate is grounded.

18. The semiconductor processing apparatus of claim 16, further comprising a controller configured to: The first plasma is ignited between the spray head and the ion trap; The precursor is introduced into the reaction chamber; Purge the reaction chamber; The reactants are introduced into the reaction chamber; Ignite the second plasma between the ion trap and the base; as well as Purge the reaction chamber.

19. The semiconductor processing apparatus of claim 16, further comprising a second RF generator connected to the base and generating a second plasma between the ion trap and the base via the base.

20. The semiconductor processing apparatus of claim 19, wherein, The first RF generator and the second RF generator are separate RF generators.

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