Silicon carbonitride gap fillers with tunable carbon content

Abstract

To provide a method for depositing a silicon carbonitride film, filling a trench having a high aspect ratio.SOLUTION: A method for depositing a flowable silicon carbonitride film includes exposing a substrate surface to a precursor and a reactant. The precursor has a structure of general formula (I) or general formula (II). In the formulas, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 are independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide. The method also includes purging a processing chamber, and then exposing the substrate to an ammonia plasma.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to silicon nitride film deposition. More particularly, embodiments of the present disclosure are directed to the deposition of silicon carbonitride films with tunable carbon content. [Background technology]

[0002] In the fabrication of microelectronic devices, many applications require filling narrow trenches with aspect ratios (AR) exceeding 10:1. One application is multicolor patterning, which requires filling trenches of approximately 20 nm to approximately 30 nm. This application requires films to be of high quality throughout the trench (e.g., with a wet etch rate ratio below 2) and with very low leakage. As feature dimensions decrease and aspect ratios increase, post-cure methods for as-deposited flowable films become challenging. The resulting film has a wide range of composition throughout the filled trench.

[0003] Conventional spin-on dielectric films, such as silicon nitride (SiN), have high shrinkage rates that can cause bowing in the structures they fill. Conventional low-temperature chemical vapor deposition (CVD) silicon nitride films have low density, are not stable in air, and rapidly oxidize and convert to silicon oxynitride (SiON) films, which compromises etch selectivity to silicon oxide (SiO).

[0004] Flowable chemical vapor deposition (FCVD) is widely used in next-generation semiconductor devices. As feature sizes decrease, the gap-fill capacity required for FCVD films can be significantly reduced compared to previous nodes (e.g., <500 Å or <300 Å). Depositing flowable films without distorting the structures is important but challenging. Therefore, methods for improving flowable gap-fill films are needed. Summary of the Invention

[0005] One or more embodiments of the present disclosure are directed to a method of depositing a film, in one or more embodiments, the method of depositing a film comprises forming a flowable film on a substrate surface by exposing the surface to a precursor and a reactant, wherein the precursor has a structure of general formula (I) or general formula (II): TIFF0007745670000001.tif58170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 forming a flowable film having a group independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide; and exposing the substrate to a plasma.

[0006] Additional embodiments of the present disclosure are directed to methods of depositing a film. In one or more embodiments, the method of depositing a film comprises treating a substrate in a processing chamber with a precursor having a structure of general formula (I) or general formula (II): TIFF0007745670000002.tif57170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12the silicon-containing film is deposited on the substrate; exposing the substrate to a reactant to react with the silicon-containing film to form a silicon carbonitride (SiCN) film on the substrate; purging the processing chamber of precursors and reactants; and exposing the substrate to a plasma.

[0007] Further embodiments of the present disclosure are directed to a non-transitory computer-readable medium. In one or more embodiments, the non-transitory computer-readable medium, when executed by a controller of a processing chamber, can be configured to control the processing chamber to perform the following operations: dispensing a precursor having a structure of general formula (I) or general formula (II) into a processing volume of the processing chamber having a substrate: TIFF0007745670000003.tif59170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 the method includes instructions to perform the operations of flowing a precursor and a reactant (independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide); flowing a reactant comprising trisilylamine (TSA) into a processing volume of a processing chamber; purging the processing chamber of the precursor and reactant; exposing the substrate to a plasma; and purging the processing chamber.

[0008] So that the above features of the present disclosure can be understood in detail, a more particular description of the present disclosure, briefly summarized above, can be had by reference to embodiments, some of which are illustrated in the accompanying drawings. It should be noted, however, that the accompanying drawings illustrate only typical embodiments of the present disclosure and therefore should not be considered as limiting its scope, since the present disclosure may admit of other equally effective embodiments. The embodiments described herein are shown by way of example and not by way of limitation to the figures of the accompanying drawings in which like references indicate like elements. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a process flow diagram of a method according to one or more embodiments. [Figure 2] 1 is a cross-sectional view of a substrate according to one or more embodiments. [Figure 3] 1 is a cross-sectional view of a substrate according to one or more embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0010] Before describing several example embodiments of the present disclosure, it is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description. The present disclosure is capable of other embodiments and of being practiced or carried out in various ways.

[0011] Many of the details, dimensions, angles, and other features shown in the figures are merely illustrative of particular embodiments. Thus, other embodiments may have other details, components, dimensions, angles, and features without departing from the spirit or scope of the present disclosure. Additionally, further embodiments of the present disclosure may be practiced without some of the details described below.

[0012] As used herein, the terms "substrate," "substrate surface," and the like refer to any substrate surface or material surface formed on a substrate on which film processing is performed during a manufacturing process. For example, substrate surfaces on which processing can be performed include materials such as silicon, silicon oxide, strained silicon, silicon-on-insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, gallium arsenide, glass, sapphire, and any other materials, such as metals, metal nitrides, metal alloys, and other conductive materials, depending on the application. Substrates include, but are not limited to, semiconductor wafers. Substrates may be exposed to pretreatment processes to polish, etch, reduce, oxidize, hydroxylate, anneal, UV cure, electron beam cure, and / or bake the substrate surface. In addition to film processing directly on the surface of the substrate itself, the present invention allows any of the disclosed film processing steps to be performed on underlying layers formed on the substrate, as disclosed in more detail below, and the term "substrate surface" is intended to include such underlying layers as the context indicates. Thus, for example, if a film / layer or partial film / layer is being deposited on a substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0013] As used herein and in the appended claims, the terms "reactive compound," "reactive gas," "reactive species," "precursor," "process gas," and the like are used interchangeably to mean a substance having species capable of reacting with a substrate surface or materials on a substrate surface in a surface reaction (e.g., chemisorption, oxidation, reduction). For example, a first "reactive gas" may simply be adsorbed onto the surface of the substrate and available for further chemical reaction with a second reactive gas.

[0014] As used herein and in the appended claims, the terms "precursor," "reactant," "reactive gas," and the like are used interchangeably to refer to any gas species capable of reacting with the substrate surface.

[0015] In one or more embodiments, bias power, and therefore plasma generation, is advantageously added during deposition or inserted into the layer by layer processing of silicon nitride (SiN) films to enhance the quality of the silicon nitride (SiN). Additionally, in one or more embodiments, a cyclotrisilazane precursor is used to adjust the carbon concentration of the deposited flowable film.

[0016] 1, one or more embodiments of the present disclosure are directed to a method 100 of depositing a film. The method illustrated in FIG. 1 is representative of a plasma-enhanced process in which reactive gases are mixed within a processing chamber to enable gas-phase reaction of the reactive gases and deposition of a thin film.

[0017] In some embodiments, the method 100 includes a pre-treatment operation 105. The pre-treatment can be any suitable pre-treatment known to those skilled in the art. Suitable pre-treatments include, but are not limited to, pre-heating, cleaning, soaking, removing native oxides, or depositing a layer (e.g., titanium nitride (TiN)).

[0018] In deposition operation 110, a process is performed to deposit a silicon carbonitride (SiCN) film on a substrate (or substrate surface). The deposition process may include one or more operations to form a film on the substrate. In operation 112, the substrate (or substrate surface) is exposed to a precursor to deposit a film on the substrate (or substrate surface). In one or more embodiments, the substrate (or substrate surface) is exposed to a precursor mixture including a silane and a precursor of general formula (I) or general formula (II). In one or more embodiments, the silane includes one or more of trisilylamine (TSA), silane, disilane, trisilane, tetrasilane, higher silanes, or substituted silanes.

[0019] In one or more embodiments, a plasma-enhanced process for forming silicon carbonitride (SiCN) films is provided using an organosilizane precursor, in one or more embodiments, the precursor has a structure corresponding to general formula (I) or general formula (II): TIFF0007745670000004.tif58170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide.

[0020] Unless otherwise stated, the terms "lower alkyl," "alkyl," or "alk," as used herein alone or as part of another group, include both straight- and branched-chain hydrocarbons containing from 1 to 20 carbons in the linear chain, for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-dimethylpentyl, octyl, 2,2,4-trimethyl-pentyl, nonyl, decyl, undecyl, dodecyl, and various branched-chain isomers thereof. Such groups may optionally contain up to 1 to 4 substituents.

[0021] As used herein, the term "alkoxy" includes any of the above alkyl groups attached to an oxygen atom.

[0022] As used herein, the term "vinyl" or "vinyl-containing" refers to a group that contains the vinyl group (-CH=CH2).

[0023] As used herein, the term "amine" refers to any organic compound containing at least one basic nitrogen atom, e.g., NR'2, where R' is independently selected from hydrogen (H) or alkyl.

[0024] As used herein, the term "silane" refers to the compound SiR'3, where R' is independently selected from hydrogen (H) or alkyl.

[0025] As used herein, the term "halide" refers to a binary system in which one part is a halogen atom and the other part is an element or radical that is less electronegative than the halogen to create a fluoride, chloride, bromide, iodide, or astatide compound. A halide ion is a negatively charged halogen atom. As known to those skilled in the art, halide anions include fluoride (F), chloride (Cl), bromide (Br), iodide (I), and astatine (At).

[0026] In one or more embodiments, the precursor is a silane (e.g., trisilylamine (TSA), silane, disilane, trisilane, tetrasilane, higher silanes, or substituted silanes) and a silane selected from the group consisting of hexamethylcyclotrisilazane, octamethylcyclotrisilazane, nonamethylcyclotrisilazane, hexaethylcyclotrisilazane, octaethylcyclotrisilazane, 2-ethyl-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-triazatrisilinane, hexapropylcyclotrisilazane, octapropylcyclotrisilazane, di(butan-2-yl)-fluoro-(2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6- triazatrisilinane-1-yl)silane, tetraethyl-dimethyl-triazatrisilinane, diethyl-tetramethyl-triazatrisilinane, hexapropyltriazatrisilinane, hexamethyltriazatrisilinane, hexaethyltriazatrisilinane, octapropyltriazatrisilinane, octamethyltriazatrisilinane, octaethyltriazatrisilinane, tetraethyl-tetramethyltriazatrisilinane, ethyl-pentamethyltriazatrisilinane, triethyltriazatrisilinane, trimethyltriazatrisilinane, tripropyltriazatrisilinane, etc. In some particular embodiments, the precursor comprises one or more of hexamethylcyclotrisilazane, hexaethylcyclotrisilazane, hexapropylcyclotrisilazane, octamethylcyclotrisilazane, octaethylcyclotrisilazane, octapropylcyclotrisilazane. In a very specific embodiment, the precursor comprises hexamethylcyclotrisilazane or octamethylcyclotrisilazane.

[0027] In one or more embodiments, the precursor consists essentially of a silane (e.g., silane, disilane, trisilane, tetrasilane, higher silanes, or substituted silanes) and one or more of hexamethylcyclotrisilazane, octamethylcyclotrisilazane, nonamethylcyclotrisilazane, hexaethylcyclotrisilazane, octaethylcyclotrisilazane, 2-ethyl-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-triazatrisilinane, hexapropylcyclotrisilazane, octapropylcyclotrisilazane, di(butan-2-yl)-fluoro-(2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane). and mixtures thereof with one or more of (trisilinane-1-yl)silane, tetraethyl-dimethyl-triazatrisilinane, diethyl-tetramethyl-triazatrisilinane, hexapropyltriazatrisilinane, hexamethyltriazatrisilinane, hexaethyltriazatrisilinane, octapropyltriazatrisilinane, octamethyltriazatrisilinane, octaethyltriazatrisilinane, tetraethyl-tetramethyltriazatrisilinane, ethyl-pentamethyltriazatrisilinane, triethyltriazatrisilinane, trimethyltriazatrisilinane, tripropyltriazatrisilinane, etc. In some specific embodiments, the precursor consists essentially of one or more of hexamethylcyclotrisilazane, hexaethylcyclotrisilazane, hexapropylcyclotrisilazane, octamethylcyclotrisilazane, octaethylcyclotrisilazane, octapropylcyclotrisilazane, etc. In a very specific embodiment, the precursor consists essentially of hexamethylcyclotrisilazane or octamethylcyclotrisilazane.When used in this manner, the term "consisting essentially of" means that the silicon precursor is, on a molecular basis, hexamethylcyclotrisilazane, octamethylcyclotrisilazane, nonamethylcyclotrisilazane, hexaethylcyclotrisilazane, octaethylcyclotrisilazane, 2-ethyl-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-triazatrisilinane, hexapropylcyclotrisilazane, octapropylcyclotrisilazane, di(butan-2-yl)-fluoro-(2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane-1-yl)silane, tetraethyl-dimethyl- By "triazatrisilinane," we mean containing about 95% or more, 98% or more, 99% or more, or 99.5% or more of one or more of triazatrisilinane, diethyl-tetramethyl-triazatrisilinane, hexapropyltriazatrisilinane, hexamethyltriazatrisilinane, hexaethyltriazatrisilinane, octapropyltriazatrisilinane, octamethyltriazatrisilinane, octaethyltriazatrisilinane, tetraethyl-tetramethyl-triazatrisilinane, ethyl-pentamethyl-triazatrisilinane, triethyltriazatrisilinane, trimethyl-triazatrisilinane, tripropyltriazatrisilinane, etc. The presence of a diluent gas, carrier gas, and / or inert gas is not taken into account in the calculation.

[0028] In one or more embodiments, the deposition process is carried out at a temperature ranging from about 0°C to about 400°C, including about 25°C, about 50°C, about 75°C, about 100°C, about 125°C, about 150°C, about 175°C, about 200°C, about 425°C, about 250°C, about 275°C, about 300°C, about 325°C, about 350°C, about 375°C, and about 400°C.

[0029] In one or more embodiments, the substrate (or substrate surface) can be any suitable surface. Suitable surfaces include silicon (Si), silicon dioxide (SiO), silicon oxide (SiO x), silicon oxycarbide (SiOC), platinum (Pt), titanium nitride (TiN), tantalum nitride (TaN), copper (Cu), cobalt (Cu), tungsten (W), ruthenium (Ru), molybdenum (Mo), or a combination thereof.

[0030] In operation 114, the substrate (or substrate surface) is exposed to a reactant to form a silicon carbonitride (SiCN) film on the substrate. In one or more embodiments, the reactant includes ammonia or other precursor containing an amino group.

[0031] In some embodiments, operations 112 and 114 are performed simultaneously, such that the substrate is exposed to the precursor and the reactant simultaneously. In other embodiments, operations 112 and 114 are performed sequentially, such that the substrate is first exposed to the precursor and then to the reactant.

[0032] In operation 116, the processing chamber is purged to remove unreacted precursors, unreacted reactants, reaction products, and by-products. When used in this manner, the term “processing chamber” also includes a portion of the processing chamber adjacent to the substrate surface, rather than encompassing the complete interior volume of the processing chamber. For example, in spatially separated processing chamber sectors, the portion of the processing chamber adjacent to the substrate surface is purged of the rhenium precursor by any suitable technique, including, but not limited to, moving the substrate through a gas curtain to a portion or sector of the processing chamber that contains no or substantially no rhenium precursor. In some embodiments, purging the processing chamber includes flowing a purge gas over the substrate. In some embodiments, a portion of the processing chamber refers to a microvolume or small-volume processing station within the processing chamber. The term “adjacent” when referring to the substrate surface refers to the physical space next to the surface of the substrate that can provide sufficient space for surface reactions (e.g., precursor adsorption) to occur.

[0033] In one or more embodiments, the deposition process includes a remote plasma enhanced chemical vapor deposition (PECVD) process. After forming the silicon carbonitride (SiCN) film on the substrate, the substrate is exposed to a plasma in operation 118. In one or more embodiments, exposing the silicon carbonitride (SiCN) film to a plasma in the processing chamber improves the film's properties. For example, in one or more embodiments, the wet etch rate is improved, indicating that the plasma treatment enhances the film's density. In one or more embodiments, the plasma includes one or more of nitrogen (N), argon (Ar), helium (He), hydrogen (H), carbon monoxide (CO), or carbon dioxide (CO). In some embodiments, the plasma is a remote plasma. In other embodiments, the plasma is a direct plasma.

[0034] In one or more embodiments, the plasma can be generated remotely or within the processing chamber. In one or more embodiments, the plasma is an inductively coupled plasma (ICP) or a conductively coupled plasma (CCP). Any suitable power can be used, depending, for example, on the reactants and other process conditions. In some embodiments, the plasma is generated at a plasma power ranging from about 10 W to about 3000 W. In some embodiments, the plasma is generated at a plasma power of about 3000 W or less, about 2000 W or less, about 1000 W or less, about 500 W or less, or about 250 W or less.

[0035] In operation 120, the processing chamber is purged after exposure to the plasma. Purging the processing chamber in operation 120 may be the same process as or a different process from the purging in operation 116. Purging the processing chamber, a portion of the processing chamber, an area adjacent to the substrate surface, etc., removes plasma, reaction products, and by-products from the area adjacent to the substrate surface.

[0036] At decision point 125, in one or more embodiments, the thickness of the deposited film or the number of precursor and reactant cycles is considered. In one or more embodiments, if the deposited film reaches a predetermined thickness or if a predetermined number of processing cycles have been performed, method 100 moves to post-processing operation 130. In one or more embodiments, if the deposited film thickness or number of processing cycles has not reached a predetermined threshold, method 100 returns to deposition operation 110, exposing the substrate surface to precursors again in operation 112, and continuing with subsequent operations.

[0037] In one or more embodiments, the post-treatment operation 130 includes, for example, a process to modify film properties (e.g., annealing) or a further film deposition process to grow an additional film (e.g., an additional ALD or CVD process). In some embodiments, the post-treatment operation 130 is a process to modify the properties of the deposited film. In some embodiments, the post-treatment operation 130 includes annealing the as-deposited film. In some embodiments, the annealing is performed at a temperature in the range of about 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C, or 1000°C. The annealing environment in some embodiments includes one or more of an inert gas (e.g., molecular nitrogen (N), argon (Ar)), or a reducing gas (e.g., molecular hydrogen (H) or ammonia (NH)), or an oxidizing agent, such as, but not limited to, oxygen (O), ozone (O), or a peroxide. In one or more embodiments, annealing is carried out for any suitable length of time. In some embodiments, the film is annealed for a predetermined time ranging from about 15 seconds to about 90 minutes, or from about 1 minute to about 60 minutes. In some embodiments, annealing the as-deposited film increases the density, decreases the resistivity, and / or increases the purity of the film.

[0038] Method 100 can be performed at any suitable temperature, depending on, for example, the precursors, reactants, or the thermal budget of the device. In some embodiments, the exposure to the precursor (operation 112) and the reactant (operation 114) occurs at the same temperature. In some embodiments, the substrate is maintained at a temperature in the range of about 0° C. to about 400° C., or in the range of about 0° C. to about 100° C., to obtain a flowable film.

[0039] In some embodiments, the exposure to the precursor (operation 112) occurs at a different temperature than the exposure to the reactant (operation 114). In some embodiments, the substrate is maintained at a first temperature in a range from about 0° C. to about 200° C. during the exposure to the precursor, and at a second temperature in a range from about 200° C. to about 500° C. during the exposure to the reactant. In such embodiments, two chambers within the mainframe may be required.

[0040] In the deposition operation 110 of the embodiment shown in FIG. 1 , the substrate (or substrate surface) is exposed to precursors and reactants sequentially. In another embodiment, not shown, the substrate (or substrate surface) is exposed to precursors and reactants simultaneously in a PE-CVD reaction, in which the substrate (or substrate surface) is exposed to a gaseous mixture of precursors and reactants to deposit a silicon carbonitride (SiCN) film having a predetermined thickness. In a PE-CVD reaction, the silicon carbonitride (SiCN) film may be deposited in a single exposure to the reactive gas mixture, or may be exposed to the reactive gas mixture multiple times with purging in between.

[0041] In one or more embodiments, the deposition process is carried out in the process volume at a pressure ranging from 0.1 mTorr to 10 Torr, including pressures of about 0.1 mTorr, about 1 mTorr, about 10 mTorr, about 100 mTorr, about 500 mTorr, about 1 Torr, about 2 Torr, about 3 Torr, about 4 Torr, about 5 Torr, about 6 Torr, about 7 Torr, about 8 Torr, about 9 Torr, and about 10 Torr.

[0042] The precursor-containing gas mixture may further include one or more diluent gases selected from helium (He), argon (Ar), xenon (Xe), nitrogen (N), or hydrogen (H). The diluent gas in some embodiments includes a compound that is inert to the reactants and substrate materials.

[0043] The plasma (e.g., capacitively coupled plasma) can be formed from either a top electrode and a bottom electrode or a side electrode. The electrodes can be formed from a single-powered electrode, a dual-powered electrode, or more electrodes with multiple frequencies, such as, but not limited to, 350 KHz, 2 MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz, and 100 MHz, alternatively or simultaneously used in a CVD system with any or all of the reactive gases described herein to deposit thin films of dielectric materials. In some embodiments, the plasma is a capacitively coupled plasma (CCP). In some embodiments, the plasma is an inductively coupled plasma (ICP). In some embodiments, the plasma is a microwave plasma.

[0044] In one or more embodiments, the silicon carbonitride (SiCN) film has a carbon content, on an atomic basis, of about 5% or more, 7.5% or more, 10% or more, 12.5% ​​or more, 15% or more, 20% or more, 25% or more, or 30% or more. In some embodiments, the silicon carbonitride (SiOCN) film comprises a carbon content, on an atomic basis, in the range of about 0.1% to about 30%, or in the range of about 3% to about 25%, or in the range of about 4% to about 20%.

[0045] The deposition operation 110 can be repeated to form a silicon carbonitride (SiCN) film having a predetermined thickness. In some embodiments, the deposition operation 110 is repeated to provide a silicon carbonitride (SiCN) film having a thickness greater than about 0.1 nm, or a thickness in the range of about 0.1 nm to about 1000 nm, including about 10 nm to about 500 nm, about 10 nm to about 100 nm, about 5 nm to about 50 nm, about 10 nm to about 50 nm, or about 20 nm to about 30 nm.

[0046] In some embodiments, the film is deposited in a chamber where the substrate pedestal is maintained at about 300° C., the pressure is maintained at about 5 Torr, and a plasma is generated at the wafer level (i.e., direct plasma) by applying a bias of about 200 Watts to the electrostatic chuck. In some embodiments, an additional RF power of about 1000 Watts at 2 MHz is also supplied to the electrostatic chuck to generate a dual bias plasma at the wafer level.

[0047] Generally, the following exemplary deposition process parameters can be used to form as-deposited films: The wafer temperature can range from about 200° C. to about 500° C. The chamber pressure can range from about 0.1 mTorr to about 10 Torr. The flow rate of the precursor-containing gas mixture can range from about 10 sccm to about 1,000 sccm. The flow rates of the dilution gases can individually range from about 50 sccm to about 50,000 sccm.

[0048] The film may be deposited to a thickness in the range of about 5 Å to about 60,000 Å, including in the range of about 300 Å to about 10,000 Å, in the range of about 2000 Å to about 3000 Å, or in the range of about 5 Å to about 200 Å.

[0049] FIG. 2 shows a cross-sectional view of a substrate 200 having a feature 210. While the drawing shows a substrate with a single feature for illustrative purposes, one skilled in the art will understand that more than one feature may be present. The shape of the feature 110 can be any suitable shape, including, but not limited to, a trench and a cylindrical via. As used in this context, the term "feature" refers to any intentional surface irregularity. Suitable examples of features include, but are not limited to, a trench having a top, two sidewalls, and a bottom, and a peak having a top and two sidewalls. The feature can have any suitable aspect ratio (ratio of the depth of the feature to the width of the feature). In some embodiments, the aspect ratio is about 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, or 40:1 or greater.

[0050] Substrate 200 has a substrate surface 220. At least one feature 210 forms an opening in substrate surface 220. Feature 210 extends from substrate surface 220 to a bottom surface 212 to a depth D. Feature 210 has a first sidewall 214 and a second sidewall 216 that define a width W of feature 210. The open area formed by the sidewalls and the bottom is also referred to as a gap.

[0051] One or more embodiments of the present disclosure are directed to a processing method in which a substrate surface having at least one feature is provided, the term "provided" as used in this context meaning that the substrate is placed in a location or environment for further processing.

[0052] 3 illustrates a cross-sectional view of a substrate 200 having a feature 210. As shown in FIG. 3, a flowable film 250 is formed on the substrate surface 220 and on a first sidewall 214, a second sidewall 216, and a bottom surface 212 of at least one feature 210. The flowable film 250 fills the at least one feature 210 such that a substantially seam-free seam is formed. A seam is a gap formed in the feature between the sidewalls of the feature 210, but not necessarily in the center of the sidewall. In this context, the term "substantially seamless" means that the gap formed in the film between the sidewalls is less than about 1% of the cross-sectional area of ​​the sidewall.

[0053] The flowable film 250 can be formed by any suitable process. In some embodiments, the flowable film is formed by plasma enhanced chemical vapor deposition (PECVD). In other words, the flowable film can be deposited by a plasma enhanced chemical vapor deposition process or by using a remote plasma.

[0054] In some embodiments, the PECVD process includes exposing the substrate surface to a reactive gas. The reactive gas can include a mixture of one or more species. For example, the reactive gas can include a precursor of General Formula I and silane mixed with a precursor of General Formula I or General Formula II. In one or more embodiments, the silencer includes one or more of silane, disilane, trisilane, tetrasilane, higher silanes, substituted silanes, or trisilylamine (TSA). The plasma gas can be any suitable gas that can be ignited to form a plasma and / or act as a carrier or diluent for the precursors. In one or more embodiments, the plasma gas includes ammonia (NH), which is used in the plasma process to activate one or more precursors.

[0055] Accordingly, one or more embodiments of the present disclosure are directed to a process for depositing a silicon nitride film having a carbon content greater than 0% on an atomic basis, the process comprising exposing a substrate or substrate surface to a first reactive gas and a second reactive gas, which are separately exposed to the substrate, in a plasma deposition process.

[0056] 3, the flowable film 250 can be formed at any suitable temperature. In some embodiments, the flowable film 250 can be formed at a temperature ranging from about 0° C. to about 200° C. The temperature can be kept low to maintain the thermal budget of the device being formed.

[0057] The composition of the flowable film can be adjusted by varying the composition of the reactive gas. In some embodiments, the flowable film includes one or more of SiCN, SiCON, and SiN. To form an oxygen-containing film, the co-reactant can include, for example, one or more of oxygen, ozone, or water. To form a nitrogen-containing film, the co-reactant can include, for example, one or more of ammonia, hydrazine, NO, or N. Those skilled in the art will understand that other species or combinations thereof can be included in the reactive gas mixture to vary the composition of the flowable film.

[0058] In one or more embodiments, a flowable CVD film is deposited on the wafer (the wafer temperature can be from −10° C. to 600° C.), and due to their flowability, the polymer flows through the trenches and fills the gaps. These films are then subjected to a curing step, such as ozone / UV / steam annealing / NH annealing, to obtain a stable film. In one or more embodiments, after the flowable CVD film 250 is formed, the film is cured to solidify the flowable CVD film and form a substantially seamless gap-fill. In one or more embodiments, curing the flowable CVD film includes exposing the flowable CVD film to one or more of ozone, UV light, steam annealing, ammonia annealing, and oxygen plasma. In some embodiments, the flowable CVD film is cured by exposing the film to a UV curing process. The UV curing process can be performed at a temperature ranging from about 10° C. to about 550° C. In one or more embodiments, the UV curing process is performed for any suitable time frame necessary to sufficiently solidify the flowable CVD film. In one or more embodiments, the UV curing is performed using various parameters, such as power, temperature, and environment.

[0059] In some embodiments, curing the flowable CVD film comprises thermal annealing, hi one or more embodiments, the thermal annealing is performed at any suitable temperature and in any suitable environment.

[0060] In some embodiments, curing the flowable CVD film comprises exposure to a plasma or an electron beam. In one or more embodiments, the plasma exposure to harden the film comprises a plasma separate from the PECVD plasma. In one or more embodiments, the plasma species and processing chamber are the same, while in other embodiments, the plasma hardening is a separate process from the PECVD process.

[0061] In some embodiments, curing the flowable CVD film includes exposing the flowable CVD film to steam annealing and / or oxygen plasma. In one or more embodiments, the use of steam annealing and / or oxygen plasma reduces the carbon content of the flowable CVD film so that the cured film has a lower carbon content than the as-deposited flowable CVD film. In one or more embodiments, the use of steam annealing and / or oxygen plasma converts the deposited flowable SiCN or SiOCN film to SiO.

[0062] In some embodiments, silane, disilane, trisilane, tetrasilane, higher silanes, substituted silanes, or trisilylamine (TSA) reactants are used with another precursor (e.g., co-flow with another Si-containing precursor) in a flowable process to deposit films of various compositions.

[0063] In some embodiments, the flowable CVD film is doped with another element. For example, in one or more embodiments, the flowable CVD film is doped with one or more of boron (B), arsenic (As), or phosphorus (P). In one or more embodiments, the flowable CVD film is doped with elements such as boron (B) and phosphorus (P) to improve the film's properties. In one or more embodiments, boron- and phosphorus-containing precursors are co-flowed with the precursor of general formula I and trisilylamine (TSA) during the deposition process, or infiltrated after deposition has occurred.

[0064] According to one or more embodiments, the substrate is subjected to processing before and / or after the formation of a layer. This processing can occur in the same chamber or in one or more separate processing chambers. In some embodiments, the substrate is transferred from the first chamber to a separate second chamber for further processing. The substrate may be transferred directly from the first chamber to the separate processing chamber, or may be transferred from the first chamber to one or more transfer chambers and then to the separate processing chamber. Thus, the processing equipment may include multiple chambers in communication with a transfer station. This type of equipment may be referred to as a "cluster tool" or a "cluster system," among other terms.

[0065] Generally, a cluster tool is a modular system with multiple chambers that perform various functions, including substrate center detection and orientation, degassing, annealing, deposition, plasma treatment, UV curing, and / or etching. According to one or more embodiments, the cluster tool includes at least a first chamber and a central transfer chamber. The central transfer chamber can house a robot capable of transferring substrates back and forth between multiple processing chambers and multiple load lock chambers. The transfer chamber is typically maintained under reduced pressure and provides an intermediate stage for transferring substrates from one chamber to another and / or to a load lock chamber located at the front end of the cluster tool. Two well-known cluster tools that may be compatible with the present disclosure are the Centura® and Endura®, both available from Applied Materials, Inc., Santa Clara, California, USA. However, the exact arrangement and combination of chambers may be varied for the purposes of performing specific steps of the processes described herein. Other processing chambers that can be used include, but are not limited to, cyclic layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etching, pre-cleaning, chemical cleaning, thermal treatments such as RTP, plasma nitridation, degassing, alignment, hydroxylation, and other substrate processing. By performing processes in the chambers of a cluster tool, surface contamination of the substrate from atmospheric impurities can be avoided without oxidation prior to deposition of subsequent films.

[0066] According to one or more embodiments, the substrate is under continuous vacuum or "load lock" and is not exposed to ambient air as it moves from one chamber to the next. Thus, the transfer chamber is under vacuum and is "pumped down" under vacuum. An inert gas may be present in the processing chamber or transfer chamber. In some embodiments, the inert gas is used as a purge gas to remove some or all of the reactants. According to one or more embodiments, the purge gas is injected into the outlet of the deposition chamber to prevent reactants from moving from the deposition chamber to the transfer chamber and / or additional processing chambers. Thus, a flow of inert gas forms a curtain at the outlet of the chamber.

[0067] Substrates can be processed in a single-substrate deposition chamber, where a single substrate is loaded, processed, and unloaded before another substrate is processed. Substrates can also be processed in a continuous manner, similar to a conveyor system, where multiple substrates are individually loaded into a first portion of the chamber, moved through the chamber, and unloaded from a second portion of the chamber. The geometry of the chamber and associated conveyor system can form a linear or curved path. Additionally, the processing chamber can be a carousel, where multiple substrates move about a central axis and are subjected to processes such as deposition, etching, annealing, cleaning, etc. throughout the carousel path.

[0068] During processing, the substrate may be heated or cooled. Such heating or cooling may be achieved by any suitable means, including, but not limited to, changing the temperature of the substrate support and flowing heated or cooled gases over the substrate surface. In some embodiments, the substrate support includes a heater / cooler that can be controlled to conductively change the substrate temperature. In one or more embodiments, the gas (reactive or inert) used is heated or cooled to locally change the substrate temperature. In some embodiments, a heater / cooler is positioned within the chamber adjacent to the substrate surface to change the substrate temperature by convection.

[0069] The substrate may also be stationary or rotating during processing. A rotating substrate may be rotated continuously or in discrete steps (about the substrate axis). For example, the substrate may be rotated throughout the entire process, or the substrate may be rotated in small increments between exposures to different reactive or purge gases. Rotating the substrate during processing (either continuously or in steps) can help achieve more uniform deposition or etching, for example, by minimizing the effects of local variations in gas flow geometry.

[0070] The processes may generally be stored in memory as software routines that, when executed by a processor, cause the processing chamber to perform the processes of the present disclosure. The software routines may also be stored and / or executed by a second processor (not shown) that is remote from the hardware being controlled by the processor. Some or all of the methods of the present disclosure may also be performed in hardware. Thus, the processes may be implemented in software and may also be performed using, for example, a computer system in hardware, as an application-specific integrated circuit or other type of hardware implementation, or a combination of software and hardware. The software routines, when executed by a processor, transform a general-purpose computer into a special-purpose computer (controller) that controls the operation of the chamber to perform the processes.

[0071] In one or more embodiments, the non-transitory computer readable medium, when executed by a controller of a processing chamber, may be configured to cause the processing chamber to perform the following operations: dispensing a substrate into a processing volume of the processing chamber having a structure of general formula (I) or general formula (II): TIFF0007745670000005.tif57170 (in the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9, R 10 , R 11 , and R 12 includes instructions to perform the operations of flowing a precursor having a group independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide; flowing a reactant comprising trisilylamine (TSA) into a process volume of a process chamber; purging the process chamber of the precursor and reactant; exposing the substrate to a plasma; and purging the process chamber.

[0072] The present disclosure will now be described with reference to the following examples. Before describing certain exemplary embodiments of the present disclosure, it is to be understood that the present disclosure is not limited to the details of construction or process steps set forth in the following description. The present disclosure is capable of other embodiments and of being practiced or carried out in various ways. [Example]

[0073] Example 1 Silicon carbonitride films were deposited on the substrates. Hexamethylcyclotrisilazane (HMCTZ) and trisilylamine (TSA) were co-flowed in a ratio of approximately 3.6:1 in a reaction chamber with helium (g) as a carrier gas. A flow of ammonia (NH) was then passed over the substrate, and the bias power was turned on at approximately 3000 W to generate a plasma. The substrates were then treated with ammonia plasma in an Ar(g) atmosphere at a pressure of approximately 0.7 T for approximately 15 seconds. Silicon carbonitride films were deposited on the substrates. A flow of argon (Ar) was then passed over the substrates for 30 seconds. The substrates were then annealed in a nitrogen (N) atmosphere at 400 °C and a pressure of 5 T for 10 minutes.

[0074] Example 2 Silicon carbonitride films were deposited on the substrates. Hexamethylcyclotrisilazane (HMCTZ) and trisilylamine (TSA) were co-flowed in a ratio of approximately 3.6:1 in a reaction chamber in a helium (g) carrier gas. A flow of ammonia (NH3) was then introduced over the substrate, and the bias power was turned on at approximately 3000 W to generate a plasma. Silicon carbonitride films were then deposited on the substrates. Next, a flow of argon (Ar) at approximately 0.7 T was passed over the substrate for 30 seconds. The substrates were annealed in a nitrogen (N2) atmosphere at 400 °C and a pressure of 5 T for 10 minutes.

[0075] Example 3 Silicon carbonitride films were deposited on the substrates. Hexamethylcyclotrisilazane (HMCTZ) and trisilylamine (TSA) were co-flowed in a ratio of approximately 3.6:1 in a reaction chamber in a helium (g) carrier gas. A flow of ammonia (NH) was then introduced over the substrate, and the bias power was turned on at approximately 3000 W to generate a plasma. Silicon carbonitride films were deposited on the substrates. The substrates were annealed in a nitrogen (N) atmosphere at 400°C and 5 T pressure for 10 minutes.

[0076] Table 1 shows the properties of the membrane. TIFF0007745670000006.tif47170

[0077] The use of the terms "a," "an," and "the," and similar referents in the context of describing the materials and methods discussed herein (particularly in the context of the claims below) should be construed to cover both the singular and the plural unless otherwise stated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each individual value falling within the range, unless otherwise stated herein, and each individual value is incorporated herein as if set forth individually herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "etc."), provided herein is intended merely to further clarify the materials and methods and does not impose limitations on the scope of the claims unless otherwise expressly stated. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosed materials and methods.

[0078] References throughout this specification to "one embodiment," "a particular embodiment," "one or more embodiments," or "an embodiment" mean that a particular feature, structure, material, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of the phrases "in one or more embodiments," "in an embodiment," "in one embodiment," or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment of the present disclosure. In one or more embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner.

[0079] Although the disclosure herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed method and apparatus without departing from the spirit and scope of the disclosure. Therefore, it is intended that the disclosure cover modifications and variations that come within the scope of the appended claims and their equivalents.

Claims

1. 1. A method for depositing a silicon carbonitride film, comprising: trisilylamine (TSA) and a precursor having the structure of general formula (II): (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ forming a flowable film on at least one feature on a substrate surface, the feature having a bottom and two sidewalls, by exposing the substrate surface to a precursor mixture comprising: Ammonia (NH ３ ) over the surface of the substrate; and Turn on the bias power to generate plasma. Including, The method, wherein the flowable film is a flowable silicon carbonitride film having a carbon content of 5 atomic % or greater, and the flowable silicon carbonitride film fills the at least one feature.

2. The method of claim 1 , wherein the substrate surface is exposed to the precursor and trisilylamine (TSA) simultaneously.

3. The plasma is ammonia (NH ３ ), nitrogen (N ２ ), argon (Ar), helium (He), hydrogen (H ２ ), carbon monoxide (CO), or carbon dioxide (CO ２ 10. The method of claim 1, comprising one or more of:

4. 10. The method of claim 1, wherein the flowable silicon carbonitride film has a thickness in the range of 50 Å to 1000 Å.

5. 10. The method of claim 1, wherein the flowable silicon carbonitride film is formed at a pressure ranging from 0.3 Torr to 10 Torr.

6. The method of claim 1 , wherein the flowable silicon carbonitride film is formed at a temperature ranging from 0° C. to 200° C.

7. 2. The method of claim 1, wherein the precursor mixture consists of the trisilylamine (TSA) and the precursor having the structure of general formula (II):

8. 1. A method of depositing a film, comprising: The substrate in the processing chamber is treated with a precursor having a structure of general formula (I) or general formula (II): (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ is independently selected from hydrogen (H), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted vinyl, silane, substituted or unsubstituted amine, or halide to deposit a silicon-containing film on the substrate; exposing the substrate to trisilylamine (TSA) to react with the silicon-containing film to form a silicon carbonitride (SiCN) film on the substrate having a carbon content of 5 atomic % or greater; purging the process chamber of the precursor and silane trisilylamine (TSA); Ammonia (NH ３ ) over the surface of the substrate; and Turn on the bias power to generate plasma. A method comprising:

9. The method of claim 8 , wherein the substrate surface is exposed to the precursor and the trisilylamine (TSA) simultaneously.

10. The precursor may be one or more of hexamethylcyclotrisilazane, octamethylcyclotrisilazane, nonamethylcyclotrisilazane, hexaethylcyclotrisilazane, octaethylcyclotrisilazane, 2-ethyl-2,4,4,6,6-pentamethyl-1,3,5,2,4,6-triazatrisilinane, hexapropylcyclotrisilazane, octapropylcyclotrisilazane, di(butan-2-yl)-fluoro-(2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane-1-yl)silane, tetraethyl-dimethyl-triaza 9. The method of claim 8, wherein the trisilinane comprises one or more of the following: trisilinane, diethyl-tetramethyl-triazatrisilinane, hexapropyltriazatrisilinane, hexamethyltriazatrisilinane, hexaethyltriazatrisilinane, octapropyltriazatrisilinane, octamethyltriazatrisilinane, octaethyltriazatrisilinane, tetraethyl-tetramethyl-triazatrisilinane, ethyl-pentamethyl-triazatrisilinane, triethyl-triazatrisilinane, trimethyl-triazatrisilinane, and tripropyl-triazatrisilinane.

11. The plasma is ammonia (NH ３ ), nitrogen (N ２ ), argon (Ar), helium (He), hydrogen (H ２ ), carbon monoxide (CO), or carbon dioxide (CO ２ 9. The method of claim 8, comprising one or more of:

12. Purging the processing chamber includes flowing a purge gas over the substrate, the purge gas being selected from the group consisting of argon (Ar), nitrogen (N ２ 9. The method of claim 8, wherein the oxygen is selected from one or more of: oxygen (O) and helium (He).

13. 1. A method for depositing a silicon carbonitride film, comprising: trisilylamine (TSA) and a precursor having the structure of general formula (I): (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , and R １２ forming a flowable film on at least one feature on a substrate surface, the feature having a bottom and two sidewalls, by exposing the substrate surface to a precursor mixture comprising: Ammonia (NH ３ ) over the surface of the substrate; and Turn on the bias power to generate plasma. Including, The method, wherein the flowable film is a flowable silicon carbonitride film having a carbon content of 5 atomic % or greater, and the flowable silicon carbonitride film fills the at least one feature.

14. 14. The method of claim 13, wherein the flowable silicon carbonitride film has a thickness in the range of 50 Å to 1000 Å.

15. 14. The method of claim 13, wherein the flowable silicon carbonitride film is formed at a pressure ranging from 0.3 Torr to 10 Torr.

16. 14. The method of claim 13, wherein the flowable silicon carbonitride film is formed at a temperature ranging from 0°C to 1200°C.

17. 14. The method of claim 13, wherein the precursor mixture consists of the trisilylamine (TSA) and the precursor having the structure of general formula (I).

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