Process and apparatus for radical enhanced vapor deposition

Abstract

The present disclosure relates to methods and systems for forming a radical treated film on a substrate surface. More specifically, the disclosed methods and systems utilize free radical treatment to treat films that have been deposited on a surface of a substrate. The radical processing takes place in a radical processing chamber and the deposition takes place in a deposition chamber where these chambers are operably coupled to allow substrates to be transferred therebetween without any air interruption.

Description

Technical Field

[0001] The present disclosure relates to methods and systems for depositing thin films on a substrate surface using plasma enhanced atomic layer deposition (PEALD), and more particularly to using radical enhanced atomic layer deposition (REALD) to deposit thin films on a substrate. Background Art

[0002] Plasma enhanced ALD (PEALD) can be used to overcome some of the limitations of thermal ALD processes. In these methods, plasma is used in at least one reaction step. The use of high-energy plasma species (such as free radicals) as reactants increases reactivity, allows lower temperature processing, and in many cases, provides improved film properties (such as density, impurity levels, and electronic properties). Various reactor configurations can be used to affect the type and density of plasma species that interact with the substrate. In direct PEALD, the plasma is generated in close proximity to the substrate surface. The flow rate of energetic species (such as ions, free radicals, etc.) can be very high, allowing uniform film formation and short plasma exposure time, but plasma-induced damage and anisotropy in the film may also occur. In contrast, in radical enhanced ALD (REALD), which is a PEALD that utilizes a remote plasma source, ions are prevented from reaching the substrate surface, and film growth relies solely on reactive free radicals in the plasma. This approach avoids the plasma-induced damage and anisotropy typically associated with the PEALD process, while still outperforming the thermal ALD process in terms of reactivity.

[0003] Plasma enhanced atomic layer deposition (PEALD) is widely used in the semiconductor industry due to its ability to deposit high quality films from a wide range of precursor chemistries using energetic ions under relatively mild conditions. However, the inherent anisotropy of the method means that its applicability is limited in the most challenging device designs, where film conformality is important. Radical enhanced ALD (REALD) has been identified as a potential solution for the conformal growth of high quality films. Unlike ions, free radicals are not accelerated to the substrate surface, so free radical processes generally result in conformal film deposition, which comes at the expense of film quality compared to PEALD processes. Summary of the invention

[0004] This summary is provided to introduce some concepts in a simplified form. These concepts are further described in detail in the detailed description of the example embodiments disclosed below. This summary is not intended to identify the key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0005] One aspect of the present disclosure is a method for forming a free radical treatment film on a substrate surface. The method includes providing a substrate and performing one or more super cycles. Each super cycle includes a deposition step and a free radical treatment step. The deposition step includes supplying a gas phase precursor into a deposition chamber to deposit a film onto the substrate. The free radical treatment step includes generating a remote plasma, obtaining a free radical stream from the remote plasma, and exposing the substrate to the free radical stream in a free radical treatment chamber. The deposition chamber and the free radical treatment chamber are operably coupled to allow the substrate to be transferred between them without any air interruption.

[0006] Another aspect of the present disclosure is a system, such as an apparatus. The system includes one or more processing chambers, each processing chamber including two or more stations, each station including an upper compartment and a lower compartment. The upper compartment is configured to contain a substrate during substrate processing. The lower compartment includes a shared intermediate space between two or more stations. The system also includes: a first transfer system configured to move a substrate from a first processing chamber to a second processing chamber in a wafer handling chamber; a second transfer system configured to move a substrate from a first station to a second station within the shared intermediate space of the processing chambers; a first heating unit configured to control the temperature of the first station independently of the temperature of the second station; a pressure system including a pump and an exhaust device, the pressure system configured to maintain a common processing chamber pressure in two or more stations; and a controller including a processor that provides instructions to the apparatus to control the following cycle:

[0007] (a) placing a substrate in a first station;

[0008] (b) depositing a film on a substrate by a vapor deposition process in a first station;

[0009] (c) placing the first substrate in a second station after depositing the film on the substrate;

[0010] (d) performing a radical treatment on the substrate by supplying a radical flow to the station to form a modified film; and

[0011] Steps (a)-(d) in the cycle are repeated until a film of desired thickness is deposited on the substrate.

[0012] Another aspect of the present disclosure is a method for film deposition. The method comprises the following steps:

[0013] (a) placing a substrate in a first station, the first station comprising an upper chamber and a lower chamber, wherein the lower chamber comprises a shared intermediate space among the first station, the second station, the third station and the fourth station;

[0014] (b) contacting the substrate in the first station with a precursor, wherein the contact with the precursor forms a first film layer on the first substrate;

[0015] (c) after contacting the substrate in the first station with the precursor, placing the substrate in a second station;

[0016] (d) performing a first radical treatment on the substrate by contacting a surface of the first film layer with a reactive gas;

[0017] (e) after performing the first free radical treatment on the substrate, placing the substrate in a third station;

[0018] (f) contacting the substrate in the third station with a precursor, wherein the contact with the precursor forms a second film layer on the first substrate;

[0019] (g) after contacting the substrate in the third station with the precursor, placing the substrate in a fourth station;

[0020] (h) performing a second radical treatment on the substrate by contacting a surface of the second film layer with a reactive gas; and

[0021] Steps (a)-(h) in the cycle are repeated until a film of desired thickness is deposited on the first substrate.

[0022] In these aspects, in some embodiments, the free radical treatment film comprises carbon.

[0023] In these aspects, in some embodiments, the depositing step includes a plurality of deposition cycles.

[0024] In these aspects, in some embodiments, an ion trap is used to obtain a flux of radicals from a remote plasma.

[0025] In these aspects, in some embodiments, an ion trap is provided in the reaction chamber between the remote plasma discharge and the substrate.

[0026] In these aspects, in some embodiments, the ion trap is an electrically grounded grid plate.

[0027] In these aspects, in some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas at a radio frequency (RF) power of 500 W or less.

[0028] In these aspects, in some embodiments, the remote plasma discharge is generated by gas phase ionization of a gas at a radio frequency (RF) power of 100 W or less.

[0029] In these aspects, in some embodiments, the temperature of the substrate is at least 40°C and no more than 550°C.

[0030] In these aspects, in some embodiments, the temperature of the substrate is at least 100°C and no more than 400°C.

[0031] In these aspects, in some embodiments, the first precursor includes silicon.

[0032] In these aspects, in some embodiments, the first precursor is selected from the group consisting of: silanes, alkylsilanes, halosilanes, aminosilanes, silicon alkoxides, siloxanes, and combinations thereof.

[0033] In these aspects, in some embodiments, the first precursor is selected from the group consisting of silane, disilane, trisilane, dimethylsilane, diethylsilane, trimethylsilane, triethylsilane, dichlorosilane, diiodosilane, hexachlorodisilane, octachlorotrisilane, bis(diethylamino)silane, bis(diethylamino)dimethylsilane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, hexamethylcyclotrisilazane, tetraethyl trisilicate, dimethoxydimethylsilane, trimethoxymethylsilane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 1,1,3,5,5,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, bis(diethoxysilyl)ethane, methoxypropyltrimethoxysilane, and combinations thereof.

[0034] In these aspects, in some embodiments, the first precursor includes boron.

[0035] In these aspects, in some embodiments, the first precursor is selected from the group consisting of: borane, alkylborane, arylborane, carborane, amineborane, aminoborane, borate ester, borazine, triethylborane, and combinations thereof.

[0036] In these aspects, in some embodiments, the first precursor is selected from: nested carborane, ortho carborane, ammonia borane, dimethylamine borane, trimethylamine borane, tert-butylamine borane, tri(dimethylamino)borane, bromobis(diethylamino)borane, bromobis(dimethylamino)borane, triethylboron, boron triiodide, boron tribromide, B-(cycloribosyl)amine borane, trimethyl borate, triethyl borate, cycloborazine, 2,4,6-trichlorocycloborazine, 2,4,6-tribromocycloborazine, diborazine, and combinations thereof.

[0037] In these aspects, in some embodiments, the remote plasma is selected from: an oxygen-containing gas, a nitrogen-containing gas, a hydrogen-containing gas, and combinations thereof.

[0038] In these aspects, in some embodiments, the radical flux includes one or more of oxygen radicals, nitrogen radicals, hydrogen radicals, and combinations thereof.

[0039] In these aspects, in some embodiments, the radical treatment film is selected from the group consisting of silicon nitride, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, silicon carbide, silicon oxycarbide, silicon oxide, and combinations thereof.

[0040] In these aspects, in some embodiments, the radical treatment film is selected from the group consisting of: boron nitride, boron carbide, boron carbonitride, boron oxide, and combinations thereof.

[0041] In these aspects, in some embodiments, the radical treatment film is selected from the group consisting of silicon oxycarbonitride, silicon carbonitride, boron nitride, boron carbonitride, hydrogenated boron carbonitride, and combinations thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The accompanying drawings are incorporated into the specification and form a part thereof to illustrate multiple examples of the present disclosure. The drawings presented herein are not meant to be actual views of any particular material, structure or device, but are merely idealized representations for describing embodiments of the present disclosure. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the sizes of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated embodiments of the present disclosure. The accompanying drawings and descriptions together explain the principles of the present disclosure. The accompanying drawings simply illustrate how to make and use preferred and alternative examples of the present disclosure, and should not be interpreted as limiting the present disclosure to only the examples shown and described. As shown in the drawings referenced below, further features and advantages will become apparent from the following more detailed description of various aspects, embodiments and configurations of the present disclosure.

[0043] Figure 1 is a process diagram of an exemplary embodiment of the present disclosure.

[0044] Figure 2A A multi-processing chamber module and process according to some embodiments herein are shown.

[0045] Figure 2B A dual chamber module and process according to some embodiments herein are shown.

[0046] Figure 3 is a schematic diagram of a reactor assembly according to some embodiments of the present disclosure, wherein plasma is generated in an upper portion of a reaction chamber.

[0047] Figure 4 is a schematic diagram of a reactor assembly according to some embodiments of the present disclosure, wherein a remote plasma unit (RPU) is used to generate plasma upstream of a radical processing chamber. DETAILED DESCRIPTION

[0048] Although certain embodiments and examples are disclosed below, those skilled in the art will appreciate that the invention extends beyond the specifically disclosed embodiments and / or uses of the invention and their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited by the specifically disclosed embodiments described below.

[0049] It should be understood that the configuration and / or method described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, because many variations are possible. The specific routine or method described herein can represent one or more of any number of processing strategies. Therefore, the various actions shown can be performed in the order shown, in other orders, or omitted in some cases.

[0050] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various processes, systems and configurations, and other features, functions, acts and / or properties disclosed herein, and any and all equivalents thereof.

[0051] As used herein, the term "substrate" may refer to any one or more underlying materials, including any one or more underlying materials that may be modified or on which a device, circuit, or film may be formed. A "substrate" may be continuous or non-continuous; rigid or flexible; solid or porous; and combinations thereof. A substrate may be in any form, such as a plate or a workpiece. A plate-like substrate may include wafers of various shapes and sizes. A substrate may be made of semiconductor materials, including, for example, silicon, silicon germanium, silicon oxide, gallium arsenide, gallium nitride, and silicon carbide.

[0052] Examples of workpieces may include medical devices (e.g., stents and syringes), jewelry, tooling equipment, components for battery manufacturing (e.g., anodes, cathodes, or separators), or components for photovoltaic cells, etc.

[0053] The continuous substrate may extend beyond the boundaries of the processing chamber in which the deposition process occurs. In some processes, the continuous substrate may be moved through the processing chamber so that the process continues until the end of the substrate is reached. The continuous substrate may be provided from a continuous substrate supply system to allow the continuous substrate to be manufactured and output in any suitable form.

[0054] Non-limiting examples of continuous substrates may include sheets, nonwoven films, rolls, foils, meshes, flexible materials, bundles of continuous filaments or fibers (eg, ceramic fibers or polymer fibers). A continuous substrate may also include a carrier or sheet on which a discontinuous substrate is mounted.

[0055] As used herein, "atomic layer deposition", abbreviated as "ALD", refers to a method of depositing a film on a substrate by sequentially exposing the substrate surface to alternating gas-phase reactants. In contrast to chemical vapor deposition, the different reactants are not present in the reactor at the same time, but are introduced as a series of continuous, non-overlapping pulses. In each of these pulses, the reactants react with the surface in a self-limiting manner or a substantially self-limiting manner. In addition, as used herein, ALD may also be meant to include processes designated by related terms, such as chemical vapor atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of reactants.

[0056] As used herein, "boron carbide" or "boron carbide" x C y " refers to a material comprising boron and carbon. In some embodiments, the boron carbide may not include a significant proportion of elements other than boron and carbon. In some embodiments, the boron carbide includes B4C. In some embodiments, the boron carbide may consist essentially of B4C. In some embodiments, the boron carbide may not include stoichiometric boron carbide. In some cases, the boron carbide may include other elements, such as hydrogen.

[0057] As used herein, "boron carbonitride" or "B x C y N z " refers to a material containing boron, carbon and nitrogen. Boron carbonitride can be represented by formula B x C y N z = , where the sum of x, y and z is equal to 3. In some cases, the boron carbonitride may include other elements, such as hydrogen. The boron carbonitride may include boron carbide and boron nitride.

[0058] As used herein, "boron oxycarbide" or "B x O y C y " refers to a material containing boron, oxygen and carbon. In some embodiments, boron oxide may not include a significant proportion of elements other than boron, oxygen and carbon. Boron oxide can be represented by formula B x O y C y , wherein x may be in the range of about 0 to about 6, y may be in the range of about 0 to about 3, and z may be in the range of about 0 to about 3. In some cases, the boron oxycarbide may not include stoichiometric boron oxycarbide. In some cases, the boron oxycarbide may include other elements, such as carbon and / or hydrogen.

[0059] As used herein, "hydrogenated carbon boron nitride" refers to a material comprising hydrogen, boron, carbon, and nitrogen. In some cases, hydrogenated carbon boron nitride may include other elements.

[0060] As used herein, "chemical vapor deposition," abbreviated "CVD," 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.

[0061] As used herein, "chemisorption" refers to an adsorption process resulting from a reaction on an exposed surface that creates, for example, covalent or ionic bonds between the surface and the adsorbate.

[0062] As used herein, "film" refers to a continuous, substantially continuous or discontinuous material extending in a direction perpendicular to the thickness direction to cover at least a portion of a surface. The film may include two-dimensional materials, three-dimensional materials, nanoparticles, or even partial or complete molecular layers or partial or complete atomic layers or clusters of atoms and / or molecules. The film may be composed of one or more indistinguishable layers (e.g., monolayers or sub-monolayers) to produce a uniform or substantially uniform material, wherein the number of layers affects the thickness of the material.

[0063] As used herein, "gas" refers to a state of matter composed of atoms or molecules that have neither a definite volume nor a definite shape. Gases include evaporated solids and / or liquids, and may consist of a single gas or a mixture of gases, depending on the circumstances.

[0064] As used herein, "plasma" refers to an ionized gas composed of approximately equal amounts of negatively and positively charged species (usually electrons and ions). Excited and reactive species are also contained in the plasma, such as atoms and free radicals, metastable atoms and molecules, and photons. Plasma discharges require an 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) plasmas, which differ in the generation of excited and reactive species, and therefore, can provide very different fluxes of various species.

[0065] As used herein, a "direct plasma generator" may refer to an active species generator configured to form and maintain a plasma within a process chamber between a perforated faceplate of a showerhead injector and a substrate support of the process chamber, and a "remote plasma generator" may refer to an active species generator configured to form and maintain a plasma within a process chamber such that an ion trap of the process chamber is disposed between the plasma and the substrate support of the process chamber. In addition, a "remote plasma generator" may refer to an active species generator configured to form and maintain a plasma outside a process chamber and introduce active species formed in the plasma into the process chamber, such as through an active species conduit or channel.

[0066] As used herein, "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 in the precursor) is incorporated into the compound or element produced by the chemical reaction. The compound or element produced by the chemical reaction can be a layer and / or film formed on the surface of the substrate.

[0067] As used herein, "silicon carbide" or "SiC" refers to a material that includes 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 includes SiC. In some embodiments, silicon carbide may consist essentially of SiC. Silicon carbide is not necessarily a stoichiometric composition. The amount of silicon may be in the range of 5% to 50%; the amount of carbon may be in the range of about 50% to about 95%. In some embodiments, in addition to silicon and carbon, the SiC film may include one or more elements, such as hydrogen and / or nitrogen.

[0068] As used herein, "silicon carbonitride" or "Si x C y N z " or "SiCN" refers to a material containing silicon, carbon and nitrogen. Silicon carbonitride can be represented by the formula Si x C y N zIn some embodiments, silicon carbonitride may include 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 by atom. In some embodiments, the 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 by atom. In some embodiments, the silicon carbonitride may contain about 0% to about 70% nitrogen by atom. In some embodiments, the silicon carbonitride may contain about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% nitrogen by atom. In some embodiments, the silicon carbonitride may contain about 0% to about 50% silicon by atom. In some embodiments, the silicon carbonitride may contain about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon by atom. In some cases, silicon carbonitride may include other elements, such as hydrogen.Silicon carbonitride may include silicon carbide and silicon nitride.

[0069] As used herein, "silicon oxycarbide" or "Si z O x C y " or "SiOC" refers to a material comprising silicon, oxygen, and carbon. As used herein, unless otherwise specified, SiOC is not intended to limit, restrict, or define bonding or chemical states, such as oxidation states of Si, O, C, and / or any other elements in the film. In some embodiments, Si z O x C ySi-C bonds and / or Si-O bonds may be included. In some embodiments, SiOC may include Si-C bonds and Si-O bonds, and may not include Si-N bonds. In some embodiments, in addition to Si-C and / or Si-O bonds, SiOC may include Si-H bonds. In some embodiments, SiOC may include more Si-O bonds than Si-C bonds, for example, the ratio of Si-O bonds to Si-C bonds may be about 1:10 to about 10:1. In some embodiments, SiOC may include about 0% to about 50% carbon by atom. In some embodiments, SiOC may include about 0.1% to about 40%, about 0.5% to about 30%, about 1% to about 30%, or about 5% to about 20% carbon by atom. In some embodiments, SiOC may include about 0% to about 70% oxygen by atom. In some embodiments, SiOC may include about 10% to about 70%, about 15% to about 50%, or about 20% to about 40% oxygen by atom. In some embodiments, SiOC may include about 0% to about 50% silicon by atom. In some embodiments, the SiOC film may include about 10% to about 50%, about 15% to about 40%, or about 20% to about 35% silicon by atom. In some embodiments, the silicon oxycarbide may be of the formula Si z O x C y Represents, wherein z may be in the range of about 0 to about 2, x may be in the range of about 0 to about 2, and y may be in the range of about 0 to about 5.

[0070] As used herein, "silicon oxycarbon nitride" or "Si z O x C y N w " or "SiOCN" refers to a material comprising silicon, oxygen, nitrogen, and carbon. As used herein, unless otherwise specified, SiOCN is not intended to limit, restrict, or define bonding or chemical states, such as the oxidation state of Si, O, C, N, and / or any other elements in the material. In some embodiments, SiOCN may be a material having the chemical formula Si z O x C y N w A material represented by wherein z may be in the range of about 0 to about 2, x may be in the range of about 0 to about 2, y may be in the range of about 0 to about 2, and w may be in the range of about 0 to about 2.

[0071] As used herein, a "substituent" refers to an atom or a group of atoms that replaces one or more atoms (such as hydrogen atoms) or groups of atoms in a parent compound, thereby becoming part of the resulting new compound. The substituent replaces the original atom or group of atoms in the parent molecule. For simplicity, a substituent can be represented as an "R" group in a chemical formula, and each "R" group in a compound can be independently selected. Examples of substituents include, but are not limited to: hydrogen atoms (H), "alkyl", such as saturated straight or branched C1 to C 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 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 or branched C1 to C6 alcohols (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl); , hydroxypentyl and hydroxyhexyl); "alkoxycarbonyl", such as straight or branched C1 to C6 carbonyl hydrocarbon (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl); thiol (SH); "alkylthiol", such as straight or branched C1 to C6 thiols (e.g., thiolmethyl, thiolethyl, thiolpropyl, thiolbutyl, thiolpentyl and thiolhexyl); halides (X), such as fluorides (F), chlorides (Cl), bromides (Br) and iodides (I); and "haloalkyl", such as straight 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 may be substituted. For example, an alkoxy group is a substituted alkyl group in which a H atom on the alkyl group is replaced by an OH group.

[0072] The articles "a" or "an" refer to one substance or a genus including a plurality of substances, depending on the situation. Therefore, the terms "a / an", "one or more", and "at least one" are used interchangeably herein. It should also be noted that the terms "include", "comprises", and "have" are used interchangeably.

[0073] The term "about" generally refers to a range of values ​​that are considered equivalent to the stated value (eg, having the same function or result). In some cases, the term "about" may include values ​​that are rounded to the nearest significant figure.

[0074] "At least one", "one or more", and "and / or" are open-ended expressions that are both conjunctive 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 alone, B alone, C alone, 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 an element (e.g., X, Y, and Z) or a class of elements (e.g., X1-X n 、Y1-Y m and Z1-Z o ), the phrase is intended to refer to individual elements selected from X, Y, and Z, combinations of elements selected from the same category (e.g., X1 and X2), and combinations of elements selected from two or more categories (e.g., Y1 and Z o ).

[0075] It should be understood that each numerical range given throughout the disclosure is considered to include the upper and lower limits, as well as each narrower numerical range that falls within such broader numerical range, just as if such narrower numerical ranges were expressly written herein. For example, the phrase "from about 2 to about 4" or "from 2 to 4" includes 2 and 4 and integers and / or integer ranges from about 2 to about 3, from about 3 to about 4, and every possible range based on real numbers (e.g., irrational numbers and / or rational numbers), such as from about 2.1 to about 3.9, from about 2.1 to about 3.4, etc.

[0076] The present disclosure generally relates to methods of forming free radical treated films on substrate surfaces using free radical enhanced atomic layer deposition and systems for performing such methods. Various aspects of the methods and systems and benefits derived therefrom will now be described.

[0077] Manufacturing modern semiconductor devices requires precise deposition of materials and careful control of thickness and composition. Ideally, the desired material composition can be directly deposited in a single-step process, but this is generally not feasible, and it is necessary to deposit a layer of material and then convert it into a layer with the desired elemental composition and properties. Plasma treatment can be a way to achieve this conversion, but this method is not suitable for carbon-containing films because any carbon present in the precursor molecules or the growing film is easily removed by the high-energy components of the plasma discharge. In this regard, methods and systems for manufacturing free radical treatment films on substrate surfaces using remote plasma are disclosed herein. The methods and systems disclosed herein advantageously expand the availability of thin film materials that are not easily manufactured using conventional processing methods. The disclosed methods can be used to deposit and adjust the elemental composition of thin film materials without losing reactive elements such as carbon. These and other advantages will become apparent from the disclosure of the various aspects, embodiments and configurations contained herein.

[0078] One aspect of the present disclosure is a method for forming a radical treatment film on a substrate surface. The method includes providing a substrate and performing one or more super cycles. A single super cycle includes a deposition step and a radical treatment step. The deposition step includes supplying a vapor phase precursor into a deposition chamber to deposit a film onto the substrate. The radical treatment step includes generating a remote plasma, obtaining a radical stream from the remote plasma, and exposing the substrate to the radical stream in a radical treatment chamber. The deposition chamber and the radical treatment chamber are operably coupled to allow the substrate to be transferred between them without any air interruption.

[0079] Figure 1 100 is a process flow chart of an embodiment of the present disclosure. At 102, a substrate is provided to a deposition chamber. A first precursor is introduced, and a film 104 is deposited on the surface of the substrate. In some embodiments, step 104 may include introducing more than one precursor into the reaction chamber in a gas phase. Deposition may be performed by any vapor deposition method, such as atomic layer deposition, chemical vapor deposition, plasma enhanced atomic layer deposition, or plasma enhanced chemical vapor deposition. The deposition temperature may be 40-550° C., and the chamber pressure may be 1-100 Torr. The deposited film may be a film comprising carbon. In addition to carbon, the film may comprise other elements, such as silicon or boron. In some embodiments, the deposited film comprises silicon, carbon, and nitrogen. In some embodiments, the deposited film comprises silicon and carbon. In some embodiments, the deposited film comprises silicon, carbon, and oxygen. In some embodiments, the deposited film comprises silicon, carbon, nitrogen, and oxygen. In one embodiment, step 104 is repeated until a target film thickness is reached. In some embodiments, the deposited film comprises boron, carbon, and nitrogen. In some embodiments, the deposited film comprises boron and carbon. In some embodiments, the deposited film comprises boron, carbon, and oxygen. In some embodiments, the deposited film comprises boron, carbon, nitrogen, and oxygen. In one embodiment, step 104 is repeated until a target film thickness is reached.

[0080] Next, the substrate with the deposited film on its surface is exposed to a radical stream 106. The radical stream is obtained from a remote plasma produced by a plasma unit. A radio frequency (RF) (e.g., 13.56 MHz or 27 MHz) plasma generator is used to generate plasma by gas phase ionization of a reactive gas. In certain embodiments, the reactive gas comprises nitrogen, hydrogen, oxygen, or a combination thereof. The plasma from the plasma unit passes through an ion trap, which captures ions from the plasma, thereby mainly free radicals passing through and arriving at the substrate surface as a radical stream. In certain embodiments, the ion trap is a mesh plate. In certain embodiments, the radical stream comprises nitrogen radicals, hydrogen radicals, oxygen radicals, or a combination thereof. Typically, the RF power used to generate the plasma is maintained between 50-1000 W.

[0081] Finally, a radical treatment film is formed on the surface of the substrate 108. In one embodiment, steps 104 and 106 may be repeated until a target film thickness 110 is reached. The number of repetition cycles (n) is not particularly limited and may be between 1 and about 5000. In some embodiments, the number of repetition cycles (n) is typically between 1 and about 2000, between 1 and about 1000, between 1 and about 500, between 1 and about 200, between 1 and about 100, or more typically between about 10 and about 1000, more typically between about 10 and about 500, more typically between about 10 and about 200, more typically between about 10 and about 100, or even more typically between about 50 and about 1000, even more typically between about 50 and about 500, or even more typically between about 50 and about 200. The number of deposition cycle repetitions (n) depends on the growth rate of the deposited material and the desired film thickness. In one embodiment, after a certain number of deposition steps 104, the substrate is exposed to the radical flux 106. For example, step 106 may be performed after 10 deposition cycles, or after 20 deposition cycles, or after 30 deposition cycles. The method and the individual process steps will be described in more detail below.

[0082] Figure 2A A multi-processing chamber module according to some embodiments is shown. In some embodiments, the multi-processing chamber module may include a four-station arrangement, which includes a deposition station (such as Figure 2A The remaining two stations (such as RC1 and RC3 in Figure 2A RC2 and RC4 in FIG. 10A ) may include a processing station where the substrate may be exposed to a free radical stream. In some embodiments, more stations may be present in a multi-processing chamber module. Typically, the additional stations will include at least one additional deposition station and at least one additional processing station.

[0083] As used herein, "station" refers broadly to a location that can contain a substrate, so that processing can be performed on the substrate in the station. Therefore, a station can refer to a reactor, or a part of a reactor, or a reaction space or reaction chamber in a reactor. In some embodiments, the stations according to the embodiments of this article are "gas-isolated" from each other or are configured to be in gas isolation when processing a substrate in a station. In some embodiments, the station is in gas isolation by a physical barrier instead of a gas bearing or a gas curtain. In some embodiments, the station is in gas isolation by a physical barrier in combination with a gas bearing and a gas curtain. In some embodiments, after or while a substrate is placed in a particular station, the substrate is placed in gas isolation from other stations (so that a processing step can be performed in the station), and after the substrate has been processed in the station, the station is separated from gas isolation, and the substrate can be removed from the station and positioned in the intermediate space. Substrates from multiple different stations can be placed in a shared intermediate space to move from one station to another. The station can be placed in gas isolation, such as by a physical barrier. In some embodiments, the station is not placed in gas isolation. In some embodiments, one or more stations include a heating and / or cooling system so that different precursors in different stations can process substrates at different temperatures at the same time. Thus, in some embodiments, the entire first station is at a lower or higher temperature than the entire second station, or the first station includes a susceptor that is at a lower or higher temperature than the susceptor in the second station, and / or the first precursor flows into the first station and the second precursor flows into the second station that is at a lower or higher temperature than the first station.

[0084] In some embodiments, the stations are separated from each other by solid materials and are not separated from each other by gas bearings or air curtains. In some embodiments, the stations are separated from each other by solid materials or air curtains and are not separated from each other by gas bearings. In some embodiments, the stations are separated from each other by solid materials or gas bearings and are not separated from each other by air curtains. Optionally, the physical barrier can move with a mobile stage that transfers substrates between the station and the intermediate space, so that the physical barrier places the station in gas isolation at the same time (or slightly earlier or later) that the substrate is placed in the station. Optionally, the physical barrier can be used in combination with a gas barrier, for example to fill some gaps left by the physical barrier. In some embodiments, a physical barrier is provided, but there is no gas barrier or air curtain.

[0085] In some embodiments, the stations include modules or chambers of the reactor such that each station includes a separate chamber or module. In some embodiments, the stations include a portion of the reaction chamber that can be placed in gas isolation from other portions of the reaction chamber by positioning a wall, gas curtain, or gas bearing between the stations. Alternatively, a given station is completely enclosed by one or more walls, gas curtains, gas bearings, or a combination of any of these items. However, in some embodiments, the stations are not separated.

[0086] like Figure 2AAs shown, during a process according to some embodiments herein, a wafer may rotate through these stations. For example, a wafer may enter a chamber at station RC1 where the wafer may undergo a first deposition process. In some embodiments, after undergoing the first deposition process, the wafer may be transferred to RC4, such as Figure 2A As shown. Alternatively, the wafer can be transferred to RC2. In either case, the wafer can undergo a first treatment process, which can include exposure to a free radical flow. After the first treatment process, the wafer can be transferred to RC3, where it can undergo a second deposition process. After undergoing the second deposition process, the wafer can be transferred to RC2 if it was previously transferred to RC4, or can be transferred to RC4 if the wafer was previously transferred to RC2. In either case, the wafer can undergo a second treatment process that is similar or identical to the first treatment process. The wafer can be transferred back to RC1 to complete a single deposition-treatment super cycle. The cycle can be repeated to obtain the desired film quality and thickness. In addition, the wafer can enter the chamber at any of RC1, RC2, RC3, or RC4 and cycle through these stations in any direction. However, in general, the deposition-treatment super cycle will begin with at least one deposition process, followed by at least one treatment process. At least one flowable deposition process can be performed simultaneously on different wafers and / or sequentially on a single wafer. In Figure 2A In the illustrated embodiment, the deposition station and the processing station of the same type are positioned diagonally. In some embodiments, this configuration can improve film uniformity. However, adjacent placement of stations of the same type is also within the scope of the embodiments disclosed herein. In some embodiments, two or more pairs of stations perform the same process on two or more substrates in parallel.

[0087] The above cycle concept can also be applied to a different number of stations. Figure 2B The dual chamber module shown can have a first station (RC1) for performing deposition and a second station (RC2) for performing a treatment process, and the substrate can be transferred cyclically between the first station and the second station. Therefore, in some embodiments, a multi-processing chamber module as described herein may include a plurality of stations, half of which can be used for deposition and the other half can be used for a treatment process. In some embodiments, the multi-processing chamber module includes at least 2 stations, for example, at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, 50, 100, 150, 200, 250, 300, 400 or 500 stations, including ranges between any two listed values. However, the number of stations is not necessarily limited.

[0088] Figure 3An example of an embodiment of the apparatus is shown, wherein the plasma is formed in the upper part of the reaction chamber 300, i.e., between the screen plate 309 and the showerhead 307. The reactive gas is supplied to the reaction chamber from the first source 303 through the gas manifold 301 via the showerhead 307 in the form of a gas. The reactive gas may be evaporated and entrained or pulsed into the carrier gas. The apparatus is also configured to allow other gases (e.g., other precursors or reactive gases, carriers, diluents, treatments, supplies and / or purge gases) to be introduced into the reaction chamber through the showerhead 307 or from other ports (not shown). Thus, the apparatus may include second and third sources 304 and 305. Unreacted gases and gaseous reaction byproducts leave the reaction chamber through an exhaust line 312. The reaction chamber 300 may optionally be equipped with a purge line and / or a pump line connected to a vacuum pump so that the reaction chamber can be purged between different reaction cycles (not shown). RF power source 313 is electrically connected to showerhead 307, allowing showerhead to be biased relative to base 311 to form plasma discharge between the two. Ion trap 309 can be located between showerhead 307 and wafer 310 to limit plasma zone 308 to the upper part of the chamber above the ion trap. For example, an electrically grounded mesh can be used as an ion trap. In some embodiments, the mesh is a metal plate that includes hundreds of holes in a showerhead-like pattern that allows free radical species to pass through to reach wafer 310 while capturing ions. For example, the mesh can include about 1000 to about 5000 holes, each having a diameter between about 0.5 mm and about 2 mm. The addition of the ion trap advantageously reduces or even eliminates the interaction of electrons and ions with the wafer surface by limiting the plasma in the plasma zone 308 at the upper part of the reaction chamber 300. The device also includes a controller 314 operably connected to the first, second, third and fourth gas valves 315-318, the RF power source 313 and other components (not shown).

[0089] The controller 314 is configured and programmed to independently control (e.g., turn on and off, etc.) the supply of various gases (e.g., first precursor, reactive gas and any diluent, process, supply and / or purge gas, etc.) and the RF power source 313 as needed to process the film on the surface of the wafer 310. In some embodiments, the controller 314 is configured to open the valve 315 to allow the carrier gas to flow from the first carrier gas source 302 into the reaction chamber. It is also configured to open the valve 316 to allow the reactive gas to flow from the first source 303 into the reaction chamber, and turn on the RF power source 313 to form a plasma. Turning on the RF power source 313 and opening the valve 316 can be performed one after another, or at the same time. After a set period of time, the controller 314 closes the valve to the reactive gas 316 and turns off the RF power source 313. The controller 314 is programmed to repeat various processing steps to process the film on the surface of the wafer 310. The controller 314 can be programmed to perform other processing steps between these different steps.

[0090] In another embodiment, the controller 314 is configured to open the valve 315 to allow the carrier gas to flow from the first carrier gas source 302 into the reaction chamber, then open the valve 316 to allow the reactive gas to flow from the first source 303 into the reaction chamber, and simultaneously turn on the RF power source 313 to form a plasma. Turning on the RF power source 313 and opening the valve 316 can be performed one after the other, or simultaneously. After a set period of time, the controller 314 closes the valve to the first precursor 316 and turns off the RF power source 313. The controller 314 is programmed to repeat various processing steps to process the film on the surface of the wafer 310. The controller 314 can be programmed to perform other processing steps between these different steps.

[0091] Figure 4 An example of an embodiment of a free radical processing chamber is shown, in which a plasma is formed using a remote plasma unit (RPU) 408 upstream of a reaction chamber 400. Optionally, a second plasma source may be provided. For example, a second plasma source 415 may be electrically connected to a showerhead 410, allowing the showerhead to be biased relative to a base 412 to form a second plasma discharge between the two. A carrier gas is supplied from a first carrier gas source 402 through a gas manifold 401 and enters the reaction chamber 400 through a showerhead 410 through RPU408, the showerhead 410 being located directly above the base 412, and a wafer 411 (i.e., a planar substrate) being placed on the base 412. Reactive gases may be evaporated and entrained in or pulsed into the carrier gas. The device is also configured to allow other gases from an optional third source 404 to flow through RPU408.

[0092] For example, in some cases, it may be beneficial to introduce a cleaning gas (e.g., NF3 diluted in an inert gas) periodically or even between each reaction cycle to remove any deposits from the decomposed precursor chemicals in one or more of the gas lines, gas manifold 401, RPU 408, and showerhead 410. Additional gases (e.g., carrier gas, diluent, process, supply, and / or purge gas) from a second source 406 may flow into the reaction chamber 400 from the second gas manifold 405 through the showerhead 410 or from other ports (not shown). Unreacted gases and gaseous reaction byproducts are exhausted from the bottom of the reaction chamber through exhaust line 413. The reaction chamber may optionally be equipped with a purge line and / or a pump line connected to a vacuum pump so that the reaction chamber can be purged between different reaction cycles (not shown). The device also includes a controller 414, which is operably connected to the first, second and third gas valves 416-418 on the first gas manifold 401, the first and second gas valves 419 and 420 on the second gas manifold 405, the RF power source for the RPU409, the second optional RF power source 415 and other components (not shown). Optionally, the device also includes an ion trap 421, which can be located between the showerhead 410 and the wafer 411 to limit the plasma zone to the upper part of the chamber above the ion trap. For example, an electrically grounded mesh can be used as an ion trap. In some embodiments, the mesh is a metal plate that includes hundreds of holes in a showerhead-like pattern that allows free radical species to pass through to the wafer 411 while capturing ions. For example, the mesh can include between about 1000 and about 5000 holes, each having a diameter between about 0.5 mm and about 2 mm. The addition of the ion trap advantageously reduces or even eliminates the interaction of electrons and ions with the wafer surface by limiting the plasma to the plasma zone in the upper part of the reaction chamber 400.

[0093] The controller 414 is configured and programmed to independently control (e.g., turn on and off, etc.) the supply of various gases (e.g., carrier gas, reactive gas and any diluent, process, supply and / or purge gas, etc.), the plasma source, and the optional second plasma source as needed to treat the film on the surface of the wafer 412 with the free radical flow. For example, in some embodiments, the controller 414 opens the valve 419 to allow the reactive gas to flow from the second source 406 into the reaction chamber 400, and turns on the RF power 409 in the RPU. After a set period of time, the controller 414 turns off the RF power 409. After a set period of time, the controller 414 closes the valve 419 to the reactive gas 406. The controller 414 is programmed to repeat various processing steps to treat the film on the surface of the wafer 411 with the free radical flow. The controller 414 can be programmed to perform other processing steps between these different steps.

[0094] The semiconductor processing apparatus or system disclosed herein may include Figure 4 Additional sources and additional components not shown in the figure, such as those typically found on semiconductor processing equipment. For example, the semiconductor processing equipment may be provided 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 gases, precursors, reactive gases, etc.) entering the reaction chamber. The semiconductor processing equipment may also be provided with a pumping system to purge the reaction chamber between various processing steps.

[0095] The radical treatment and deposition chamber may form part of an ALD assembly and may be a single wafer reactor or may include 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 may be performed in multiple reaction chambers, such as reaction chambers of a combination tool. In some embodiments, the method is performed in a single reaction chamber of a combination tool, but other, previous or subsequent manufacturing steps of the structure or device are performed in additional reaction chambers of the same combination 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. Reactants, precursors and other gases may be introduced into the chamber using a showerhead reaction chamber or a cross-flow reaction chamber or a combination thereof.

[0096] The above discussion has been provided for illustration using a two-step cycle. The two-step cycle shown is sufficient to explain the disclosed method, but those skilled in the art will appreciate that the principles and advantages of the embodiments taught herein can be easily extended to more complex ALD processes. A skilled technician will readily appreciate that each cycle may include additional steps (e.g., a third reactant pulse, a fourth reactant pulse, etc. may be introduced), or the same reactants, and that not all cycles need be the same (e.g., a third reactant may be introduced every five cycles to combine different elements in the desired percentage). This flexibility is provided and allows a variety of films to be produced without departing from the spirit of the present disclosure.

[0097] The methods and systems disclosed herein can be used to deposit many films, such as, as non-limiting examples, silicon (Si)-containing films and boron (B)-containing films. The methods and systems disclosed herein can be used to change the elemental composition of many films, such as, as non-limiting examples, silicon (Si)-containing films and boron (B)-containing films. In one embodiment, the methods and systems disclosed herein can be used to change the elemental composition of carbon-containing films. The first precursor may include one or more of silicon and boron. Suitable precursors may include those known to be useful in ALD, PEALD, CVD, or PECVD processes. In some embodiments, the first precursor may be used in a CVD-type deposition process, but it may not react in an ALD-type deposition process, and vice versa.

[0098] The methods and systems disclosed herein can be used to deposit silicon (Si) containing films, such as, as non-limiting examples, low dielectric constant (k) films, high-k gate silicates, low temperature silicon epitaxial films, and films containing silicon oxycarbonitride, silicon carbonitride, silicon carbide, and silicon oxycarbon. In some embodiments, the Si-containing film is selected from silicon oxycarbonitride, silicon carbonitride, silicon carbide, silicon oxycarbon, and combinations thereof. In some embodiments, the Si-containing film is selected from silicon oxycarbonitride, silicon carbonitride, and combinations thereof. In these embodiments, the first precursor comprises silicon. In some embodiments, the first precursor comprises silicon, and may further 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, silicon alkoxides, siloxanes, and combinations thereof. In some embodiments, the silicon-containing precursor is silane. Silanes contain silicon and hydrogen, and may optionally contain one or more carbon, oxygen, nitrogen, and halogen atoms. Examples of silanes include monosilane (SiH 4-n (R) n , wherein n is an integer from 0 to 4), disilane (S2H 6-n (R) n , wherein n is an integer from 0 to 6) and trisilane (S3H 8-n (R) n, wherein n is an integer from 0 to 8), etc., wherein each R is an independently selected substituent, preferably an alkyl or aryl group. Examples of suitable silane precursors are silane (SiH4), disilane (Si2H6) and organosilanes, such as dimethylsilane (H2Si(CH3)2), diethylsilane (H2Si(C2H5)2), trimethylsilane (HSi(CH3)3) and triethylsilane (HSi(C2H5)3), etc. In some embodiments, the silicon-containing precursor is a halogenated silane. A halogenated silane 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 halogenated silanes include halogenated silanes, halogenated disilanes (Si-Si), halogenated trisilanes (Si-Si-Si), etc. Examples of suitable halosilane precursors are dichlorosilane (SiH2Cl2), dibromosilane (SiH2Br2), diiodosilane (SiH2I2), hexachlorodisilane (Si2Cl6) and octachlorotrisilane (Si3Cl8), etc. In some embodiments, the silicon-containing precursor is an aminosilane. Aminosilane (or silylamine) includes at least one nitrogen atom bonded to a silicon atom (Si-N) and carbon and / or hydrogen, and may also optionally include one or more oxygen and halogen atoms. Examples of aminosilanes include mono-, di-, tri- and tetra-aminosilanes (e.g., H3Si(NH2), H2Si(NH2)2, HSi(NH2)3 and Si(NH2)4, respectively), silazanes (e.g., NH(SiH3)2) and trisilylamine (e.g., N(SiH3)2)) and substituted linear and cyclic derivatives thereof, 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), bis(diethylamino)dimethylsilane (C 10 H 26 N2Si), diisopropylaminosilane (C6H 17 NSi), N-(diethylaminosilyl)-N-ethylethylamine (C8H 22 N2Si), hexamethylcyclotrisilazane (C6H 21 N3Si3), hexamethyldisilazane (C6H 19NSi2) and the like. In some embodiments, the silicon-containing precursor is a silicon alkoxide. The silicon alkoxide includes at least one Si-OC bond and may also optionally include one or more hydrogen, nitrogen and halogen atoms. Examples of silicon alkoxides include mono-, di-, tri- and tetra-silicon alkoxides (e.g., H3Si(OCH3), H2Si(OCH3)2, HSi(OCH3)3 and Si(OCH3)4, respectively) and substituted linear and cyclic derivatives thereof, wherein one or more hydrogen atoms on the methyl and / or silane groups are independently substituted by a substituent (R), preferably an alkyl or aryl group. Examples of silicon alkoxide precursors are tetraethyl orthosilicate (TEOS, Si(OC2H5)4), dimethoxydimethylsilane (Si(OCH3)2(CH3)2 and trimethoxymethylsilane (Si(OCH3)3CH3), methoxypropyltrimethoxysilane (Si(OCH3)3C3H6OCH3), etc. In some embodiments, the silicon-containing precursor is a siloxane. Siloxane includes at least one Si-O-Si bond and may also optionally contain one or more hydrogen, carbon and halogen atoms. Examples of siloxanes include linear and cyclic siloxanes, such as cyclotrisiloxane, cyclotetrasiloxane and silsesquioxane. 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-tetramethyl-cyclotetrasiloxane (TMCTS, C4H 16 O4Si4), etc. In some embodiments, the silicon-containing precursor is selected from dimethylsilane, diethylsilane, trimethylsilane, triethylsilane, dichlorosilane, diiodosilane, hexachlorodisilane, octachlorotrisilane, bis(diethylamino)silane, bis(diethylamino)dimethylsilane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, hexamethylcyclotrisilane, tetraethyl trisilicate, dimethoxydimethylsilane, trimethoxymethylsilane, octamethylcyclotetrasiloxane, 1,1,3,5,5,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and combinations thereof.

[0099] The methods and systems disclosed herein can be used to deposit boron (B) containing films, such as, by way of non-limiting example, hard masks, low dielectrics, liner layers, boron doped films (e.g., borosilicate glass), and films containing boron nitride, boron carbide, boron carbonitride, and boron oxide. In some embodiments, the boron containing film is selected from boron carbide, boron carbonitride, hydrogenated boron carbide, hydrogenated boron carbonitride, and combinations thereof. In these embodiments, the first precursor comprises boron. In some embodiments, the first precursor comprises boron, and may further comprise one or more of carbon (C), hydrogen (H), nitrogen (N), and oxygen (O). The boron containing precursor may comprise one or more BC bonds, BH bonds, BN bonds, and BO bonds. Suitable boron containing precursors may be selected from borane, alkyl borane, aryl borane, carborane, amine or amino borane, borate ester, cycloborazine, and combinations thereof. In some embodiments, the boron containing precursor is borane (B x H Y Examples of suitable borane precursors are diborane (B2H6), tetraborane (B4H 10 ), pentaborane (B5H9), decaborane (B 10 H 14 ), octadecadiene (B 18 H 22 ) and the like. In some embodiments, the borane precursor is substituted with one or more alkyl groups, aryl groups, and combinations thereof. For example, one or more hydrogen atoms in 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), and the like. In some embodiments, the boron-containing precursor is carborane. Carborane contains boron, carbon, and hydrogen, and may optionally be substituted with one or more oxygen, nitrogen, and halogen atoms. Examples of suitable carborane precursors are nested carborane (C2B4H8), ortho carborane (C2B 10 H 12 ) etc. In some embodiments, the boron-containing precursor is an amine or an aminoborane. Examples of amine boranes include ammonia borane (NH3BH3) and its substituted derivatives (e.g., NR n H 3-nBH3, wherein n is an integer from 1 to 3 and each R is independently a substituent, preferably an alkyl or aryl group). Examples of aminoboranes include mono-, di-, tri-aminoboranes (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 an alkyl or aryl group). Examples of suitable amine and aminoborane precursors are ammonia borane (NH3BH3), methylamine borane (CH3NH2BH3), dimethylamine borane ((CH3)2NHBH3, trimethylamine borane ((CH3)3NBH3), tert-butylamine borane ((CH3)3CNH2BH3), tris(dimethylamino)borane B(N(CH3)2)3, B-(cycloribosyl)amine borane (B4N4H 16 ) and the like. 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)), borate esters (B(OR)3) and metaborate esters (B3O3(OR)3), wherein each R is independently a substituent, preferably an alkyl or aryl group. Examples of suitable borate ester precursors are trimethyl borate (B(OCH3)3), triethyl borate (B(OCH2CH3)3), and the like. In some embodiments, the boron-containing precursor is borazine or a substituted borazine. The chemical structure of borazine is B3H6N3. In substituted borazines, one or more H atoms are replaced by a substituent (R), preferably an alkyl or aryl group. Additionally or alternatively, one or more boron or nitrogen atoms in the borazine ring may be replaced by a carbon atom. Examples of suitable borazine precursors are borazine (B3H6N3), 2,4,6-trichloroborazine (B3H3Cl3N3), 2,4,6-tribromoborazine (B3H3Br3N3), diborazine (C3B2H3N), etc. In some embodiments, the boron-containing precursor is selected from the group consisting of nidoxycarborane, o-carborane, ammonia borane, dimethylamine borane, trimethylamine borane, tert-butylamine borane, tris(dimethylamino)borane, B-(cycloribosyl)amine borane, trimethyl borate, triethyl borate, borazine, 2,4,6-trichloroborazine, 2,4,6-tribromoborazine, diborane, and combinations thereof.

[0100] A plasma is generated using a reactive gas to form free radicals and / or excited species that react with a deposited layer on the substrate surface. In some embodiments, the reactive gas in the remote plasma is selected from: an oxygen-containing gas, a nitrogen-containing gas, a hydrogen-containing gas, and a combination thereof. In some embodiments, the reactive gas may include ammonia or nitrous oxide. When the reactive gas forms free radicals, in other words, this may be referred to as a free radical stream. The free radical stream includes one or more of oxygen free radicals, nitrogen free radicals, hydrogen free radicals, and a combination thereof. In some embodiments, the free radical stream may include ammonia free radicals or nitrous oxide free radicals.

[0101] The method and system disclosed herein can provide several benefits, including enhanced control over the elemental composition of the deposited film material. It can also provide a method for obtaining a conformal film containing a carbon oxide or nitride material. The method and system can also manufacture such films in an efficient manner, increase yield and avoid exposing the film material to impurities such as moisture.

[0102] Although certain embodiments and examples are disclosed herein, it will be understood by those skilled in the art that the disclosed methods and systems go beyond the specifically disclosed embodiments and include all novel and non-obvious combinations and sub-combinations of various processes, systems and configurations, as well as any and all equivalents thereof. It should be understood that the methods and / or systems described herein are exemplary in nature, and these specific embodiments or examples should not be considered restrictive, as many variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. Therefore, the various actions shown may be performed in the order shown, in other orders, or omitted in some cases. In addition, for the purpose of simplifying the present disclosure, various features of the present disclosure are combined together in one or more aspects, embodiments and configurations. The features of the aspects, embodiments and configurations of the present disclosure may be combined in alternative aspects, embodiments and configurations other than those discussed above. The methods and systems of the present disclosure should not be interpreted as reflecting the intention that the claimed disclosure requires more features than those explicitly stated in each claim. On the contrary, as reflected in the following claims, the inventive aspects are less than all features of the aspects, embodiments and configurations of the single aforementioned disclosure. Thus the following claims are hereby incorporated into this Detailed Description, with each claim standing on its own as a separate preferred embodiment of the disclosure.

Claims

1. A method for forming a free radical treatment film on a substrate surface, comprising: a. Providing a substrate; as well as b. performing one or more super cycles, each super cycle comprising a deposition step and a radical treatment step; wherein the deposition step comprises supplying a vapor phase precursor into a deposition chamber to deposit a film onto a substrate; wherein the free radical treatment step comprises generating a remote plasma, obtaining a free radical flow from the remote plasma, and exposing the substrate to the free radical flow in a free radical treatment chamber; and Therein, the deposition chamber and the radical processing chamber are operably coupled to allow substrates to be transferred therebetween without any air interruption.

2. The method according to claim 1, wherein: The radical treatment film comprises carbon.

3. The method according to claim 1, wherein: The depositing step includes a plurality of deposition cycles.

4. The method according to claim 1, wherein: The radical flux is obtained from the remote plasma using an ion trap.

5. The method according to claim 4, wherein: An ion trap is provided in the reaction chamber between the remote plasma discharge and the substrate.

6. The method according to claim 4, wherein: The ion trap is an electrically grounded grid plate.

7. The method according to claim 5, wherein: The remote plasma discharge is generated by gas-phase ionization of a gas at a radio frequency (RF) power of 500 W or less.

8. The method according to claim 5, wherein: The remote plasma discharge is generated by gas-phase ionization of a gas at a radio frequency (RF) power of 100 W or less.

9. The method according to claim 1, wherein: The temperature of the substrate is at least 40°C and no more than 550°C.

10. The method according to claim 1, wherein: The temperature of the substrate is at least 75°C and no more than 400°C.

11. The method according to claim 1, wherein: The precursor includes silicon.

12. The method according to claim 11, wherein: The precursor is selected from the group consisting of: silane, alkylsilane, halosilane, aminosilane, silicon alkoxide, siloxane, silazane and combinations thereof.

13. The method according to claim 11, wherein: The precursor is selected from the group consisting of: silane, disilane, trisilane, dimethylsilane, diethylsilane, trimethylsilane, triethylsilane, dichlorosilane, diiodosilane, hexachlorodisilane, octachlorotrisilane, bis(diethylamino)silane, bis(diethylamino)dimethylsilane, diisopropylaminosilane, N-(diethylaminosilyl)-N-ethylethylamine, hexamethylcyclotrisilazane, tetraethyl trisilicate, dimethoxydimethylsilane, trimethoxymethylsilane, tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, 1,1,3,5,5,7-hexamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, bis(diethoxysilyl)ethane, methoxypropyltrimethoxysilane, and combinations thereof.

14. The method according to claim 1, wherein: The precursor includes boron.

15. The method according to claim 1, wherein: The precursor is selected from the group consisting of borane, alkyl borane, aryl borane, carborane, amine borane, amino borane, borate ester, cycloborazine, triethylborane and combinations thereof.

16. The method according to claim 1, wherein: The precursor is selected from: nested carborane, ortho carborane, ammonia borane, dimethylamine borane, trimethylamine borane, tert-butylamine borane, tri(dimethylamino)borane, bromobis(diethylamino)borane, bromobis(dimethylamino)borane, triethylboron, boron triiodide, boron tribromide, B-(cycloribosyl)amine borane, trimethyl borate, triethyl borate, cycloborazine, 2,4,6-trichlorocycloborazine, 2,4,6-tribromocycloborazine, diborazine and combinations thereof.

17. The method according to claim 1, wherein: The remote plasma includes a reactive gas, wherein the reactive gas in the remote plasma is selected from: an oxygen-containing gas, a nitrogen-containing gas, a hydrogen-containing gas, and a combination thereof.

18. The method according to claim 1, wherein: The radical stream includes one or more of oxygen radicals, nitrogen radicals, hydrogen radicals or a combination thereof.

19. The method according to claim 1, wherein: The free radical treatment film is selected from the group consisting of silicon oxycarbonitride, silicon carbonitride, silicon carbide, silicon oxycarbide and combinations thereof.

20. The method according to claim 1, wherein: The free radical treatment film is selected from the group consisting of boron carbide, boron carbonitride, boron oxycarbide, hydrogenated boron carbonitride and combinations thereof.

21. The method according to claim 1, wherein: The free radical treatment film is selected from the group consisting of silicon oxycarbonitride, silicon oxycarbide, silicon carbonitride, boron carbonitride, hydrogenated boron carbonitride and combinations thereof.

22. A semiconductor processing device comprising: one or more processing chambers, each processing chamber comprising two or more stations, each station comprising an upper compartment and a lower compartment, wherein the upper compartment is configured to contain a substrate during substrate processing; wherein the lower compartment comprises a shared intermediate space between two or more stations; a first transfer system configured to move a substrate from a first processing chamber to a second processing chamber in the wafer handling chamber; a second transfer system configured to move the substrate from the first station to the second station within the shared intermediate space of the processing chamber; a first heating unit configured to control the temperature of the first station independently of the temperature of the second station; a pressure system including a pump and an exhaust, the pressure system being configured to maintain a common process chamber pressure in two or more stations; and A controller including a processor that provides instructions to the device to control the following loop: (a) placing a substrate in a first station; (b) depositing a film on a substrate by a vapor deposition process in a first station; (c) placing the first substrate in a second station after depositing the film on the substrate; (d) performing a radical treatment on the substrate by supplying a radical flow to the station to form a modified film; and Steps (a)-(d) in the cycle are repeated until a film of desired thickness is deposited on the substrate.

23. A method for film deposition, the method comprising: (a) placing a substrate in a first station, the first station comprising an upper chamber and a lower chamber, wherein the lower chamber comprises a shared intermediate space among the first station, the second station, the third station and the fourth station; (b) contacting the substrate in the first station with a precursor, wherein the contact with the precursor forms a first film layer on the first substrate; (c) after contacting the substrate in the first station with the precursor, placing the substrate in a second station; (d) performing a first free radical treatment on the substrate by contacting a surface of the first film layer with a free radical flow; (e) after performing the first free radical treatment on the substrate, placing the substrate in a third station; (f) contacting the substrate in the third station with a precursor, wherein the contact with the precursor forms a second film layer on the first substrate; (g) after contacting the substrate in the third station with the precursor, placing the substrate in a fourth station; (h) performing a second free radical treatment on the substrate by contacting a surface of the second film layer with a free radical flow; as well as Steps (a)-(h) in the cycle are repeated until a film of desired thickness is deposited on the first substrate.

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