Hybrid atomic layer deposition

Abstract

Methods and apparatus for depositing silicon nitride using hybrid atomic layer deposition techniques are provided. Methods and apparatus for forming a halogen-free undercoat in a processing chamber using a halogen-free aminosilane precursor are provided. Methods and apparatus for forming silicon oxynitride using a single crystal wafer chamber are provided herein. The methods and apparatus also include forming graded silicon oxynitride using cyclic deposition and in-situ nitridation and / or oxidation techniques.

Description

Incorporated by Reference The PCT application form is filed concurrently with this specification as a part of this application. Each application identified in the concurrently filed PCT application form to which this application claims the benefit or priority is incorporated herein by reference in its entirety and for all purposes. Background Art

[0001] Semiconductor manufacturing processes involve depositing silicon-containing materials, including silicon nitride materials, on low-k dielectric materials. When forming high-quality silicon nitride, it is challenging to reduce damage to the low-k dielectric during the deposition of the silicon nitride.

[0002] Semiconductor processing methods may involve the use of a variety of chemicals, some of which may interact with materials of chamber components within the processing chamber during processing. Therefore, chamber components may be protected by first forming an undercoat film on the components prior to processing semiconductor wafers therein. Various chamber components may be subjected to different conditions during processing and may involve undercoat deposition methods that vary from component to component.

[0003] Semiconductor manufacturing processes involve the deposition of silicon-containing materials, including graded films having graded amounts of oxygen and nitrogen molecules within the film. Controlling the oxygen gradient or nitridation of silicon-containing materials using certain methods and apparatus is challenging.

[0004] The background description provided here is for the purpose of generally presenting the context of the present disclosure. The work of the presently designated inventors is neither explicitly nor implicitly admitted to be prior art against the present disclosure to the extent that it is described in this background section and to aspects of the specification that could not be determined as prior art at the time of filing the application. Summary of the invention

[0005] One aspect relates to a method of processing a substrate, the method comprising: providing a substrate having features thereon; exposing the substrate to a silicon-containing precursor in a gas phase for a duration sufficient to cause at least some of the silicon-containing precursor to adsorb onto a surface of the substrate to form an adsorbed silicon-containing precursor; exposing the substrate to a first nitrogen-containing gas in a plasma-free environment; and exposing the substrate to a plasma resulting from igniting a second nitrogen-containing gas to form silicon nitride on the surface of the substrate. In some embodiments, after exposing the substrate to the silicon-containing precursor in a gas phase, the substrate is exposed to the first nitrogen-containing gas in a plasma-free environment. In some embodiments, after exposing the substrate to the first nitrogen-containing gas in a plasma-free environment, the substrate is exposed to a plasma resulting from igniting the second nitrogen-containing gas to form silicon nitride on the surface of the substrate.

[0006] In various embodiments, the plasma includes radical species selected from the group consisting of nitrogen radicals, hydrogen radicals, and nitrogen-hydrogen radicals.

[0007] In various embodiments, the first nitrogen-containing gas includes ammonia (NH 3 ) gas.

[0008] In various embodiments, exposing the substrate to the first nitrogen-containing gas in the plasma-free environment further comprises exposing the substrate to hydrogen gas.

[0009] In various embodiments, the second nitrogen-containing gas includes two or more gases.

[0010] In various embodiments, the second nitrogen-containing gas is one or more of nitrogen (N 2 ) gas and ammonia (NH 3 ) gas.

[0011] In various embodiments, the silicon-containing precursor is a halogen-containing precursor. For example, in some embodiments, the silicon-containing precursor is one of dichlorosilane (DCS), hexachlorodisilane (HCDS), and tetrachlorosilane.

[0012] In various embodiments, the plasma is generated remotely.

[0013] In various embodiments, at least one of the first nitrogen-containing gas and the second nitrogen-containing gas is diluted with nitrogen (N 2 ) gas.

[0014] In various embodiments, exposing the substrate to a silicon-containing precursor in a gas phase and exposing the substrate to a first nitrogen-containing gas in a plasma-free environment in time-separated pulses is performed for one or more cycles prior to exposing the substrate to a plasma generated by igniting a second nitrogen-containing gas.

[0015] In various embodiments, the chamber pressure during at least one of exposing the substrate to the silicon-containing precursor in a vapor phase and exposing the substrate to the first nitrogen-containing gas in a plasma-free environment is about 5 Torr to about 25 Torr.

[0016] In various embodiments, the chamber pressure during ignition of the second nitrogen-containing gas to generate the plasma is from about 1 Torr to about 10 Torr.

[0017] In various embodiments, the chamber pressure during ignition of the second nitrogen-containing gas to generate the plasma is at least about 40% lower than the chamber pressure during at least one of exposing the substrate to the silicon-containing precursor in a gas phase and exposing the substrate to the first nitrogen-containing gas in a plasma-free environment.

[0018] In various embodiments, exposing the substrate to the plasma generated by igniting the second nitrogen-containing gas includes exposing the substrate to hydrogen gas.

[0019] In various embodiments, exposing the substrate to the plasma generated by igniting the second nitrogen-containing gas is performed for a duration of about 1 second to about 30 seconds.

[0020] In various embodiments, exposing the substrate to a silicon-containing precursor in a gas phase, exposing the substrate to a first nitrogen-containing gas in a plasma-free environment, and exposing the substrate to a plasma generated by igniting a second nitrogen-containing gas are performed without breaking vacuum.

[0021] In various embodiments, exposing the substrate to a silicon-containing precursor in a vapor phase, exposing the substrate to a first nitrogen-containing gas in a plasma-free environment, and exposing the substrate to a plasma generated by igniting a second nitrogen-containing gas are performed in the same chamber.

[0022] In various embodiments, at least one or more of exposing the substrate to a silicon-containing precursor in a gas phase, exposing the substrate to a first nitrogen-containing gas in a plasma-free environment, and exposing the substrate to a plasma generated by igniting a second nitrogen-containing gas is performed in a single wafer chamber.

[0023] In any of the above embodiments, the method may further include purging a processing chamber housing the substrate before or after exposing the substrate to any one or more of a silicon-containing precursor in a gas phase, exposing the substrate to a first nitrogen-containing gas in a plasma-free environment, and exposing the substrate to a plasma generated by igniting a second nitrogen-containing gas.

[0024] In some embodiments, the chamber pressure of the processing chamber is reduced during the purge.In any of the above embodiments, the substrate is heated to a temperature of at least about 500°C.

[0025] In certain embodiments, the method further comprises exposing the formed silicon nitride to an in-situ nitridation or oxidation process to combine nitrogen or oxygen to form a second silicon-containing film. In certain embodiments, the method further comprises setting a temperature of one or more chamber components of a processing chamber for accommodating a substrate to at least about 650° C. before providing the substrate having features thereon; after setting the temperature to at least about 650° C., introducing a halogen-free aminosilane precursor to the processing chamber; and introducing a nitrogen-containing reactant and igniting a plasma to form a silicon nitride undercoat on at least one of the one or more chamber components.

[0026] Another aspect relates to an apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber comprising a chuck; one or more gas inlets leading to the processing chambers and associated flow control hardware; a plasma generator; and a controller having a memory and at least one processor, wherein the memory and the at least one processor are communicatively coupled to each other, the at least one processor is operably coupled to at least the flow control hardware, and the memory stores computer executable instructions for controlling the at least one processor to control at least the flow control hardware to: cause a silicon-containing precursor to be introduced into the one or more processing chambers for a duration sufficient to adsorb at least some of the silicon-containing precursor to adsorb to a surface of a substrate without igniting a plasma; cause a first nitrogen-containing gas to be introduced without igniting a plasma; and cause a plasma to be generated using a second nitrogen-containing gas to form silicon nitride.

[0027] In any of the above embodiments, the plasma generator is a remote plasma generator.

[0028] Another aspect relates to a method of processing a processing chamber without a substrate therein, the method comprising: setting a temperature of one or more chamber components of the processing chamber to at least about 650° C.; introducing a halogen-free aminosilane precursor to the processing chamber after setting the temperature to at least about 650° C.; and introducing a nitrogen-containing reactant and igniting a plasma to form a silicon nitride undercoating on at least one of the one or more chamber components.

[0029] In various embodiments, the method further includes, prior to setting the temperature of the one or more chamber components of the processing chamber to at least about 650°C, cleaning at least one of the one or more chamber components at a temperature of about 400°C.

[0030] In some embodiments, cleaning is performed at a chamber pressure of about 4 Torr to about 8 Torr.

[0031] In some embodiments, cleaning includes flowing nitrogen and transferring aluminum fluoride to a pump. For example, in some embodiments, nitrogen flows at a flow rate of about 10 slm to about 40 slm.

[0032] In various embodiments, the method further includes purging the process chamber after introducing the halogen-free aminosilane precursor and before introducing the nitrogen-containing reactant.

[0033] In various embodiments, the method further includes purging the process chamber after introducing the nitrogen-containing reactant.

[0034] In various embodiments, the method further comprises cyclically repeating the introduction of the halogen-free aminosilane precursor and the introduction of the nitrogen-containing reactant. In some embodiments, about 100 to about 5000 cycles are performed.

[0035] In various embodiments, the method further comprises: a halogen-free aminosilane precursor having the formula (R′) 4-x Si(NR″2) x wherein x is 1, 2, 3 or 4; R′ is one of hydrogen, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazine, azido, hydroxy, alkyl, siloxy, cyanoxy, isocyanate, cyano, isocyano and substituted variations thereof; and R″ is one of hydrogen, aliphatic, heteroaliphatic, aromatic, heteroaromatic or amino.

[0036] In various embodiments, the aminosilane precursor is diisopropylaminosilane, tert-butylaminosilane, methylaminosilane, tert-butylsilylamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2, BTBAS), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), bis(diethylamino)silane (BDEAS) and trisilylamine (N(SiH3)3).

[0037] In various embodiments, the one or more chamber components include a base.

[0038] In various embodiments, the chamber pressure is constant during the cyclic introduction of the halogen-free aminosilane precursor and the introduction of the nitrogen-containing reactant.

[0039] In various embodiments, the silicon nitride undercoat is deposited to at least about Thickness.

[0040] In various embodiments, the method includes, after forming the silicon nitride base coating, treating one or more substrates in the processing chamber with a halogen-containing gas.

[0041] Another aspect relates to an apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber comprising a chuck; one or more gas inlets into the processing chambers and associated flow control hardware; and a controller having at least one processor and a memory, wherein the at least one processor is communicatively coupled to the memory, the at least one processor is at least operably coupled to the flow control hardware, and the memory stores computer executable instructions for controlling the at least one processor to at least control the flow control hardware to: set a temperature of one or more chamber components of the processing chamber to at least about 650° C.; after setting the temperature to at least about 650° C., introduce a halogen-free aminosilane precursor into the processing chamber; and introduce a nitrogen-containing reactant and generate a plasma to form a silicon nitride base coating on at least one of the one or more chamber components.

[0042] In some embodiments, the memory further includes computer executable instructions for introducing nitrogen at a temperature of about 400°C to pre-clean the processing chamber prior to setting the temperature of the one or more chamber components of the processing chamber to at least about 650°C.

[0043] One aspect relates to a method of processing a substrate, the method comprising: introducing a substrate having features; exposing the substrate to a silicon-containing precursor for a duration sufficient to cause at least some of the silicon-containing precursor to adsorb to a surface of the substrate; exposing the substrate to a reactant species to form a first silicon-containing film; exposing the first silicon-containing film to an in-situ nitridation or oxidation process to incorporate nitrogen or oxygen to form a second silicon-containing film.

[0044] In various embodiments, an in-situ nitridation or oxidation process converts the first silicon-containing film into the second silicon-containing film.

[0045] In various embodiments, the first silicon-containing film is silicon oxide. For example, in some embodiments, the silicon oxide has an atomic ratio of silicon to oxygen of about 33.5:66.5.

[0046] In various embodiments, the first silicon-containing film is silicon nitride. For example, in some embodiments, the silicon nitride has an atomic ratio of silicon to nitrogen of about 43:57.

[0047] In various embodiments, the second silicon-containing film is silicon oxynitride.

[0048] In various embodiments, the second silicon-containing film is a graded film.

[0049] In various embodiments, the second silicon-containing film is a graded silicon oxynitride film.

[0050] In various embodiments, exposing the substrate to the silicon-containing precursor and exposing the substrate to the reactant species are performed cyclically. In some embodiments, the in-situ nitridation or oxidation process is performed every n cycles, where n is about 1 to about 100.

[0051] In various embodiments, the silicon-containing precursor is a halogen-containing silicon-containing precursor. In some embodiments, the halogen-containing silicon-containing precursor is dichlorosilane.

[0052] In various embodiments, the silicon-containing precursor is an aminosilane. In some embodiments, the aminosilane is diisopropylaminosilane (DIPAS).

[0053] In various embodiments, the silicon-containing precursor is diluted with nitrogen.

[0054] In various embodiments, exposing the substrate to the silicon-containing precursor, exposing the substrate to the reactant species, and exposing the first silicon-containing film to an in-situ nitridation or oxidation process are performed in the same processing chamber.

[0055] In various embodiments, exposing the substrate to the reactant species includes exposing the substrate to a first reactant species in the absence of a plasma, followed by exposing the substrate to a plasma generated by igniting a second reactant gas.

[0056] In various embodiments, exposing the substrate to the reactant species includes flowing a mixture of oxygen and hydrogen in a plasma-free environment.

[0057] In various embodiments, exposing the substrate to the reactant species includes generating a plasma from oxygen, hydrogen, or a mixture of oxygen and hydrogen.

[0058] In various embodiments, the reactant species is an oxygen-containing species. In some embodiments, the oxygen-containing species is one of oxygen, carbon dioxide, carbon monoxide, ozone, hydrogen peroxide, and plasmas thereof.

[0059] In various embodiments, exposing the substrate to the reactant species includes flowing a nitrogen-containing gas in a plasma-free environment.

[0060] In various embodiments, the reactant species is a nitrogen-containing species. For example, in some embodiments, the nitrogen-containing species is one of ammonia, nitrogen, nitrous oxide, nitric oxide, and plasmas thereof.

[0061] In various embodiments, the substrate is introduced into a processing chamber set at a chamber pressure of about 5 Torr to about 25 Torr.

[0062] In various embodiments, the silicon-containing precursor is introduced using a flow rate of about 100 seem to about 2000 seem.

[0063] In various embodiments, the substrate is exposed to the silicon-containing precursor for a duration of about 0.1 seconds to about 10 seconds.

[0064] In various embodiments, the silicon-containing precursor flows with the dilution gas having a flow rate of about 500 seem to about 2000 seem.

[0065] In various embodiments, the reactant species flow using a flow rate of about 100 seem to about 10,000 seem.

[0066] In various embodiments, the reactant species flow using a flow rate of about 100 seem to about 5000 seem.

[0067] In various embodiments, the reactant material includes a mixture of oxygen and hydrogen. In some embodiments, the oxygen flows at a flow rate of about 100 sccm to about 5000 sccm, and the hydrogen flows at a flow rate of about 0 sccm to about 5000 sccm.

[0068] In various embodiments, the reactant species flow using a flow rate of about 2,000 seem to about 10,000 seem.

[0069] In some embodiments, the reactant material includes a mixture of ammonia and hydrogen. In various embodiments, ammonia flows at a flow rate of about 2000 sccm to about 10000 sccm, and hydrogen flows at a flow rate of about 0 sccm to about 10000 sccm.

[0070] In various embodiments and in any of the above embodiments, the silicon oxide film is conformal.

[0071] In various embodiments and in any of the above embodiments, the method further comprises sweeping after exposing the substrate to the silicon-containing precursor and before exposing the substrate to the reactant species.

[0072] In various embodiments and in any of the above embodiments, the method further comprises sweeping after exposing the surface of the substrate to the in-situ oxidation or nitridation.

[0073] In various embodiments and in any of the above embodiments, the second silicon-containing film is a silicon oxynitride film formed as a tunnel layer in a 3D-NAND structure.

[0074] Another aspect relates to an apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber comprising a chuck; one or more gas inlets leading to the processing chambers and associated flow control hardware; and a controller having a memory and at least one processor, wherein the memory and the at least one processor are communicatively connected to each other, the at least one processor is at least operably connected to the flow control hardware, and the memory stores computer executable instructions, the computer executable instructions being used to control the at least one processor to control at least the flow control hardware to: cause a silicon-containing precursor to be introduced into the one or more processing chambers for a duration sufficient to adsorb at least some of the silicon-containing precursor to adsorb to a surface of the substrate; cause an oxygen-containing or nitrogen-containing gas to be introduced; and optionally cause a plasma to be generated by igniting the oxygen-containing or nitrogen-containing gas; and cause oxidation or nitridation of the silicon-containing film to form a silicon oxynitride film.

[0075] In various embodiments, the device includes instructions for causing any of the above-described embodiments to be executed in the device.

[0076] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] Figure 1A A process flow diagram is provided to depict operations that may be performed in accordance with certain disclosed embodiments.

[0078] Figure 1B A process flow diagram is provided to depict operations that may be performed in accordance with certain disclosed embodiments.

[0079] Figure 1C A process flow diagram is provided to depict operations that may be performed in accordance with certain disclosed embodiments.

[0080] Figure 1D Illustrative schematic diagrams of layers deposited and oxidized according to certain disclosed embodiments are shown.

[0081] Figure 2 A timing diagram is provided to illustrate operations that may be performed in accordance with certain disclosed embodiments.

[0082] Figure 3 is a schematic diagram of an exemplary processing chamber for performing certain disclosed embodiments.

[0083] Figure 4 is a schematic diagram of an exemplary processing tool for performing certain disclosed embodiments.

[0084] Figure 5 is a schematic diagram of an exemplary processing tool for performing certain disclosed embodiments.

[0085] Figure 6 is a graph showing the growth of silicon nitride per cycle.

[0086] Fig. 7A , 7B and 7C are FTIR of silicon nitride films.

[0087] Figure 8 A graph showing the impurity concentration of a silicon nitride film.

[0088] Fig. 9 The growth per cycle of silicon nitride film as a function of susceptor temperature is shown.

[0089] Fig.10 The film thickness uniformity of the silicon nitride film is shown.

[0090] Fig.11A and 11B Depicted are graphs of growth per cycle and refractive index for films deposited according to certain disclosed embodiments.

[0091] Fig. 12A and 12B Depicted are graphs of growth per cycle and refractive index for films deposited according to certain disclosed embodiments.

[0092] Fig.13A and 13B Graphs depicting growth and refractive index per cycle for films deposited according to certain disclosed embodiments.

[0093] Fig.14 FTIR spectra of silicon oxynitride materials deposited using certain disclosed embodiments.

[0094] Fig.15 Graphs showing sidewall thickness and depth within features for silicon oxynitride films deposited using certain disclosed embodiments. DETAILED DESCRIPTION

[0095] In the following description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be implemented without some or all of these specific details. In other respects, well-known process operations are not described in detail in order to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that they are not intended to limit the disclosed embodiments.

[0096] Semiconductor manufacturing processes may involve depositing silicon nitride ("SiN") material. While SiN can be deposited using thermal atomic layer deposition (ALD) in a furnace, furnace deposition is limited in the ability to tune and control the properties of the deposited SiN film. Alternatively, plasma-based processes using remote plasma may be utilized, but the controllability of film properties may also be limited, and in some cases, damage to the underlying deposited SiN layer may still occur.

[0097] Semiconductor manufacturing processes may involve the use of halogen-containing precursors. For example, the deposition of silicon nitride may involve the use of halogen-containing precursors, such as dichlorosilane (DCS) and / or hexachlorodisilane (HCDS), and the use of ammonia during the conversion. However, the processing chamber used to process semiconductor wafers using these chemicals may include metal components, such as aluminum-containing pedestals, aluminum-containing focus rings, and aluminum-containing showerheads and lift pins. Although aluminum is provided as an example herein, it should be understood that other metals may also be used for the metal components. For example, some components may be made of nickel.

[0098] When the halogen-containing precursor contacts the metal surface, metal halides may be formed, and the metal halides may cause metal contamination during semiconductor substrate processing within the chamber. For example, metal halides may be formed at temperatures above about 450° C. In a specific example, when a dichlorosilane precursor is used to form an undercoat film on a metal component, corrosive hydrochloric acid (HCl) may be formed when the undercoat is exposed to ammonia during semiconductor wafer processing. Therefore, halogen-containing precursors may not be used to deposit undercoat films on metal-containing chamber components to protect the components during processing. Although ceramic materials can be used for chamber components so that halogen-containing precursors can be used to form undercoat films, it may be advantageous to use a processing chamber having one or more surfaces made of metal.

[0099] Semiconductor manufacturing processes involve the deposition of a variety of materials, including but not limited to silicon-containing materials. Exemplary silicon-containing materials that may be deposited during semiconductor manufacturing include silicon oxide (SiO x), silicon nitride (SiN), silicon carbide (SiC), silicon oxynitride (SiON), silicon oxycarbide (SiOC), and silicon carbide nitride (SiCN). In some manufacturing applications, it may be necessary to form a graded material. A material is graded when the concentration of one or more atoms within a material varies within a portion of the material. For example, a material layer is graded when the concentration of one or more atoms of a material is different in one region of the layer than in another region of the material. In some cases, a graded layer is used, wherein the layer has a gradually changing composition, wherein a portion of the layer has more or less oxygen or nitrogen than another portion of the layer. In some cases, a material is graded so that the atomic concentration at or near the exposed surface of the material is lower than the atomic concentration at a specific depth through the thickness of the material. For example, a blanket material layer deposited horizontally on a semiconductor substrate may be graded, wherein the atomic concentration at the top exposed surface is less than or greater than the atomic concentration at the bottom of the layer contacting the semiconductor substrate. In SiON materials, the relative amounts of nitrogen concentration and oxygen concentration affect the refractive index, so graded SiON materials may also have a variable and controllable refractive index. For example, a nitrogen-rich SiON (N-rich SiON) region may have a higher refractive index than an oxygen-rich SiON (O-rich SiON) region of the same SiON layer. A nitrogen-rich SiON may have an oxygen to nitrogen atomic ratio of less than about 50%. An oxygen-rich SiON may have an oxygen to nitrogen atomic ratio of greater than about 50%. In non-graded SiON materials, the refractive index is fixed and may be from about 1.45 to about 2.15; the tunability of the refractive index is limited to tuning the refractive index of the entire material, not certain regions or layers within the material.

[0100] One method of depositing graded SiON is by using a furnace to deposit SiN material, followed by incorporation of oxygen through controlled furnace oxidation or steam annealing to form a graded SiON film. However, furnace processing is challenging, for example involving the use of high temperature processing, which may be incompatible with certain materials already deposited on the semiconductor substrate, and may pose challenges in terms of thermal cost, long processing time, and limited tunability.

[0101] Provided herein is a method for depositing SiN using a hybrid ALD technique. Certain disclosed embodiments involve performing one or more deposition cycles, wherein each deposition cycle includes dosing of a silicon-containing precursor, exposure to a nitrogen-containing gas or plasma, and plasma exposure. In some embodiments, the deposition cycle includes dosing of a silicon-containing precursor, thermal conversion using a nitrogen-containing gas, and exposure to a nitrogen-containing plasma including N* radicals, H* radicals, NH2* radicals, NH* radicals, and other derivatives. Compared to H* radicals, nitrogen-containing plasma species may primarily include NH* radicals, wherein the ratio of NH* to H* is greater than about 10. Certain disclosed embodiments allow tuning of process conditions to affect the properties of the deposited SiN film. Exemplary tunable process conditions include, but are not limited to, relative flow rates of one or more process gases, plasma conditions during plasma exposure (including gas flow, radio frequency (RF) power, chamber pressure, exposure time, etc.).

[0102] Certain disclosed embodiments are capable of depositing highly conformal films. The conformality of the film can be measured by step coverage. Step coverage can be calculated by comparing the average thickness of the deposited film on the bottom, sidewalls, or top of the groove with the average thickness of the deposited film on the bottom, sidewalls, or top of the feature or groove. A "feature" of a substrate may be a through hole or a contact hole, which may be characterized by one or more of a narrow and / or concave opening, a constriction within a feature, and a high aspect ratio. A high aspect ratio may refer to a feature having an aspect ratio of at least about 10:1, or at least about 15:1, or at least about 20:1, or at least about 50:1, or at least about 100:1, or at least about 1:1, or at least about 150:1, or at least about 200:1. The terms "groove" and "feature" are used interchangeably in the present invention and will be understood to include any hole, through hole, or recessed area of ​​a substrate.

[0103] An example of step coverage can be calculated by dividing the average thickness of the deposited film on the sidewalls by the average thickness of the deposited film at the top of the feature and multiplying it by 100 to obtain a percentage. Although ALD can deposit highly conformal films, depositing films into high aspect ratio features becomes challenging. The step coverage and uniformity of film features along the sidewalls depends, among other factors, on the delivery of the deposition precursors, reactant ions and / or radicals (such as those generated by igniting the reactant gas with a plasma), and byproducts. As the trench size decreases, delivery in the trench becomes increasingly difficult, resulting in the formation of seams and / or voids in high aspect ratio trenches.

[0104] Certain disclosed embodiments deposit SiN with at least about 80%, or at least about 90%, or at least about 99%, or about 100% conformality in high aspect ratio features.

[0105] Certain disclosed embodiments enable the deposition of films having excellent film properties. For example, SiN deposited using certain disclosed embodiments can exhibit lower roughness (e.g., less than about 25% compared to thermal SiN films), reduced impurities (e.g., less than about 50% oxygen atoms), reduced intra-wafer non-uniformity, stress modulation (e.g., changing stress from tensile to compressive), density improvement, and reduced wet etch rate in 100:1 dilute hydrofluoric acid.

[0106] The technology described herein relates to thermal atomic layer deposition (ALD). That is, in various embodiments, the reaction between aminosilane or halosilane and nitrogen-containing reactants to form silicon nitride is carried out without igniting a plasma. ALD is a technology that uses continuous self-limiting reactions to deposit thin layers of materials. Generally, an ALD cycle includes the operation of delivering and adsorbing at least one reactant to a substrate surface, followed by reacting the adsorbed reactant with one or more reactants to form a portion of a film layer. As another example, a silicon nitride deposition cycle may include the following operations: (i) delivering / adsorbing a silicon-containing precursor, (ii) purging the silicon-containing precursor from the chamber, (iii) delivering a nitrogen-containing gas, and (iv) purging the nitrogen-containing gas from the chamber.

[0107] Unlike chemical vapor deposition (CVD) techniques, the ALD process uses a surface-mediated deposition reaction to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface having a group of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, which is provided in a certain dosage to a chamber containing the substrate. Molecules of the first precursor are adsorbed onto the substrate surface, including chemically adsorbed species and / or physically adsorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound and derivatives of the compound. For example, the adsorption layer of a silicon-containing precursor may include a silicon-containing precursor and a derivative of the silicon-containing precursor. After the first precursor is dosed, the chamber is evacuated to remove most or all of the silicon-containing precursor remaining in the gas phase, so that most or only the adsorbed species remain. In some implementations, the chamber may not be completely evacuated. For example, the chamber may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant, such as a nitrogen-containing reactant, is introduced into the chamber so that some of these molecules react with the silicon-containing precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed silicon-containing precursor. The chamber can then be evacuated again to remove unbound silicon-containing reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

[0108] In some embodiments, the ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dosing phase of the ALD cycle ends before the precursor contacts the substrate to saturate the surface evenly. Typically, at this time, the precursor flow is shut off or diverted, and only the sweep gas flows. By operating in this saturated state, the ALD process reduces cycle time and increases throughput. However, because precursor adsorption is not saturation-limited, the concentration of the adsorbed precursor may vary slightly across the substrate surface. An example of an ALD process operating in a subsaturated state is provided in U.S. Patent Application No. 14 / 061,587 (now U.S. Patent No. 9,355,839), filed on October 23, 2013, entitled "SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILMDEPOSITION," the entire contents of which are incorporated herein by reference.

[0109] In certain implementations, the ALD method may include plasma activation. However, in the thermal ALD process described herein, no plasma is ignited. As described herein, the ALD method and apparatus described herein may be a conformal film deposition (CFD) method generally described in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION” (now U.S. Patent No. 8,728,956), and described in U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled “SILICON NITRIDE FILMS AND METHODS,” the entire contents of which are incorporated herein by reference.

[0110] Figure 1A Flowcharts are provided that depict operations that may be performed in accordance with certain disclosed embodiments.

[0111] In operation 102, a substrate is provided to a processing chamber. In various embodiments, the processing chamber is a single wafer chamber. In some embodiments, the processing chamber is a station in a multi-station chamber. The process conditions described herein are applicable to a single wafer chamber.

[0112] The processing chamber can be set to a chamber pressure between about 5 mTorr and about 25 Torr or about 0.5 Torr and about 25 Torr. Such a chamber pressure can be used in all operations 104 to 116 as described herein. In some embodiments, the chamber pressure during different operations may be different. The chamber pressure may also depend on the chemistry selected for many of the operations described herein.

[0113] During operations 104 to 108, the substrate may be heated to a substrate temperature of about 25° C. to about 800° C., or about 500° C. to about 700° C., or at least about 650° C. It should be understood that substrate temperature as used herein refers to the temperature at which the pedestal holding the substrate is set, and in some embodiments, when the substrate is provided to the processing chamber pedestal, the substrate may be heated to a desired substrate temperature before processing the substrate. The substrate temperature may be the same in all operations 102 to 108 as described herein.

[0114] The substrate may be any suitable substrate. The substrate may be a silicon wafer, such as a 200-mm wafer, a 300-mm wafer, including a wafer having one or more material layers, such as dielectric, conductive, or semiconductor materials deposited thereon. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxide, metal nitride, metal carbide, and metal layers. In some embodiments, the substrate includes silicon oxide and silicon. In some embodiments, the substrate includes a portion of a fabricated 3D-NAND structure.

[0115] In some embodiments, the features may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or at least about 20:1, or at least about 50:1, or at least about 100:1, or at least about 150:1, or at least about 200:1 or more. The features may also have a size close to the opening, such as an opening diameter or line width between about 10nm and 500nm, such as between about 25nm and about 300nm. The disclosed method may be performed on a substrate with features having an opening less than about 150nm. A through hole, groove, or other recessed feature may be referred to as an unfilled feature or features. According to various embodiments, the feature profile may taper and / or include a protrusion at the feature opening. A concave profile is a profile that tapers from the bottom, closed end, or interior of the feature to the feature opening. The concave profile may result from asymmetric etch dynamics during patterning and / or from protrusions resulting from non-conformal film step coverage in a previous film deposition, such as deposition of a diffusion barrier layer. In various examples, the width of the feature at its top opening may be less than the width of the feature bottom. One or more features may have a high aspect ratio, which is defined as having an aspect ratio greater than about 100:1, or greater than about 150:1, or greater than about 180:1.

[0116] In some embodiments, the substrate may be partially fabricated for forming a memory device. In some embodiments, the exposed area of ​​the substrate includes a silicon-containing surface, including but not limited to low-k dielectric materials, silicon oxides, silicon nitrides, silicon oxynitrides, silicon oxycarbides, carbon silicon nitrides, and silicon carbides. In some embodiments, the exposed area of ​​the substrate includes silicon oxynitrides.

[0117] In operation 104, a silicon-containing precursor can be introduced into the processing chamber. In various embodiments, the silicon-containing precursor is a silane. Non-limiting examples of silanes that can be used include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. Additional examples of silicon-containing precursors may be included elsewhere herein, such as in the definitions and precursors section. In some embodiments, the silicon-containing precursor is a halosilane, such as one or more of the following: dichlorosilane (DCS), hexachlorodisilane (HCDS), tetrachlorosilane or other chlorosilane precursors.

[0118] In some embodiments, for a single wafer chamber, a silicon-containing precursor may flow at a flow rate of about 100 sccm to about 2000 sccm. The silicon-containing precursor may flow with an inert push gas (e.g., nitrogen or argon or a mixture of nitrogen and argon). For a single wafer chamber, the flow rate of the inert push gas may be about 300 sccm to about 1500 sccm. Operation 104 may be performed for a duration of about 0.1 seconds to about 10 seconds. During operation 104, the processing chamber may have a chamber pressure of about 5 Torr to about 25 Torr. In some embodiments, additional nitrogen may be introduced with the silicon-containing precursor and / or the inert push gas for dilution, for pressure stabilization, or both. For a single wafer chamber, additional nitrogen may flow at a flow rate of about 500 sccm to about 2000 sccm. In one example, dichlorosilane is introduced into a chamber containing a substrate at a chamber pressure of about 9.5 Torr in a plasma-free environment at a flow rate of about 1000 sccm for about 5 seconds.

[0119] The process chamber is optionally purged in operation 106. Operation 106 involves stopping the flow of the silicon-containing precursor and introducing a flow of an inert gas or purge gas to remove excess silicon-containing precursor molecules that are not adsorbed onto the substrate surface or silicon-containing precursor molecules in a gas phase in a process region of the process chamber above the substrate.

[0120] Exemplary inert or sweeping gases include, but are not limited to, nitrogen and argon. For a single wafer chamber, the flow rate of the inert or sweeping gas during operation 106 is about 1000 sccm to about 40000 sccm. The introduction of the inert or sweeping gas may be performed for a duration of about 0.1 seconds to about 10 seconds. During operation 106, the chamber pressure may be about 0.5 Torr to about 22 Torr. In some embodiments, a lower pressure may be used to purge more effectively. For example, in some embodiments, a pressure of less than about 0.1 Torr or about 0.1 Torr may be used. In some embodiments, the chamber pressure during operation 106 is the same as the chamber pressure during operation 104. In one example, nitrogen is introduced at a flow rate of about 10000 sccm at a chamber pressure of about 9.5 Torr for about 10 seconds. The flow rate, duration, and chamber pressure may depend on the precursor used in operation 106. Operation 106 is performed without igniting plasma. Operation 106 is performed in a plasma-free environment.

[0121] In operation 108, the substrate is exposed to a nitrogen-containing gas for thermal conversion. The nitrogen-containing gas may be introduced without igniting a plasma. The nitrogen-containing gas may be introduced in a plasma-free environment. For a single wafer chamber, the nitrogen-containing gas system is introduced at a flow rate of about 2000 sccm to about 10000 sccm.

[0122] Nitrogen-containing reactants are reactants or reactant mixtures containing at least one nitrogen. Non-limiting examples include nitrogen (N2), ammonia, hydrazine, amines (amines with carbon), such as methylamine, dimethylamine, ethylamine, isopropylamine, tert-butylamine, di-tert-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isopentylamine, 2-methylbutyl-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-tert-butylhydrazine, and aromatic amines, such as aniline, pyridine and benzylamine. Amines can be primary, secondary, tertiary or quaternary (e.g., tetraalkylammonium compounds). Nitrogen-containing reactants can contain heteroatoms other than nitrogen, such as hydroxylamine, tert-butyloxycarbonylamine and N-tert-butylhydroxylamine as nitrogen-containing reactants. Exemplary nitrogen-containing reactants include nitrogen, ammonia and amines. Exemplary hydrazine is N2H4. Exemplary amine is tributylamine. Nitrogen-containing gases can also be hydrogen-containing. In various embodiments, nitrogen-containing gases can be ammonia (NH3) gas.

[0123] In some embodiments, a hydrogen-containing gas may also flow during operation 108. In some embodiments, the hydrogen-containing gas is hydrogen (H2) gas. For a single wafer chamber, hydrogen may flow at a flow rate of about 0 sccm to about 5000 sccm.

[0124] In some embodiments, NH is introduced with one or more diluent gases, such as nitrogen or argon or both. In some embodiments, during exposure to a nitrogen-containing gas without igniting a plasma, nitrogen is flowed as a diluent gas at a flow rate of about 500 sccm to about 2000 sccm for a single wafer chamber. Argon may flow at a flow rate of about 10 slm to about 40 slm for a single wafer chamber.

[0125] The exposure to the nitrogen-containing gas without igniting the plasma may be performed for a duration of about 1 second to about 120 seconds. The exposure to the nitrogen-containing gas without igniting the plasma may be performed at a chamber pressure of about 5 Torr to about 25 Torr.

[0126] In some embodiments, higher pressures may be used to improve conformality of the film being deposited in operation 108. For example, in some embodiments, pressures of at least about 20 Torr, or at least about 22 Torr, or at least about 30 Torr, or about 20 Torr to about 30 Torr may be used.

[0127] In one example, NH3 is introduced at a flow rate of about 4500 sccm at a chamber pressure of 9.5 Torr for 60 seconds. During this operation, the silicon-containing precursor is at least partially converted to silicon nitride, so that the nitrogen-containing gas thermally converts the adsorbed silicon-containing precursor into silicon nitride.

[0128] In operation 110, the chamber is optionally purged. The purging may be performed using any one or more of the process gases and conditions described above with respect to operation 106. In one example, nitrogen gas is flowed at a flow rate of about 10,000 seem for about 10 seconds in a chamber having a chamber pressure of about 9.5 Torr.

[0129] In some implementations, operations 106 - 110 may be performed for multiple cycles before operation 112 is performed.

[0130] In operation 112, the substrate is exposed to a nitrogen-containing plasma. Operation 112 may involve flowing or introducing a nitrogen-containing plasma to the substrate. The nitrogen-containing plasma may be generated by igniting one or more nitrogen-containing gases, including but not limited to ammonia and nitrogen. For a single wafer chamber, nitrogen may flow at a flow rate of about 5000sccm or about 25000sccm or about 10000sccm to about 25000sccm or about 12000sccm. Ammonia may flow at a flow rate of about 0sccm to about 500sccm or about 50sccm to about 250sccm or about 125sccm. In some embodiments, the nitrogen-containing gas is a gas that does not contain ammonia. In some embodiments, the nitrogen-containing gas does not include ammonia. In some embodiments, ammonia is 0sccm. In some embodiments, hydrogen also flows during operation 112. Hydrogen may flow at a flow rate of about 0sccm to about 100sccm. Operation 112 may be performed for a duration of about 1 second to about 30 seconds. Operation 112 may be performed in a chamber having a chamber pressure of about 1 Torr to about 10 Torr. Operation 112 may be performed at a chamber pressure of less than about 40% of the chamber pressure used in operations 108 or 104. In some embodiments, a chamber pressure of about 3 Torr to about 6 Torr may be used to tune the conformality of the film being deposited. In some embodiments, lower pressures may be used to tune film properties.

[0131] The plasma generated in this operation may have a plasma power of about 500 W to about 6000 W. In various embodiments, the plasma may be an inductively coupled plasma or a capacitively coupled plasma. The inductively coupled plasma may be set to a plasma between about 500 W and about 6000 kW. In some embodiments, a bias voltage between about 0 V and about 1000 V may be applied.

[0132] In one example, nitrogen gas flows at a flow rate of about 12,000 sccm, ammonia gas flows at a flow rate of about 125 sccm, and plasma is generated from the gas mixture in a chamber having a pressure of about 6 Torr and exposed to the substrate for about 10 seconds.

[0133] In various embodiments, a remote plasma may be used. The plasma introduced into the processing chamber may be primarily free radical based. In some embodiments, the substrate is exposed to only N* radicals or a mixture of N* and NH* radicals. In some embodiments, the ratio of H* to NH* radicals may be from about 0.1:1 to about 0:1.

[0134] Different gas mixtures in the plasma may produce different radical mixtures. For example, in some embodiments, a plasma produced from pure nitrogen gas may contain N* radicals, or a majority of N* radicals, or only N* radicals. In some embodiments, a plasma produced from a nitrogen-containing gas mixture with nitrogen, ammonia, and / or hydrogen may include N* radicals as well as H* radicals and NH* radicals. In some embodiments, a large amount of N* is present in the chamber, and the relative concentration of N* is several orders of magnitude higher than that of NH*.

[0135] In operation 114, the process chamber is optionally purged. The purge may be performed using any one or more of the process gases and conditions described above with respect to operation 106 or operation 108. In one example, nitrogen gas is flowed at a flow rate of about 10,000 seem for about 10 seconds in a chamber having a chamber pressure of about 9.5 Torr.

[0136] In operation 116, it is determined whether the film has been deposited to a sufficient thickness. If not, operations 104, 108, and 112 may optionally be repeated, or operations 104-114 may optionally be repeated in a loop.

[0137] Certain disclosed embodiments can deposit silicon nitride films into features whereby the growth rate on the feature sidewalls is increased by about 1.7 times or about 2 times or more compared to performing only thermal conversion (e.g., only exposing to cycles of silicon-containing precursors and nitrogen-containing gases in the absence of plasma, without additional exposure to nitrogen-containing plasma after or during the cycles). For example, compared to thermal conversion (which may have a growth rate of about 1.7 times or about 2 times per cycle), the growth rate on the feature sidewalls is increased by about 1.7 times or about 2 times or more compared to performing only thermal conversion (e.g., only exposing to cycles of silicon-containing precursors and nitrogen-containing gases in the absence of plasma, without additional exposure to nitrogen-containing plasma after or during the cycles). wherein one cycle includes dosing of a silicon-containing precursor and thermal conversion using ammonia), the growth rate may be about (One cycle includes dosing of a silicon-containing precursor, thermal conversion using ammonia gas, and exposure to an RF plasma generated by ammonia and nitrogen gases).

[0138] Additionally, combining thermal conversion and exposure to a nitrogen-containing plasma results in improved step coverage compared to plasma-only processing (eg, a cycle of silicon-containing precursor dosing and exposure to a nitrogen-containing plasma without thermal conversion may result in approximately 75% step coverage).

[0139] Also provided herein is a method for depositing an undercoat film on a metal-containing chamber component using a halogen-free deposition precursor and a device having the undercoat film. The method involves using an aminosilane precursor with a nitrogen plasma to form an undercoat film on a metal-containing component of the chamber. These undercoat films can then protect the chamber components during semiconductor wafer processing (e.g., when the components are exposed to a halogen-containing precursor to deposit silicon nitride). The undercoat film is deposited using a halogen-free process. The undercoat film is deposited using an ammonia-free process. In various embodiments, the undercoat film is deposited using a halogen-free and ammonia-free process. Certain disclosed embodiments also allow the undercoat film to be deposited on components that can be set at different temperatures. For example, the susceptor can be set at a temperature of about 650°C, while the showerhead and chamber walls can be set at a temperature of 100°C. A chamber with an undercoat film deposited using certain disclosed embodiments can be used to process a substrate with little or no metal contamination. Certain disclosed embodiments may also have the advantage of increasing the life of one or more chamber components.

[0140] Certain disclosed embodiments may be used in any processing chamber having metal-containing components, or in any processing chamber involving semiconductor wafer processing using halogen-containing precursors or ammonia-containing reactants.

[0141] Figure 1B A process flow diagram with operations that can be performed according to certain disclosed embodiments is provided. In operation 122, a temperature cleaning operation is performed. In some embodiments, the temperature cleaning operation is referred to as a "pre-clean" operation. During operation 122, the processing chamber does not contain any substrate. In some embodiments, the processing chamber in operation 122 undergoes a temperature cleaning operation because it was previously used for semiconductor wafer processing and may have materials deposited on components from the processing operation therein, which are removed before processing the next semiconductor wafer or multiple wafers. For example, if the processing chamber has residual silicon nitride material on its surface, nitrogen trifluoride can be used to perform temperature cleaning at a temperature of about 350°C to about 550°C, or about 400°C. In some embodiments, on a susceptor having aluminum, some aluminum fluoride may be formed.

[0142] In operation 124, one or more chamber components may be heated to a temperature of at least about 650°C. In various embodiments, operation 124 is performed to perform controlled heating on one or more chamber components to prevent evaporation of metal halides, such as aluminum fluoride, which may have been produced from operation 122. The evaporation of these metal halides may cause deposition at or near the showerhead and cause metal contamination at or near the top of the wafer when the wafer is subsequently processed in the processing chamber. Operation 124 may be performed with a flow rate of at least about 10 slm (from the showerhead) to transfer the metal halide (e.g., aluminum fluoride) to the pump. The flow rate may be about 10 slm to about 40 slm. The gas flowing out of the showerhead may be any one or more inert gases, including but not limited to nitrogen. During operation 104, the chamber pressure may be set at a temperature of at least about 0.5 Torr and about 4 Torr to about 8 Torr. Without being bound by a particular theory, it is believed that flow dynamics corresponding to pressure influence the effectiveness of certain disclosed embodiments, and using a pressure of at least about 0.5 Torr with certain disclosed embodiments allows for adequate cleaning of the chamber.During operation 124, the substrate is still not present in the processing chamber.

[0143] In operation 126, a halogen-free aminosilane precursor is introduced into the processing chamber. In operation 126, the processing chamber still does not contain a substrate, or there is no substrate. An aminosilane precursor is introduced to provide a precursor for forming a primer film. In some embodiments, the aminosilane precursor is diisopropylaminosilane (DIPAS). Additional examples of precursors are described in the precursor section elsewhere herein.

[0144] exist Figure 1A In operation 126 of , atomic layer deposition (ALD) may be used to deposit the undercoat film. The undercoat may be deposited by plasma enhanced atomic layer deposition (PEALD). That is, in various embodiments, a plasma is used to carry out a reaction between an aminosilane and a nitrogen-containing reactant to form a silicon nitride undercoat. ALD is a technique for depositing a thin layer of material using a continuous self-limiting reaction. Typically, an ALD cycle includes an operation of delivering and adsorbing at least one reactant to a substrate surface, followed by reacting the adsorbed reactant with one or more reactants to form a partial film layer. As another example, a silicon nitride deposition cycle may include the following operations: (i) delivering / adsorbing an aminosilane precursor, (ii) purging an aminosilane precursor from a chamber, (iii) delivering plasma species generated by a nitrogen-containing gas, and (iv) purging plasma species from a chamber.

[0145] Unlike chemical vapor deposition (CVD) techniques, the ALD process uses a surface-mediated deposition reaction to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface having a group of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, which is provided to a chamber containing the substrate in a certain dosage. Molecules of the first precursor are adsorbed onto the substrate surface, including chemically adsorbed species and / or physically adsorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound and derivatives of the compound. For example, the adsorption layer of an aminosilane precursor may include an aminosilane precursor and a derivative of the aminosilane precursor. After the first precursor is dosed, the chamber is evacuated to remove most or all of the aminosilane precursor remaining in the gas phase, so that most or only the adsorbed substances remain. In some implementations, the chamber may not be completely emptied. For example, the chamber may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant, such as a nitrogen-containing reactant, is introduced into the chamber so that when the plasma is generated, some of these molecules react with the aminosilane precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed aminosilane precursor. The chamber can then be evacuated again to remove unbonded second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

[0146] In some embodiments, the ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dosing phase of the ALD cycle ends before the precursor contacts the substrate to saturate the surface evenly. Typically, at this time, the precursor flow is shut off or diverted, and only the sweep gas flows. By operating in this saturated state, the ALD process reduces cycle time and increases throughput. However, because precursor adsorption is not saturation-limited, the concentration of the adsorbed precursor may vary slightly across the substrate surface. An example of an ALD process operating in a subsaturated state is provided in U.S. Patent Application No. 14 / 061,587 (now U.S. Patent No. 9,355,839), filed on October 23, 2013, entitled "SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILMDEPOSITION," the entire contents of which are incorporated herein by reference.

[0147] In certain implementations, the ALD method may include plasma activation. However, in the thermal ALD process described herein, no plasma is ignited. As described herein, the ALD method and apparatus described herein may be a conformal film deposition (CFD) method generally described in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION” (now U.S. Patent No. 8,728,956), and described in U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled “SILICON NITRIDE FILMS AND METHODS,” the entire contents of which are incorporated herein by reference.

[0148] During operation 126, for a single wafer chamber, the aminosilane precursor may flow at a flow rate of about 100 sccm to about 2000 sccm. In some embodiments, for a single wafer chamber, the aminosilane precursor may flow with a push gas (e.g., nitrogen) using a flow rate of about 300 sccm to about 1500 sccm. The push gas may flow to the ampoule, and both the precursor and the push gas flow into the chamber. The use of a push gas may allow more precursor to be delivered to the chamber. In some embodiments, the push gas may also dilute the precursor flow. In some embodiments, the aminosilane precursor is diluted with a dilution gas. The dilution gas may be used to dilute the precursor so that the precursor is evenly distributed to all parts of the chamber during cleaning. The dilution gas may flow using a flow rate of about 500 sccm to about 2000 sccm. The flow rate ratio of the dilution gas to the aminosilane precursor may be about 0.1:1 to about 10:1.

[0149] During operation 126, the chamber pressure may be set at a pressure of about 1 Torr to about 25 Torr. Operation 126 may be performed for a duration of about 0.1 seconds to about 10 seconds.

[0150] Back to Figure 1B, in operation 128, optionally purge the chamber. Purging the chamber may involve flowing a purge gas or purge gases, which may be a carrier gas used for other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Examples of purge gases include argon (Ar), nitrogen (N2), hydrogen (H2), helium (He), oxygen (O2), krypton (Kr), xenon (Xe), neon (Ne) and combinations thereof. In various embodiments, the purge gas is an inert gas. The purge gas may include one or more gases. In some embodiments, operation 128 may include one or more evacuation substages for evacuating the process chamber. Alternatively, it should be understood that operation 128 may be omitted in some embodiments. In some embodiments, increasing the flow rate of one or more purge gases may reduce the duration of operation 128. For example, the purge gas flow rate may be adjusted according to various reactant thermodynamic properties and / or geometric properties of the process chamber and / or process chamber conduit to modify the duration of operation 128. In a non-limiting example, the duration of the sweep phase can be adjusted by adjusting the sweep gas flow rate. This can reduce the deposition cycle time, thereby improving substrate throughput. After sweeping, the aminosilane molecules remain adsorbed on the substrate surface.

[0151] For a single wafer chamber, the flow rate of the purge gas may be about 1000 sccm to about 40000 sccm. The duration of operation 108 may be about 0.1 seconds to about 10 seconds. The chamber pressure during operation 108 may be about 0.5 Torr to about 25 Torr.

[0152] In operation 130, a nitrogen-containing gas is introduced and a plasma is generated to convert the adsorbed aminosilane precursor molecules into silicon nitride. In various embodiments, the nitrogen-containing gas is nitrogen. For a single wafer chamber, the flow rate of the nitrogen-containing gas may be about 5000 sccm to about 25000 sccm. The duration of operation 130 may be about 0.1 seconds to about 30 seconds. The chamber may be set to a pressure of about 1 Torr to about 10 Torr.

[0153] During this operation, plasma is used to generate plasma or active species containing nitrogen. The plasma can be generated using a single frequency or dual frequency plasma. For dual frequency plasma, a high frequency plasma is generated for a single wafer chamber at a plasma power of about 100 W to about 6000 W, while a low frequency plasma is generated for a single wafer chamber at a plasma power of about 0 W to about 2500 W. Inductively coupled plasma, microwave plasma, and capacitively coupled plasma can be used. Relative to operation 106, the flow rate ratio of nitrogen to aminosilane precursor gas can be about 1:100 to about 1:5. In some embodiments, operation 130 is performed using an ion filter in a showerhead so that only or most of the plasma species entering the processing chamber are nitrogen radicals.

[0154] In operation 132, the chamber is optionally purged. The purge may be performed using any of the chemicals, methods, and process conditions described above with respect to operation 128. In some embodiments, nitrogen is used as the purge gas to purge the chamber. For a single wafer chamber, the nitrogen may flow at a flow rate of about 1000 sccm to about 40000 sccm. Operation 130 may be performed for a duration of about 0.1 seconds to about 10 seconds. The chamber pressure may be about 0.5 Torr to about 25 Torr.

[0155] Operations 126, 128, 130, and 132 may constitute an atomic layer deposition cycle. In each cycle, the thickness of the silicon nitride film formed may be about to about In various embodiments, about 100 to about 5000 cycles or about 1000 cycles may be performed until a desired thickness of the silicon nitride undercoat is formed. In various embodiments, the undercoat is deposited to at least about The growth rate per cycle on some parts (e.g., parts set to a temperature of about 100°C) can be about The growth rate per cycle on some parts (e.g., parts set to a temperature of about 650°C) can be about

[0156] Although not shown, after forming a sufficient thickness of the undercoat film, the substrate may be provided to a processing chamber for processing, including processing that may involve the introduction of a halogen-containing gas or species.

[0157] In some embodiments, operations 126-132 are performed at a constant chamber pressure. In various embodiments, operations 126-132 are performed using a halogen-free process. In various embodiments, operations 126-132 are performed using an ammonia-free process. In various embodiments, operations 126-132 are performed using a halogen-free and ammonia-free process. Because there is no halogen during the formation of the undercoat film, metal halides are not formed, and metal contamination in the wafer subsequently processed in the processing chamber is reduced and / or eliminated.

[0158] Also provided herein are methods and apparatus for forming SiON using a single wafer non-furnace deposition tool. Certain disclosed embodiments are capable of forming conformal SiON. Certain disclosed embodiments are also capable of forming a gradient SiON film, which may also be conformal. The disclosed embodiments may be implemented to form SiON in a variety of applications, including but not limited to forming SiON in high aspect ratio features, forming gradient SiON in very thin SiON layers, and forming tunnel layers in 3D-NAND memory applications. Certain disclosed embodiments allow for a wide adjustable range for controlling the gradient of oxidation and refractive index. Deposition and oxidation control may be performed in situ or in the same chamber or in the same tool. Certain disclosed embodiments relate to forming a first silicon-containing film, such as silicon nitride or silicon oxide, by ALD, followed by in-situ oxidation or in-situ nitridation to convert the first silicon-containing film into a second silicon-containing film, such as SiON. For example, in-situ oxidation may convert silicon nitride into SiON. In-situ nitridation may convert silicon oxide into SiON. The amount of in-situ oxidation or nitridation may be used to adjust the amount of oxygen and / or nitrogen in the deposited film.

[0159] The technology described herein relates to thermal atomic layer deposition (ALD). That is, in various embodiments, a reaction between an aminosilane precursor and a reactant is performed to form a silicon oxide or silicon nitride film, which can then be adjusted to form SiON. ALD is a technology that uses a continuous self-limiting reaction to deposit a thin layer of material. Generally, an ALD cycle includes the operation of delivering and adsorbing at least one reactant to a substrate surface, and then reacting the adsorbed reactant with one or more reactants to form a partial film layer. As another example, a silicon oxide deposition cycle may include the following operations: (i) delivering / adsorbing a silane precursor, (ii) purging a silane precursor from a chamber, (iii) delivering an oxygen-containing gas, and (iv) purging an oxygen-containing gas from a chamber.

[0160] Unlike chemical vapor deposition (CVD) techniques, the ALD process uses a surface-mediated deposition reaction to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface having a group of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, which is provided in a certain dosage to a chamber containing the substrate. Molecules of the first precursor are adsorbed onto the substrate surface, including chemically adsorbed species and / or physically adsorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound and derivatives of the compound. For example, the adsorption layer of a silicon-containing precursor may include a silicon-containing precursor and a derivative of the silicon-containing precursor. After the first precursor is dosed, the chamber is evacuated to remove most or all of the silicon-containing precursor remaining in the gas phase, so that most or only the adsorbed species remain. In some implementations, the chamber may not be completely evacuated. For example, the chamber may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant, such as an oxygen-containing reactant or a nitrogen-containing reactant, is introduced into the chamber so that some of these molecules react with the silicon-containing precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed silicon-containing precursor. The chamber can then be evacuated again to remove unbonded second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

[0161] In some embodiments, the ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dosing phase of the ALD cycle ends before the precursor contacts the substrate to saturate the surface evenly. Typically, at this time, the precursor flow is shut off or diverted, and only the sweep gas flows. By operating in this saturated state, the ALD process reduces cycle time and increases throughput. However, because precursor adsorption is not saturation-limited, the concentration of the adsorbed precursor may vary slightly across the substrate surface. An example of an ALD process operating in a subsaturated state is provided in U.S. Patent Application No. 14 / 061,587 (now U.S. Patent No. 9,355,839), filed on October 23, 2013, entitled "SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILMDEPOSITION," the entire contents of which are incorporated herein by reference.

[0162] In some implementations, the ALD method may include plasma activation. In some implementations, the ALD method may not include plasma activation. As described herein, the ALD method and apparatus described herein may be a conformal film deposition (CFD) method, which is generally described in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION" (now U.S. Patent No. 8,728,956), and described in U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled "SILICON NITRIDE FILMS AND METHODS", the entire contents of which are incorporated herein by reference.

[0163] Figure 1C A process flow diagram depicting operations that may be performed according to certain disclosed embodiments is shown. It should be understood that the selection of gases in operations 148 and 152 determines the type of materials and the graded levels or relative concentrations of oxygen and nitrogen, as well as the process conditions for the various operations described herein.

[0164] In operation 142, a substrate is provided to a processing chamber. In various embodiments, the processing chamber is a single wafer chamber. In some embodiments, the processing chamber is a station in a multi-station chamber. The process conditions described herein are applicable to a single wafer chamber.

[0165] The processing chamber can be set to a chamber pressure between about 5 mTorr and about 25 Torr or about 10 Torr and about 25 Torr. Such a chamber pressure can be used in all operations 142 to 156 as described herein. In some embodiments, the chamber pressure during different operations may be different. The chamber pressure may also depend on the chemistry selected for many of the operations described herein.

[0166] During operations 144 to 154, the substrate may be heated to a substrate temperature of about 25° C. to about 800° C., or about 500° C. to about 700° C., or at least about 650° C. It should be understood that substrate temperature as used herein refers to the temperature at which the pedestal holding the substrate is set, and in some embodiments, when the substrate is provided to the processing chamber pedestal, the substrate may be heated to a desired substrate temperature before processing the substrate. The substrate temperature may be the same in all operations 142 to 154 as described herein.

[0167] The substrate may be any suitable substrate. The substrate may be a silicon wafer, such as a 200-mm wafer, a 300-mm wafer, including a wafer having one or more material layers, such as dielectric, conductive, or semiconductor materials deposited thereon. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxide, metal nitride, metal carbide, and metal layers. In some embodiments, the substrate includes silicon oxide and silicon. In some embodiments, the substrate includes a portion of a fabricated 3D-NAND structure.

[0168] In some embodiments, the features may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or at least about 20:1, or at least about 50:1, or at least about 100:1, or at least about 150:1, or at least about 200:1 or more. The features may also have a size close to the opening, such as an opening diameter or line width between about 10nm and 500nm, such as between about 25nm and about 300nm. The disclosed method may be performed on a substrate with features having an opening less than about 150nm. A through hole, groove, or other recessed feature may be referred to as an unfilled feature or features. According to various embodiments, the feature profile may taper and / or include a protrusion at the feature opening. A concave profile is a profile that tapers from the bottom, closed end, or interior of the feature to the feature opening. The reentrant profile may result from asymmetric etch dynamics during patterning and / or protrusions resulting from non-conformal film step coverage in a previous film deposition, such as deposition of a diffusion barrier layer. In various examples, the width of the feature at its top opening may be less than the width of the feature bottom.

[0169] One or more features may have a high aspect ratio, which is defined as having an aspect ratio greater than about 100:1, or greater than about 150:1, or greater than about 180:1.

[0170] In some embodiments, the substrate can be partially fabricated for use in forming a memory device. In some embodiments, the exposed region of the substrate includes a silicon-containing surface, including but not limited to silicon and SiON.

[0171] In operation 144, a silicon-containing precursor may be introduced into the processing chamber. In various embodiments, the silicon-containing precursor is a silane. Non-limiting examples of usable silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In particular embodiments, the silicon-containing precursor includes a halosilane precursor. In particular embodiments, the silicon-containing precursor includes an aminosilane precursor. Additional examples of silicon-containing precursors may be included elsewhere herein, such as in the definitions and precursor sections.

[0172] The flow rate range of the silicon-containing precursor in operation 144 may be about 100 sccm to about 5000 sccm for a 4-station chamber, or about 100 sccm to about 4000 sccm for a 4-station chamber, or about 100 sccm to about 2000 sccm for a single wafer chamber. The exposure in operation 144 may be in the range of about 0.1 seconds to about 10 seconds. The chamber pressure during operation 144 may be about 5 Torr to about 25 Torr. In some embodiments, the silicon-containing precursor flows with a dilution gas. For a single wafer chamber, the dilution gas may flow at a flow rate of about 500 sccm to about 2000 sccm. In some embodiments, the dilution gas is an inert gas. In some embodiments, the dilution gas is nitrogen (N2). In some embodiments, the dilution gas flows together with the silicon-containing precursor. In some embodiments, the dilution gas flows together with the silicon-containing precursor and then turns before being transported to the processing chamber. In some embodiments, the silicon-containing precursor flows into the processing chamber together with the dilution gas.

[0173] In various embodiments, a plasma is not ignited in operation 144. In some embodiments, operation 144 is plasma-free. In some embodiments, the silicon-containing gas is introduced into the processing chamber in a plasma-free environment.

[0174] In various embodiments, a silicon-containing gas is introduced into the process chamber to form at least a partial adsorption layer of the silicon-containing gas on the exposed surface of the substrate. In some embodiments, introducing the silicon-containing gas into the process chamber is referred to as "dosing". In some embodiments, introducing the silicon-containing gas into the process chamber is "dosing" of an ALD cycle.

[0175] In one example, during dosing, dichlorosilane or hexachlorodisilane or silicon tetrachloride is introduced into a single wafer processing chamber at a chamber pressure of about 5 Torr to about 25 Torr or about 9.5 Torr using nitrogen having a dilution gas of about 500 sccm to about 2000 sccm at a flow rate of about 100 sccm to about 2000 sccm or about 1000 sccm for about 0.1 second to about 10 seconds or about 5 seconds.

[0176] In one example, during dosing, aminosilane (e.g., DIPAS or BTBAS) is introduced into a single wafer processing chamber at a chamber pressure of about 5 Torr to about 25 Torr or about 18 Torr with a flow rate of about 100 sccm to about 2000 sccm or about 900 sccm using nitrogen having about 500 sccm to about 2000 sccm as a diluent gas for about 0.1 second to about 10 seconds or about 2 seconds.

[0177] In operation 146, the treatment chamber may be optionally purged. Purge may be performed using any of the gases, flow rates, temperatures, pressures, and other process conditions described above with respect to operation 104b, without evacuating the chamber. Purge the chamber may include flowing a purge gas or purge gas, which may be a carrier gas for other operations or may be a different gas. In some embodiments, purge may involve evacuating the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, operation 146 may include one or more evacuation substages for evacuating the treatment chamber. Alternatively, it should be understood that operation 146 may be omitted in some embodiments. Operation 146 may have any suitable duration, such as between about 0 seconds and about 60 seconds, or about 0.1 seconds to about 10 seconds. In some embodiments, increasing the flow rate of one or more purge gases may reduce the duration of operation 146. For example, the purge gas flow rate may be adjusted according to many reactant thermodynamic properties and / or the geometric properties of the treatment chamber and / or the treatment chamber pipeline to modify the duration of operation 106. In a non-limiting example, the duration of the sweep phase can be adjusted by adjusting the sweep gas flow rate. This can reduce the deposition cycle time, thereby improving substrate throughput. After sweeping, the silicon-containing precursor remains adsorbed on the substrate surface.

[0178] The flow rate of the one or more purge gases may be about 1000 sccm to about 40000 sccm. The chamber pressure during the purge may be about 0.5 Torr to about 22 Torr. Lower pressures may be used to purge more efficiently.

[0179] In one example, during operation 146 , nitrogen gas is flowed at a flow rate of about 10,000 seem for 10 seconds at a chamber pressure of about 9.5 Torr.

[0180] In operation 148, a reactant substance is introduced to convert the silicon-containing precursor or react with the silicon-containing precursor to form a first silicon-containing film. For example, an oxygen-containing substance can be used to form a silicon oxide film. A nitrogen-containing substance can be used to form a silicon nitride film. The reactant substance can be a gas or a plasma or can be both. In some embodiments, an oxygen-containing gas or a nitrogen-containing gas is introduced into the processing chamber to form silicon oxide or silicon nitride, respectively. For example, an oxygen-containing gas can be introduced to react with a silicon-containing precursor adsorbed on the surface of the substrate, thereby converting the adsorbed silicon-containing precursor into silicon oxide. In another example, a nitrogen-containing gas can be introduced to react with a silicon-containing precursor adsorbed on the surface of the substrate to convert the adsorbed silicon-containing precursor into silicon nitride.

[0181] In some embodiments, operation 148 is performed as part of a thermal process. In some embodiments, operation 148 is performed as part of a plasma-free deposition process. In some embodiments, operation 148 also includes igniting a plasma. Plasma can be ignited in situ, such as in a chamber, so that when an oxygen-containing gas or a nitrogen-containing gas flows into the chamber, the gas is ignited to form an oxygen-containing plasma or a nitrogen-containing plasma, respectively. Plasma can be ignited remotely so that an oxygen-containing plasma substance or a nitrogen-containing plasma substance (rather than an oxygen-containing gas or a nitrogen-containing gas or together with an oxygen-containing gas or a nitrogen-containing gas) is directed into the processing chamber. When operation 148 involves forming silicon oxide, operation 152 may involve nitridation. When operation 148 involves forming silicon nitride, operation 152 may involve oxidation. In some embodiments, one or more operations of introducing an oxygen-containing gas or a nitrogen-containing gas can be used to adjust or control the relative amount of oxygen and nitrogen in the deposited film.

[0182] The following description relates to an embodiment that utilizes the conversion in operation 148 to form an oxide.

[0183] If an oxygen-containing gas or an oxygen-containing plasma substance (generated by an oxygen-containing gas) is introduced in operation 148, one or more of the following process conditions may be used. The oxygen-containing gas may be any suitable oxygen-containing gas, such as, but not limited to, oxygen (O2), carbon dioxide, carbon monoxide, hydrogen peroxide, other peroxides, and ozone. The oxygen-containing gas may be mixed with one or more inert gases or diluted with one or more inert gases. In some embodiments, the oxygen-containing gas is mixed with hydrogen or diluted with hydrogen. In some embodiments, the oxygen-containing gas is mixed with hydrogen and diluted with nitrogen. For a single wafer chamber, the flow rate of the oxygen-containing gas may be from about 100 sccm to about 5000 sccm. The flow rate of hydrogen or an inert gas may be from about 0 sccm to about 5000 sccm. The flow rate of the diluent gas or nitrogen may be from about 500 sccm to about 2000 sccm. Operation 148 may be performed for a duration of from about 1 second to about 30 seconds, or from about 5 seconds to about 15 seconds. After several deposition cycles, for example, about 25 deposition cycles, a longer conversion time of about 300 seconds to about 900 seconds, or about 300 seconds, or about 900 seconds may be utilized. In the mixture of oxygen and hydrogen, the ratio of oxygen to hydrogen may be about 1:10 to about 10:1. In some embodiments, hydrogen is not used. In some embodiments, the flow rate of hydrogen is 0 seem.

[0184] In some embodiments, hydrogen is ignited to form a hydrogen plasma. In some embodiments, a plasma containing oxygen and hydrogen may be used in operation 108. In some embodiments, and in some deposition cycles, operation 148 may be oxygen-free. In some embodiments and in some deposition cycles, operation 148 may involve only introducing a hydrogen plasma. In some embodiments, operation 146 uses a hydrogen plasma and is oxygen-free. The hydrogen plasma may be used to reduce the chlorine content or the fluorine content in the deposited film.

[0185] The process conditions used in operation 146 can be used to adjust film properties, such as changing the stress of the deposited film. In some embodiments, the operation may also involve subsequent exposure to nitrogen plasma. In some embodiments, the film may be annealed using an inert plasma after conversion to improve film quality. In one example, plasma is used for annealing. For example, an RF power of about 2000W to about 6000W may be used to ignite nitrogen of about 5000sccm to about 20000sccm (for a 4-station chamber) for a duration of about 0.1 seconds to about 30 seconds. Plasma may be generated in situ. In some embodiments, plasma may be generated remotely.

[0186] The plasma conditions for operation 148 vary depending on the chemistry used. In one example, the plasma can be ignited using a plasma power of about 2000 W to about 6000 W with a frequency of 13.6 MHz. In one example, the plasma containing oxygen and hydrogen is generated in situ using a mixture of oxygen and hydrogen at a flow rate of about 4500 sccm, and the substrate is exposed to the plasma containing oxygen and hydrogen for a duration of about 15 seconds at a chamber pressure of about 18 Torr.

[0187] The following description relates to an embodiment that utilizes the conversion in operation 148 to form a nitride.

[0188] If a nitrogen-containing gas or nitrogen-containing plasma material (generated by a nitrogen-containing gas) is introduced in operation 148, one or more of the following process conditions may be used. The nitrogen-containing gas may be any suitable nitrogen-containing gas, such as, but not limited to, nitrogen (N2), nitrous oxide, nitric oxide, deuterated ammonia (ND3), and ammonia. The nitrogen-containing gas may be mixed with one or more inert gases or diluted with one or more inert gases. In some embodiments, the nitrogen-containing gas is mixed with hydrogen or diluted with hydrogen. For a single wafer chamber, the flow rate of the nitrogen-containing gas may be from about 2000sccm to about 40000sccm. The flow rate of hydrogen or an inert gas may be from about 0sccm to about 5000sccm. The flow rate of the diluent gas or additional nitrogen may be from about 500sccm to about 2000sccm. Operation 148 may be performed for a duration of from about 1 second to about 30 seconds. In a mixture of ammonia and hydrogen, the amount of hydrogen in the mixture is from about 0% to about 90% of the flow rate.

[0189] In some embodiments, a nitrogen-containing plasma is used. The plasma can be generated by flowing about 5,000 to about 40,000 sccm of nitrogen, about 50 to about 250 sccm of ammonia, and about 0 to about 100 sccm of hydrogen in a chamber having a pressure of about 1 Torr to about 10 Torr for about 1 second to about 30 seconds.

[0190] In some embodiments, a thermal conversion may be performed followed by a plasma conversion. For example, operation 148 may involve flowing a nitrogen-containing gas without plasma, then flowing the nitrogen-containing gas and igniting a plasma. In some embodiments where a thermal conversion followed by a plasma conversion is performed, an optional purge operation may be performed after the thermal conversion and before the plasma conversion. The purge may be performed using any of the techniques, gases, and process conditions described above with respect to operation 146.

[0191] For plasma conversion, the plasma conditions for operation 148 vary depending on the chemistry used. In one example, the plasma can be ignited using a plasma power of about 1000 W to about 6000 W with a frequency of 13.6 MHz. In one example, about 4500 sccm of ammonia is introduced at a chamber pressure of about 9.5 Torr for about 15 seconds to convert the silicon-containing precursor into silicon nitride.

[0192] refer to Figure 1C The process chamber may optionally be purged again in operation 150. The purge may be performed using any of the techniques, gases, and process conditions described above with respect to operation 146.

[0193] Operations 144-150 may optionally be repeated cyclically. Operations 144-150 may constitute one ALD cycle. In some embodiments, about 1 to about 1000 or about 1 to about 100 cycles of ALD are performed.

[0194] In operation 152, an in-situ nitridation or oxidation operation is performed to convert the first silicon-containing film into a second silicon-containing film, which may be a conversion film, by nitriding or oxidizing the film deposited by operations 144 and 148. In an example of in-situ oxidation, a mixture of hydrogen, oxygen, and an inert gas (e.g., nitrogen and / or argon) may be used. The higher partial pressure of P O2 With P H2 May cause oxidation to occur more rapidly. In some embodiments, a higher partial pressure of P O2 With P H2It can be caused by reducing the inert gas flow rate and increasing the pressure. In a specific non-limiting example, in an experiment of performing oxidation at a pressure of 22 Torr with a hydrogen flow rate of about 4500 sccm, an oxygen flow rate of about 4500 sccm, and an inert gas flow rate of about 4200 sccm, when the inert gas flow rate increases, the oxidation efficiency decreases. When the pressure decreases, the oxidation efficiency decreases.

[0195] Operation 152 may be performed in situ. In some embodiments, operation 152 is performed in the same chamber as any one or more of operations 144 and 148. The choice of nitridation and oxidation depends on whether the deposited film is modified to contain more nitrogen atoms or more oxygen atoms. For example, in some embodiments, operations 144 and 148 may be performed to form a silicon nitride layer. In order to oxidize silicon nitride to form SiON, in-situ oxidation may be performed. In another example, in some embodiments, operations 144 and 148 may be performed to form a silicon oxide layer. In order to oxidize silicon oxide to form SiON, in-situ nitridation may be performed. In some embodiments, after oxidation or nitridation or other ALD cycles, nitridation and / or oxidation may be further performed to modify the composition of the deposited film. In some embodiments, operation 152 is performed to form a gradient layer having a gradient oxygen content, a gradient nitrogen content, or both. In some embodiments, the gradient layer includes a gradient oxygen content and a gradient nitrogen content, whereby a region having an increased amount of oxygen also has an increased amount of nitrogen, or a region having a reduced amount of oxygen also has a reduced amount of nitrogen.

[0196] In-situ oxidation can be performed by introducing an oxygen-containing reactant (e.g., an oxygen-containing gas or plasma material). The oxygen-containing plasma material can be generated by igniting an oxygen-containing gas. An exemplary oxygen-containing reactant is oxygen. Another exemplary oxygen-containing reactant is carbon dioxide. In some embodiments, any one or more of the chemical substances and / or process conditions used for exposure to oxygen-containing gas or plasma to form silicon oxide in operation 148 as described above can be performed in operation 152 as an in-situ oxidation operation. For example, in some embodiments, if an oxygen-containing gas or an oxygen-containing plasma material (generated by an oxygen-containing gas) is introduced in operation 152, one or more of the following process conditions can be used. The oxygen-containing gas can be any suitable oxygen-containing gas, such as, but not limited to, oxygen (O2), carbon dioxide, carbon monoxide, hydrogen peroxide, other peroxides, and ozone. The oxygen-containing gas can be mixed with one or more inert gases or diluted with one or more inert gases. In some embodiments, the oxygen-containing gas is mixed with hydrogen or diluted with hydrogen. In some embodiments, the oxygen-containing gas is mixed with hydrogen and diluted with nitrogen. For a single wafer chamber, the flow rate of the oxygen-containing gas may be about 100 sccm to about 5000 sccm. The flow rate of hydrogen or an inert gas may be about 0 sccm to about 5000 sccm. The flow rate of the diluent gas or nitrogen may be about 500 sccm to about 2000 sccm. Operation 152 may be performed for a duration of about 1 second to about 900 seconds. In a mixture of oxygen and hydrogen, the ratio of oxygen to hydrogen may be about 1:2 to about 1:1.

[0197] In some embodiments, hydrogen is ignited to form a hydrogen plasma. In some embodiments, a plasma containing oxygen and hydrogen may be used in operation 148. In some embodiments, and in some deposition cycles, operation 148 may be oxygen-free. In some embodiments and in some deposition cycles, operation 148 may involve only introducing a hydrogen plasma. In some embodiments, operation 106 uses a hydrogen plasma and is oxygen-free. The hydrogen plasma may be used to reduce the chlorine content or the fluorine content in the deposited film.

[0198] The process conditions used in operation 152 can be used to adjust film properties, such as changing the stress of the deposited film. In some embodiments, this operation can also involve subsequent exposure to a nitrogen plasma. In some embodiments, the film can be annealed using an inert plasma after conversion to improve film quality.

[0199] The plasma conditions for operation 152 vary depending on the chemistry used. In one example, the plasma can be ignited using a plasma power of about 1000 W to about 6000 W with a frequency of 13.56 MHz. In one example, the plasma containing oxygen and hydrogen is generated in situ using a mixture of oxygen and hydrogen at a flow rate of about 4500 sccm, and the substrate is exposed to the plasma containing oxygen and hydrogen for a duration of about 15 seconds at a chamber pressure of about 18 Torr.

[0200] In-situ nitridation can be performed by introducing a nitrogen-containing reactant (e.g., a nitrogen-containing gas or plasma substance). The nitrogen-containing plasma substance can be generated by igniting a nitrogen-containing gas. An exemplary nitrogen-containing reactant is ammonia. Another exemplary nitrogen-containing reactant is nitrogen. In some embodiments, any one or more of the chemical substances and / or process conditions used for exposure to a nitrogen-containing gas or plasma to form silicon nitride in operation 148 as described above can be performed in operation 152 as an in-situ nitridation operation. For example, in some embodiments, if a nitrogen-containing gas or a nitrogen-containing plasma substance (generated by a nitrogen-containing gas) is introduced in operation 148, one or more of the following process conditions can be used. The nitrogen-containing gas can be any suitable nitrogen-containing gas, such as, but not limited to, nitrogen (N2) and ammonia. The nitrogen-containing gas can be mixed with one or more inert gases or diluted with one or more inert gases. In some embodiments, the nitrogen-containing gas is mixed with hydrogen or diluted with hydrogen. For a single wafer chamber, the flow rate of the nitrogen-containing gas can be about 2000 sccm to about 40000 sccm. The flow rate of hydrogen or inert gas may be from about 0 sccm to about 5000 sccm. The flow rate of diluent gas or additional nitrogen may be from about 500 sccm to about 2000 sccm. Operation 148 may be performed for a duration of about 1 second to about 30 seconds. In a mixture of ammonia and hydrogen, the amount of hydrogen in the mixture may be from about 0% to about 90% flow or partial pressure.

[0201] In some embodiments, a nitrogen-containing plasma is used. The plasma can be generated by flowing about 5000 sccm to about 10000 sccm of nitrogen, about 50 sccm to about 250 sccm of ammonia, and about 0 sccm to about 100 sccm of hydrogen in a chamber at a pressure of about 1 Torr to about 10 Torr for about 1 second to about 30 seconds.

[0202] In some embodiments, a thermal conversion may be performed followed by a plasma conversion. For example, operation 148 may involve flowing a nitrogen-containing gas without plasma, then flowing the nitrogen-containing gas and igniting a plasma. In some embodiments where a thermal conversion is performed followed by a plasma conversion, an optional purge operation may be performed after the thermal conversion and before the plasma conversion. The purge may be performed using any of the techniques, gases, and process conditions described above with respect to operation 146.

[0203] The plasma conditions for operation 152 vary depending on the chemistry used. In one example, the plasma can be ignited using a plasma power of about 1000 W to about 6000 W with a frequency of 13.56 MHz. In one example, about 4500 sccm of ammonia is introduced at a chamber pressure of about 9.5 Torr for about 15 seconds to convert the silicon-containing precursor into silicon nitride.

[0204] Operation 152 adjusts the nitrogen and / or oxygen content of the film as well as the refractive index and other properties. In some embodiments, operation 152 helps convert the deposited film into a SiON film. In some embodiments, after operation 152, a graded film, such as a graded SiON film, is formed.

[0205] In operation 154, the processing chamber may optionally be purged. The purge may be performed using any of the chemistries and / or process conditions described above with respect to operation 146. In some embodiments, if the desired film thickness has not been achieved, operations 144, 148, and 152 may be repeated cyclically. Performing each of operations 144, 148, and 152 once may constitute one cycle. The total number of cycles may be used to control the thickness of the film.

[0206] In some embodiments, performing operation 144, operation 148 of using an oxygen-containing gas or plasma, and operation 152 of performing in-situ nitridation involve forming a graded film in which a region of the film closer to the exposed surface of the deposited film may have a higher refractive index and / or be nitrogen-rich, while another region of the film may have a lower refractive index and / or be oxygen-rich. In-situ nitridation time and pressure may be used to adjust the amount of gradation and refractive index in different regions of the film. In contrast, in a non-graded film, more ALD cycles (e.g., operations 144 and 148) may result in a higher refractive index, and a reduction in in-situ nitridation time and pressure may be used to reduce the refractive index. The non-graded film may have a refractive index of about 1.45 to about 2.15.

[0207] In some embodiments, performing operation 144, operation 148 using a nitrogen-containing gas or plasma, and operation 152 performing in-situ oxidation involve forming a graded film in which a region of the film closer to the exposed surface of the deposited film may have a higher refractive index and / or be nitrogen-rich, while another region of the film may have a lower refractive index and / or be oxygen-rich. The in-situ oxidation time and pressure may be used to adjust the amount of gradation and refractive index in different regions of the film. Conversely, in a non-graded film, more ALD cycles (e.g., operations 144 and 148) may result in a higher refractive index, and a reduction in the in-situ oxidation time and pressure may be used to reduce the refractive index. The non-graded film may have a refractive index of about 1.45 to about 2.15.

[0208] Nitriding or oxidation may be performed to a specific depth of the film thickness deposited by one or more cycles of operations 144 and 148 . Figure 1D Three non-limiting examples of depositing silicon nitride by ALD and using in-situ oxidation to form SiON are shown. Although the examples relate to ALD cycles and in-situ oxidation for forming silicon nitride, it should be understood that these examples can also be used to form silicon oxide with in-situ nitridation and other embodiments described herein.

[0209] In the first example including graphs 160, 161 and 162, each bar 190 represents one ALD cycle for depositing silicon nitride. In 160, one ALD cycle is performed. In 161, oxidation is performed to a penetration depth d to form an oxidized silicon nitride material 199. Deposition and oxidation cycles are performed to form a fully oxidized film 162 having an oxidized silicon nitride material 199.

[0210] In a second example comprising graphs 170, 171 and 172, each bar also represents one ALD cycle for depositing silicon nitride. In 170, one ALD cycle is performed. In 171, the example shows that after 4 ALD cycles, oxidation is performed. The oxidation is performed only to a certain penetration depth; here, it is shown penetrating into both layers deposited by ALD to form silicon oxide nitride material 199. In 172, multiple cycles of deposition and oxidation are performed such that for every 4 ALD cycles, oxidation is performed through both deposited films; this forms a nanolaminate within the material, which can be used to control the refractive index.

[0211] In a third example including graphs 180 and 181, each bar also represents one ALD cycle for depositing silicon nitride. In 180, one ALD cycle is performed. In 181, after multiple ALD cycles are performed, oxidation is performed. Oxidation is performed only to a certain penetration depth; here, it is shown that although 8 ALD cycles were performed, only the last two layers of material deposited by the ALD cycles were penetrated by oxidation. This can be performed to form a graded SiON material; here, the top region has a higher oxygen concentration than the bottom region. Oxidation time and process conditions can be used to adjust the oxygen and nitrogen content of the film.

[0212] The level of gradation of the graded film may vary.In some areas of the deposited material, the SiON film may have from about 0.1 atomic % to about 67 atomic % oxygen or from about 57 atomic % to about 0.1 atomic % nitrogen.

[0213] The film deposited by certain disclosed embodiments can be conformal. The film deposited by ALD is generally conformal. The conformality of the film can be measured by step coverage. Step coverage can be calculated by comparing the average thickness of the deposited film on the bottom, sidewall or top of the groove with the average thickness of the deposited film on the bottom, sidewall or top of the feature or groove. The "feature" of the substrate can be a through hole or a contact hole, which can be characterized as one or more of a narrow and / or concave opening, a constriction in a feature, and a high aspect ratio. The terms "groove" and "feature" are used interchangeably in the present invention and will be understood to include any hole, through hole or recessed area of ​​the substrate.

[0214] An example of step coverage can be calculated by dividing the average thickness of the deposited film on the sidewalls by the average thickness of the deposited film at the top of the feature and multiplying it by 100 to get a percentage. Although ALD can deposit highly conformal films, depositing films into high aspect ratio features becomes challenging. The step coverage and uniformity of film features along the sidewalls depends on many factors, including the delivery of deposition precursors, reactant ions and / or radicals (such as those generated by igniting reactant gases with plasma), and byproducts. As trench dimensions decrease, delivery in the trench becomes increasingly difficult, resulting in the formation of seams and / or voids in high aspect ratio trenches.

[0215] Films deposited using certain disclosed embodiments may have a step coverage of at least about 90% or about 98% to about 102%.

[0216] Certain disclosed embodiments may also be applicable to a variety of applications, including but not limited to forming SiON tunnel layers in 3D-NAND structures. Certain disclosed embodiments may also be applicable to forming SiON films in high aspect ratio features, such as features having an aspect ratio of at least 100:1 or more.

[0217] Certain disclosed embodiments may also be used in conjunction with a deposition-etch-deposition process. For example, to fill certain features (e.g., high aspect ratio features or concave features or features with sloped sidewalls or sidewalls with topography), it may be advantageous to partially deposit a film, then preferentially etch the film at or near the feature opening, and then deposit more film into the feature. When integrated with certain disclosed embodiments, etching may be performed after operation 148 and before operation 152, or may be performed after operation 152 and between cycles of performing operations 144, 148, and 152, or in other variations. In one example, etching may be performed every 5 cycles of operations 144 and 148, for several cycles, and then operation 152 is performed. The time to perform etching may be determined by when the feature opening is closed or expected to be closed or nearly closed. Etching may be performed using a variety of chemicals, such as, but not limited to, fluorine-containing etchants, such as nitrogen trifluoride.

[0218] Figure 2 It is shown that according to the above Figure 1A An example timing diagram of the method described herein illustrates various stages that may be used according to an example method of performing certain disclosed embodiments. Figure 2 Certain phases and certain relative amounts are shown in the drawings, but it should be understood that other changes can be made according to certain disclosed embodiments. Figure 2 Six process conditions are shown, but it should be understood that fewer or more process conditions may be switched during each stage according to certain disclosed embodiments, and although specific gases (Ar, N2, and NH3) are listed, other suitable gases as described herein may also be used.

[0219] Example 200 includes two deposition cycles—deposition cycle 200A and deposition cycle 220B. It will be appreciated that more or less than two deposition cycles may be performed, and that multiple sub-cycles may be performed within a deposition cycle. For example, stages 204A, 206A, 208A, and 210A may constitute sub-cycles that may be repeated for multiple cycles within a deposition cycle 220A or 220B. However, the repetition of sub-cycles is not depicted in FIG. Figure 2 In this particular example.

[0220] Deposition cycle 220A includes silicon-containing precursor exposure phase 204A, sweep phase 206A, thermal conversion phase 208A, sweep phase 210A, plasma exposure phase 212A, and sweep phase 214A. Silicon-containing precursor exposure phase 204A may correspond to Figure 1A During the silicon-containing precursor exposure phase 204A, the argon flow is on and constant and can be used as an inert gas, a diluent gas, or a carrier gas; the silicon-containing precursor flow is on and constant; the nitrogen flow is on and is lower and constant than in other phases; the ammonia flow is off; the plasma is off; and the pressure is higher than in some other phases. The sweep phase 206A may correspond to Figure 1A Operation 106 of . In sweep phase 206A, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow is turned off; the nitrogen flow continues to flow, and its flow rate can be slightly increased to a medium flow rate (compared to the other phases); the ammonia flow continues to be turned off; the plasma continues to be turned off; and the pressure can be kept constant. The thermal conversion phase 208A can correspond to Figure 1A Operation 108 of . In thermal conversion phase 208A, the flow of argon continues to flow, as it may be used as a carrier gas or an inert gas or a diluent gas; the flow of the silicon-containing precursor remains off; the flow of nitrogen may continue and may be reduced relative to sweep phase 206A; the flow of ammonia may be turned on; the plasma remains off; and the pressure may remain constant. Sweep phase 210A may correspond to Figure 1AOperation 110 of . During sweep phase 210A, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow remains off; the nitrogen flow continues and its flow rate can be slightly increased to a medium flow rate (compared to thermal conversion phase 208A); the ammonia flow is turned off; the plasma continues to be off; and the pressure can be held constant. Plasma exposure phase 212A can correspond to Figure 1A Operation 112 of FIG. 214A. During plasma exposure phase 212A, the flow of argon continues to flow, as it can be used as a carrier gas or an inert gas or a diluent gas; the flow of the silicon-containing precursor remains off; the flow of nitrogen gas can be increased, which can be used to promote the generation of a nitrogen-containing plasma (e.g., N* radicals); the flow of ammonia gas can be turned on, but at a lower flow rate relative to thermal conversion phase 208A; the plasma is turned on; and the chamber pressure is lower relative to the other phases. Sweep phase 214A can correspond to Figure 1A Operation 114 of . During sweep phase 214A, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow remains off; the nitrogen gas continues to flow, and its flow rate can be slightly reduced relative to plasma exposure phase 212A; the ammonia flow is turned off; the plasma is turned off; and the pressure is increased to a pressure that can be the same as during phases other than plasma exposure phase 212A.

[0221] It can be determined that the film thickness of the deposited silicon nitride is not thick enough, and the Figure 1A The operation 116 repeats the cycle, such as Figure 1A As shown in the example of a deposition cycle 220B of FIG. 1 , it includes a silicon-containing precursor exposure phase 204B, a sweep phase 206B, a thermal conversion phase 208B, a sweep phase 210B, a plasma exposure phase 212B, and a sweep phase 214B.

[0222] The silicon-containing precursor exposure phase 204B may correspond to Figure 1A Repeating operation 104. During the silicon-containing precursor exposure phase 204B, the argon flow is turned on and constant and can be used as an inert gas, a diluent gas, or a carrier gas; the silicon-containing precursor flow is turned on and constant; the nitrogen flow is turned on and is lower and constant than in other phases; the ammonia flow is turned off; the plasma is turned off; and the pressure is higher than in some other phases. The sweep phase 206B may correspond to Figure 1A Repeating operation 106. In sweep phase 206B, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow is turned off; the nitrogen flow continues to flow, and its flow rate can be slightly increased to a medium flow rate (compared to the other phases); the ammonia flow continues to be turned off; the plasma continues to be turned off; and the pressure can be kept constant. The thermal conversion phase 208B can correspond to Figure 1ARepeat operation 108. In thermal conversion phase 208B, the argon flow continues to flow, as it can be used as a carrier gas or an inert gas or a diluent gas; the silicon-containing precursor flow remains off; the nitrogen flow can continue to flow and can be reduced relative to the sweep phase 206B; the ammonia flow can be turned on; the plasma remains off; and the pressure can be held constant. Sweep phase 210B may correspond to Figure 1A Repeating operation 110. During sweep phase 210B, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow remains off; the nitrogen flow continues and its flow rate can be slightly increased to a medium flow rate (compared to thermal conversion phase 208B); the ammonia flow is turned off; the plasma continues to be turned off; and the pressure can be kept constant. Plasma exposure phase 212B may correspond to Figure 1A Repeating operation 112. During the plasma exposure phase 212B, the argon flow continues to flow, as it can be used as a carrier gas or an inert gas or a diluent gas; the silicon-containing precursor flow remains off; the nitrogen flow can be increased, which can be used to promote the generation of nitrogen-containing plasma (e.g., N* radicals); the ammonia flow can be turned on, but at a lower flow rate relative to the thermal conversion phase 208B; the plasma is turned on; and the chamber pressure is lower than the other phases. The sweep phase 214B may correspond to Figure 1A Repeating operation 114. During sweep phase 214B, the argon flow continues to flow because it can be used as a sweep gas; the silicon-containing precursor flow remains off; the nitrogen gas continues to flow, and its flow rate can be slightly reduced relative to the plasma exposure phase 212B; the ammonia flow is turned off; the plasma is turned off; and the pressure is increased to a pressure that can be the same as during the phases other than the plasma exposure phase 212B.

[0223] In some embodiments, certain disclosed embodiments may be combined. Figure 1B Use a primer in the chamber, which can Figure 1A or Figure 1C In addition, in some embodiments, Figure 1A and 1C The operations in operation 152 may also be combined. For example, the in-situ nitridation or oxidation in operation 152 may be performed in combination with exposing the substrate to a nitrogen-containing plasma in operation 112. Device

[0224] Figure 3 A schematic diagram of an embodiment of an atomic layer deposition (ALD) processing station 300 is depicted, and the ALD processing station 300 has a processing chamber body 302. In various embodiments, in Figure 4 A single processing station 300 is implemented in the tool shown. In some embodiments, multiple ALD processing stations 300 may be included in a low pressure processing tool environment. For example, Figure 3An embodiment of a multi-station processing tool 300 is depicted. In some embodiments, one or more hardware parameters of the ALD processing station 300 are programmably adjustable by one or more computer controllers 350, including those parameters discussed in detail below.

[0225] The ALD processing station 300 is in fluid communication with a reactant delivery system 301a to deliver process gases to the showerhead 306. The reactant delivery system 301a includes a mixing vessel 304 for mixing and / or regulating process gases, such as silicon-containing precursor gases or nitrogen-containing gases, for delivery to the showerhead 306. One or more mixing vessel inlet valves 320 can control the introduction of process gases to the mixing vessel 304. One or more valves 305 can control the introduction of process gases to the showerhead 306.

[0226] As an example, Figure 3 Embodiments include a vaporization point 303 for vaporizing liquid reactants to be supplied to a mixing container 304. In some embodiments, the vaporization point 303 may be a heated vaporizer. The saturated reactant vapor produced from such a vaporizer may condense in the downstream transport pipeline. Incompatible gases may be exposed to condensed reactants and may produce small particles. These small particles may block the pipeline, hinder valve operation, contaminate substrates, etc. Some ways to deal with these problems involve cleaning and / or emptying the transport pipeline to remove residual reactants. However, cleaning the transport pipeline may increase the processing station cycle time and reduce the processing station productivity. Therefore, in some embodiments, the transport pipeline downstream of the vaporization point 303 may be heated. In some examples, the mixing container (not shown) may also be heated. In a non-limiting example, the pipeline downstream of the vaporization point 303 has a temperature increase curve extending from about 40°C to about 55°C at the mixing container or from about 60°C to about 65°C at the mixing container.

[0227] In some embodiments, a liquid precursor or liquid reactant can be vaporized at a liquid injector. For example, a liquid injector can inject a pulse of a liquid reactant into a carrier gas stream upstream of a mixing vessel. In one embodiment, a liquid injector can vaporize a reactant by flashing a liquid from a higher pressure to a lower pressure. In another example, a liquid injector can atomize a liquid into dispersed micro-droplets, which are then vaporized in a heated delivery line. Smaller droplets can vaporize faster than larger droplets and reduce the delay between liquid injection and complete vaporization. Faster vaporization can reduce the length of the pipeline downstream of the vaporization point 303. In one case, a liquid injector can be mounted directly to a mixing vessel. In another case, a liquid injector can be mounted directly to a spray head 306.

[0228] In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 303 may be provided to control the mass flow rate of the liquid used for vaporization and delivery to the ALD processing station 300. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-differential (PID) controller electrically connected to the MFM. However, it may take one second or more to stabilize the liquid flow using feedback control. This may extend the time for dosing the liquid reactants. Therefore, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by deactivating the induction tube and PID controller of the LFC.

[0229] The showerhead 306 distributes process gases toward the substrate 312. Figure 3 In the embodiment shown, substrate 312 is located below showerhead 306 and is shown disposed on pedestal 308. Showerhead 306 may have any suitable shape and may have any suitable number and arrangement of ports to distribute process gases to substrate 312.

[0230] In some embodiments, the pedestal 308 may be raised or lowered to expose the substrate 312 to the volume between the substrate 312 and the showerhead 306. It should be appreciated that in some embodiments, the pedestal height may be programmatically adjusted by a suitable computer controller 350.

[0231] In another case, adjusting the height of the pedestal 308 can allow the plasma density to be varied during plasma activation in a process in an embodiment of igniting a plasma. At the end of a process phase, the pedestal 308 can be lowered to allow the substrate 312 to be removed from the pedestal 308 during another substrate transfer phase.

[0232] In some embodiments, the susceptor 308 can be temperature controlled via a heater 310. In some embodiments, the susceptor 308 can be heated to a temperature of about 25° C. to about 800° C., or about 200° C. to about 700° C. during silicon nitride film deposition as described in the disclosed embodiments. In some embodiments, the susceptor is set at a temperature of about 45° C. to about 800° C., or about 500° C. to about 700° C. In some embodiments, the same susceptor 308 is used for multiple operations according to certain disclosed embodiments.

[0233] Additionally, in some embodiments, pressure control of the ALD processing station 300 may be provided by a butterfly valve 318. Figure 3In the embodiment shown, butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of ALD process station 300 can also be adjusted by changing the flow rate of one or more gases introduced into ALD process station 300.

[0234] In some embodiments, the position of the showerhead 306 can be adjusted relative to the pedestal 308 to change the volume between the pedestal 312 and the showerhead 306. In addition, it should be understood that the vertical position of the pedestal 308 and / or the showerhead 306 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 308 can include a rotation axis for rotating the orientation of the substrate 312. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more appropriate computer controllers 350.

[0235] In some embodiments where a plasma may be used as discussed above, the showerhead 306 and the pedestal 308 are in electrical communication with a radio frequency (RF) power source 314 and a matching network 316 for supplying energy to the plasma. For example, the plasma may be used to ignite a nitrogen-containing plasma in a hybrid ALD. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse time. For example, the RF power source 314 and the matching network 316 may be operated at any suitable power to form a plasma having a desired composition of free radical species. Examples of suitable powers for a single station chamber are about 150W to 10,000W or about 500W to about 6,000W. For a 3-station chamber, the plasma power may include four generators, each supplying up to about 10,000W, for a total of about 30,000W.

[0236] In some embodiments, the substrate may be exposed to a nitrogen-containing gas while igniting a plasma during the plasma exposure phase. The plasma may be generated remotely (e.g., in a remote plasma generator) or directly in a chamber containing the substrate (i.e., in situ). The RF power supply 314 may provide RF power of any suitable frequency. In some embodiments, the RF power supply 314 may be configured to control high-frequency and low-frequency RF power sources independently of each other. Examples of low-frequency RF frequencies may include, but are not limited to, frequencies between 0kHz and 500kHz. Exemplary high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8MHz and 3.45GHz, or greater than about 13.56MHz, or greater than about 27MHz, or greater than about 30MHz, or greater than about 60MHz. It should be understood that any suitable parameter may be adjusted discretely or continuously to provide plasma energy for surface reactions.

[0237] In some embodiments, the plasma can be monitored in situ by one or more plasma monitors. In one case, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another case, the plasma density and / or the concentration of the process gas can be measured by one or more optical emission spectrometer sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on the measurement results from such in-situ plasma monitors. For example, an OES sensor can be used in a feedback loop to provide programmatic control of the plasma power. It should be understood that in some embodiments, other monitors can be used to monitor plasma and other processing characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0238] In some embodiments, instructions for the controller 350 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process stage may be included in a corresponding recipe stage of a process recipe. In some cases, the process recipe stages may be configured sequentially so that all instructions for a process stage are executed synchronously with the process stage. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe stage. For example, a first recipe stage may include instructions for setting a flow rate of a silicon-containing precursor gas, instructions for setting a flow rate of a carrier gas (e.g., argon), and time delay instructions for the first recipe stage. A second recipe stage may include instructions for adjusting or stopping the flow rate of an inert and / or reactant gas, instructions for optionally heating, instructions for setting a flow rate of a carrier gas (e.g., argon), and time delay instructions for the second recipe stage. A subsequent third recipe stage may include instructions for adjusting or stopping the flow rate of an inert and / or reactant gas, instructions for adjusting the flow rate of a nitrogen-containing gas, and time delay instructions for the third recipe stage. The fourth recipe stage may include instructions for adjusting or stopping the flow rates of the inert and / or reactant gases, instructions for adjusting the flow rates of the carrier gas or the purge gas, and time delay instructions for the fourth recipe stage. A subsequent fifth recipe stage may include instructions for setting the flow rate of the nitrogen-containing gas, instructions for igniting the plasma, and instructions for adjusting the flow rates of the carrier gas or the purge gas, and time delay instructions for the fifth recipe stage. The sixth recipe stage may include instructions for adjusting or stopping the flow rates of the inert and / or reactant gases, instructions for modulating the flow rates of the carrier gas or the purge gas, and time delay instructions for the sixth recipe stage.

[0239] In another example, a first recipe stage may include instructions for setting the flow rate of aminosilane gas, instructions for setting the flow rate of carrier gas (e.g., argon), and time delay instructions for the first recipe stage. A second recipe stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gas, instructions for setting the flow rate of carrier gas (e.g., argon), and time delay instructions for the second recipe stage. A third subsequent recipe stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gas, and instructions for adjusting the flow rate of oxygen-containing gas, and time delay instructions for the third recipe stage. A fourth recipe stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gas, instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fourth recipe stage. A fifth subsequent recipe stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gas, instructions for heating or igniting plasma, and instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fifth recipe stage.

[0240] In another example, a first recipe stage may include instructions for setting a flow rate of a silicon-containing gas, instructions for setting a flow rate of a carrier gas (e.g., argon), and time delay instructions for the first recipe stage. A second recipe stage may include instructions for adjusting or stopping the flow rates of an inert and / or reactant gas, instructions for setting the flow rate of a carrier gas (e.g., argon), and time delay instructions for the second recipe stage. A third subsequent recipe stage may include instructions for adjusting or stopping the flow rates of an inert and / or reactant gas, and instructions for adjusting the flow rate of an oxygen-containing or nitrogen-containing gas, and time delay instructions for the third recipe stage. A fourth recipe stage may include instructions for adjusting or stopping the flow rates of an inert and / or reactant gas, instructions for adjusting the flow rate of a carrier gas or a purge gas, and time delay instructions for the fourth recipe stage. A fifth subsequent recipe stage may include instructions for setting a flow rate of a nitriding or oxidizing gas, instructions for optionally heating or igniting the plasma, and instructions for adjusting the flow rate of a carrier gas or a purge gas, and time delay instructions for the fifth recipe stage.

[0241] It should be understood that these recipe stages may be further segmented and / or repeated in any suitable manner within the scope of the present disclosure. In some embodiments, the controller 350 may include the following Figure 4 The system controller 450 and Figure 3 Any features described by the system controller 350.

[0242] The processing station may be included in e.g. Figure 4 In a single station chamber or single chamber tool as shown in . Figure 4An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 400 includes a processing chamber 414 having a processing station 490 that can process a wafer. Processing chamber 414 is configured to deposit silicon oxide, deposit silicon nitride, anneal a substrate using thermal annealing or plasma annealing, and the like.

[0243] The tool 400 also includes a wafer transfer unit configured to transfer wafers within the tool 400. Other features of the tool 400 will be discussed in more detail below, and various features related to certain of the described techniques are discussed herein. In the depicted figure, the wafer transfer unit includes a first robot unit 426 in a first wafer transfer module and a second robot unit 406 in a second wafer transfer module, which can be considered as an equipment front end module (EFEM) configured to receive a container of wafers, such as a front opening unified module (FOUP) 408. The first robot unit 426 is configured to transfer wafers between a processing chamber 414 and the second robot unit via a module 404, which can hold multiple wafers, such as shown in the module 402 with a substrate 412. The second robot unit 406 is configured to transfer wafers between a FOUP and a module 404, or from a module 402 to a FOUP. After the wafers are prepared in the module 404, the wafer transfer unit can transfer the wafers to the first processing chamber 414 for in-situ deposition and optional annealing.

[0244] Similar to the above, the first wafer transfer module can be a vacuum transfer module (VTM). An air lock or module 404, also known as a load lock, is shown and can be optimized individually to perform various manufacturing processes. Tool 400 also includes a FOUP 408 configured to reduce the pressure of tool 400 to a vacuum or a low pressure, such as between about 1 mTorr and about 10 Torr, and maintain tool 400 at this pressure. This includes maintaining the processing chamber 414 and the first wafer transfer module under vacuum or low pressure. The second wafer transfer module can be at a different pressure, such as atmospheric pressure. Since the wafers are transferred throughout the tool 400, the wafers are maintained under vacuum or low pressure.

[0245] In a further example, the substrate is placed in one of the FOUP 408 and the second robot unit 406, or the front end robot transfers the substrate from the FOUP 418 to an aligner that allows the substrate to be properly centered before it is etched, deposited, or otherwise processed. After alignment, the substrate is moved into the airlock module 404 by the second robot unit 406. Because the airlock module has the ability to match an environment between the ATM and the VTM, the substrate can be moved between the two pressure environments without damage. The substrate is moved from the airlock module 404 to the processing chamber 414 via the first wafer transfer module, or the VTM, by the first robot unit 426. To achieve this substrate movement, the first robot unit 426 uses an end effector on each of its arms.

[0246] Figure 4 Also depicted is an embodiment of a system controller 450 for controlling process conditions and hardware states of the processing tool 400. The system controller 450 may include one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. The processor 452 may include a CPU or computer 458, analog and / or digital input / output connections, a stepper motor controller board, etc. In some embodiments, the system controller 450 includes a processor for performing, for example, the above-described Figure 5 And the following about Figure 5 Machine readable instructions for these operations described.

[0247] As described above, one or more processing stations may be included in a multi-station processing tool. Figure 5 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 500 includes a first processing chamber 502 and a second processing chamber 504. The first processing chamber 502 includes a plurality of processing stations, four stations 580A to 580D, each of which can process one wafer. The first processing chamber 502 is configured to perform plasma processing operations on a wafer. The second processing chamber 504 is configured to perform deposition on a wafer and can be considered a deposition chamber. The second processing chamber 504 also includes a plurality of processing stations, four stations 582A to 582D, each of which can process one wafer and can be controlled by module 590. The first and second processing chambers 502 and 504 can be considered multi-station processing chambers.

[0248] The tool 500 also includes a wafer transfer unit configured to transfer one or more wafers within the tool 500. Other features of the tool 500 will be discussed in more detail below, and various features related to certain of the described techniques are discussed herein. In the depicted figure, the wafer transfer unit includes a first robot unit 508 in a first wafer transfer module 510 and a second robot unit 512 in a second wafer transfer module 514, which can be viewed as an equipment front end module (EFEM) configured to receive a container for wafers, such as a front opening unified module (FOUP) 516. The first robot unit 508 is configured to transfer wafers between the first processing chamber 502 and the second processing chamber 504, and between the second robot unit 512. The second robot unit 512 is configured to transfer wafers between the FOUP and the first robot unit 508. After the wafers have been processed in the first processing chamber 502, the wafer transfer unit can transfer the wafers from the first processing chamber 502 to the second processing chamber 504, where one or more layers of encapsulation material can be deposited on one or more wafers.

[0249] Similar to the above, the first wafer transfer module 510 can be a vacuum transfer module (VTM). An air lock 520, also referred to as a load lock or transfer module, is shown and can be optimized individually to perform various manufacturing processes. The tool 500 also includes a FOUP 516 configured to reduce the pressure of the tool 500 to a vacuum or a low pressure, such as between about 1mTorr and about 10Torr, and maintain the tool 500 at this pressure. This includes maintaining the first and second processing chambers 502 and 504, and the first wafer transfer module 510 at a vacuum or low pressure. The second wafer transfer module 514 can be at a different pressure, such as atmospheric pressure. Since the wafer is transferred throughout the tool 500, the wafer is maintained at a vacuum or low pressure. For example, since the wafer is transferred from the first processing chamber 502 into the first wafer transfer module 510 and arrives at the second processing chamber 504, the wafer is maintained at a vacuum or low pressure without being exposed to atmospheric pressure.

[0250] In a further example, the substrate is placed in one of the FOUP 518 and the second robot unit 512, or the front end robot transfers the substrate from the FOUP 518 to an aligner that allows the substrate to be properly centered before it is etched, deposited, or otherwise processed. After alignment, the substrate is moved into the airlock 520 by the second robot unit 512. Because the airlock module has the ability to match the environment between the ATM and the VTM, the substrate can be moved between the two pressure environments without damage. The substrate is moved from the airlock 520 via the first wafer transfer module 510, or the VTM510 into the first processing chamber 502 by the first robot unit 508. To achieve this substrate movement, the first robot unit 508 uses an end effector on each of its arms.

[0251] Figure 5 Also depicted is an embodiment of a system controller 529 for controlling process conditions and hardware states of the tool 500. The system controller 529 may include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). The processor may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0252] In some embodiments, the system controller 529 controls all activities of the tool 500. The system controller 529 executes system control software stored in a mass storage device, loaded into a memory device, and executed on a processor. Alternatively, the control logic may be hard-coded in the system controller 529. Application-specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays, or FPGAs) and the like may be used for these purposes. In the following discussion, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software may include instructions for controlling the timing, mixing of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestals, chuck and / or sensor positions, and parameters of a particular process performed by the tool 500. The system control software may be configured in any suitable manner. For example, various processing tool component subroutines or control targets may be written to control the operation of processing tool components used to implement the processes of various processing tools. The system control software may be encoded in any suitable computer-readable programming language.

[0253] In some embodiments, the system control software may include input / output control (IOC) sequence instructions for controlling the various parameters described above. Other computer software and / or programs stored on mass storage devices and / or memory devices associated with the system controller 529 may be employed in some embodiments. Examples of programs or program segments for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0254] The substrate positioning program may contain program code for processing tool components used to load a substrate onto a pedestal and control the spacing between the substrate and other parts of the tool 500.

[0255] The process gas control program may include code for controlling gas composition (e.g., silicon-containing precursor gas, nitrogen-containing gas, carrier gas, inert gas, and / or purge gas as described herein) and flow rate, and optionally code for flowing gas into one or more process stations to stabilize pressure in the process station prior to deposition. The pressure control program may include code for controlling pressure in a process station by adjusting, for example, a throttle valve in an exhaust system of the process station, gas flow into the process station, and the like.

[0256] The heater control program may include code for controlling the current to a heating unit for heating the substrate.Alternatively, the heater control program may control the delivery of a heat transfer gas (eg, helium or nitrogen) to the substrate.

[0257] The plasma control program may include code for setting RF power levels applied to process electrodes in one or more process stations according to embodiments herein.

[0258] The pressure control program may include code for maintaining pressure in a reaction chamber according to embodiments herein.

[0259] In some embodiments, there may be a user interface associated with the system controller 529. The user interface may include a display screen, a graphical software display of apparatus and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0260] In some embodiments, the parameters adjusted by the system controller 529 relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters can be provided to the user in the form of a recipe, which can be entered using the user interface.

[0261] Signals for monitoring the process may be provided from various process tool sensors by analog and / or digital input connections of the system controller 529. Signals for controlling the process may be output through analog and / or digital output connections of the process tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (e.g., manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain process conditions.

[0262] The system controller 529 may provide program instructions for implementing the above-described deposition process. The program instructions may control various process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate the in-situ deposition of the film stack according to various embodiments described herein.

[0263] The system controller 529 will typically include one or more memory devices and one or more processors configured to execute instructions so that the apparatus will perform methods according to the disclosed embodiments. A machine-readable medium containing instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 529.

[0264] In some implementations, the controller 529 is part of a system, which can be part of the above examples. Such a system can include a semiconductor processing device, which includes one or more processing tools, one or more chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronic devices for controlling their operation before, during, and after the processing of semiconductor wafers or substrates. The electronic device can be referred to as a "controller", which can control various components or subcomponents of one or more systems. Depending on the processing system and / or system type, the system controller 529 can be programmed to control any process disclosed herein, including the delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out tools and other transfer tools and / or load locks connected or docked with a specific system.

[0265] In a broad sense, the system controller 529 can be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions sent to the system controller 529 in the form of various individual settings (or program files) that define operating parameters for performing a particular process on or for a semiconductor wafer or system. In some embodiments, the operating parameters may be part of a recipe defined by a process engineer to complete one or more processing steps during the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0266] In some implementations, the system controller 529 may be part of or coupled to a computer that is integrated with the system, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the system controller 529 may be in the "cloud" or may be all or part of a wafer fab host system that may allow remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, examine the history of past manufacturing operations, examine trends or performance criteria for multiple manufacturing operations, change parameters of a current process, set processing steps to follow the current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system via a network (which may include a local network or the Internet). The remote computer may include a user interface that enables input or programming of parameters and / or settings, which are then sent from the remote computer to the system. In some examples, the system controller 529 receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the system controller 529 is configured to interface with or control. Thus, as described above, the system controller 529 can be distributed, for example, by including one or more discrete controllers networked together and working toward a common purpose (e.g., process and control as described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber that communicate with one or more integrated circuits remotely (e.g., at a platform level or as part of a remote computer), which combine to control the process on the chamber.

[0267] Example systems may include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfer edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, ALD chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the manufacture and / or preparation of semiconductor wafers.

[0268] As described above, depending on one or more processing steps to be performed by the tool, the system controller 529 can communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a host computer, another controller, or tools used in the transport of materials for transporting wafer containers to and from tool locations and / or load ports in a semiconductor manufacturing facility.

[0269] Suitable apparatus for performing the methods disclosed herein are further discussed and described in U.S. patent application Ser. No. 13 / 084,399, filed on Apr. 11, 2011, and entitled “PLASMA ACTIVATED CONFORMAL FILMDEPOSITION” (now U.S. Patent No. 8,728,956); and U.S. patent application Ser. No. 13 / 084,305, filed on Apr. 11, 2011, and entitled “SILICON NITRIDE FILMS AND METHODS,” each of which is incorporated herein in its entirety.

[0270] The apparatus / processes described herein can be used in conjunction with photolithographic patterning tools or processes, e.g., for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, though not necessarily, these tools / processes will be used or operated together in a common manufacturing facility. Photolithographic patterning of films typically includes some or all of the following operations, each of which enables multiple available tools: (1) coating a workpiece, i.e., substrate, with photoresist using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or UV curing tool; (3) exposing the photoresist to visible light or UV light or X-rays using a tool such as a wafer stepper; (4) developing the resist so as to selectively remove the resist and thereby pattern it using a tool such as a wet cleaning station; (5) transferring the resist pattern to an underlying film or workpiece by using a dry or plasma assisted etching tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper. experiment Experiment 1

[0271] According to certain disclosed embodiments, silicon nitride is deposited onto a substrate having high aspect ratio features, performing thermal atomic layer deposition (ALD) and hybrid ALD. For thermal ALD, silicon nitride is deposited by exposing the substrate to one or more deposition cycles, each deposition cycle comprising: dosing of a silicon-containing precursor, sweeping, thermal conversion of ammonia, and sweeping. For hybrid ALD, silicon nitride is deposited by exposing the substrate to one or more deposition cycles, each deposition cycle comprising: dosing of a silicon-containing precursor, sweeping, thermal conversion of ammonia, sweeping, exposure to ammonia and nitrogen plasma, and sweeping. The sidewall thickness of the deposited silicon nitride film is measured at a depth of approximately 0.5 μm at the top of the feature near the opening, in the middle (using a planar cutting TEM), and at the bottom measured 0.5 μm from the bottom of the feature. The growth per cycle at the top, middle, and bottom is measured and plotted on Figure 6 middle. Figure 6 The growth rate of the feature sidewalls is shown to increase when using the hybrid ALD process, showing at least a 1.7x increase in growth rate. Conformality appears to be about 100%. Experiment 2

[0272] FTIR was performed on silicon nitride deposited by thermal ALD and silicon nitride deposited by hybrid ALD. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, and sweep. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, sweep, ammonia and nitrogen plasma exposure, and sweep.

[0273] Fig. 7A , 7B FTIR is depicted in 7A (partial zoom in on the vicinity of the 3000-3500 wavenumber region) and 7C (partial zoom in on the vicinity of the 2000-2500 wavenumber region).

[0274] Circle 702 is drawn to show that although hybrid ALD silicon nitride generally has more Si-N bonds (see 800 cm -1 However, FTIR shows that there is some variation at 702 due to Si-N from the substrate itself and it is an artifact.

[0275] Figure 7B Shows the Fig. 7A The circled portion is magnified 40 times. Compared to silicon nitride deposited by thermal ALD, silicon nitride deposited by hybrid ALD exhibits a higher NH bond concentration.

[0276] Figure 7C Shows the Fig. 7A The circled portion is magnified 100 times. Compared to silicon nitride deposited by thermal ALD, silicon nitride deposited by hybrid ALD exhibits a lower Si-H bond concentration.

[0277] These results suggest that thermal ALD results in H bonding to Si as well as N, whereas hybrid ALD may tend to form H bonds primarily to N. In some embodiments, Si-H bonds may be shallow, low energy electron traps that may be useful in some applications. In some cases, controlling the concentration of Si-H bonds in the deposited silicon nitride may be useful for high energy trap states. Varying the RF plasma exposure during hybrid ALD may help tune how hydrogen bonds in the deposited film. Experiment 3

[0278] The roughness of silicon nitride films deposited by thermal ALD and by hybrid ALD was evaluated. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweeping, ammonia thermal conversion, and sweeping. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweeping, ammonia thermal conversion, sweeping, ammonia and nitrogen plasma exposure, and sweeping.

[0279] The film roughness in thermal ALD silicon nitride had a root mean square (rms) of 0.232 nm and an average of 0.179 nm. The film roughness in hybrid ALD silicon nitride had a root mean square of 0.179 nm and an average of 0.135 nm.

[0280] These results show that film roughness is reduced when using the hybrid ALD process compared to the thermal ALD process. Experiment 4

[0281] Impurities of silicon nitride films deposited by thermal ALD and by hybrid ALD were measured. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweeping, ammonia thermal conversion, and sweeping. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweeping, ammonia thermal conversion, sweeping, ammonia and nitrogen plasma exposure, and sweeping.

[0282] Figure 8 Results for thermal ALD at 801 and hybrid ALD at 803 are shown. Results show that F and Cl impurity concentrations are reduced in hybrid ALD compared to thermal ALD. Chlorine may be present due to the use of a chlorine-containing silicon-containing precursor. Fluorine may be present due to the use of a nitrogen trifluoride clean chamber.

[0283] Table 1 shows a comparison of the C, O, F, Cl, and H concentrations in thermal ALD silicon nitride and hybrid ALD silicon nitride as measured by secondary ion mass spectroscopy (SIMS). Table 1 - Reduction of Carbon, Oxygen, Fluorine, Chlorine, and Hydrogen Concentrations in SiN Deposited by Thermal ALD Only and Hybrid ALD

[0284] While hydrogen shows an increase in the hybrid ALD silicon nitride, this is likely due to hydrogen bonding differently in silicon nitride compared to thermal ALD silicon nitride. Other elements show decreased impurities. Experiment 5

[0285] Growth per cycle as a function of susceptor temperature was measured for silicon nitride films deposited by thermal ALD and for silicon nitride deposited by hybrid ALD. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, and sweep. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, sweep, ammonia and nitrogen plasma exposure, and sweep.

[0286] The results are Fig. 9 Data 901 shows the temperature dependence of hybrid ALD, while data 902 shows the temperature dependence of thermal-only ALD. In thermal-only ALD, the growth rate changes dramatically with changes in susceptor temperature, while hybrid ALD shows a gradual increase in growth per cycle with increasing changes in susceptor temperature. Experiment 6

[0287] Film thickness and within-wafer uniformity of silicon nitride films deposited by thermal ALD and by hybrid ALD were evaluated. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, and sweep. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, sweep, ammonia and nitrogen plasma exposure, and sweep.

[0288] The results are Fig.10 The solid line for hybrid ALD shows a reduction in relative within-wafer non-uniformity (e.g., a flatter line in this line scan with a non-uniformity of about 3%) compared to silicon nitride deposited by thermal ALD alone (which has a non-uniformity of about 6%). Compared to thermal conversion alone, the uniformity is reduced by more than 50%. Experiment 7

[0289] Density, wet etch rate in 100:1 dilute hydrofluoric acid, and stress were evaluated for silicon nitride films deposited by thermal ALD and by hybrid ALD. For thermal ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, and sweep. For hybrid ALD, silicon nitride was deposited by exposing the substrate to one or more deposition cycles, each deposition cycle including: silicon-containing precursor dosing, sweep, ammonia thermal conversion, sweep, ammonia and nitrogen plasma exposure, and sweep.

[0290] The results are in Table 2 below. These results show that stress can be tuned by varying the plasma time, and that going from tensile to compressive films can be achieved by adjusting the process conditions, and that when using hybrid ALD, density increases and wet etch rates decrease, indicating improved film quality. Table 2 - Density, wet etch rate, and stress of hybrid ALD silicon nitride versus thermal ALD-only silicon nitride Experiment 8

[0291] The growth of undercoat films deposited as blanket films was evaluated. The films were deposited at 650°C using 100 atomic layer deposition cycles, where each cycle involved flowing 100 seem of diisopropylaminosilane at 3 Torr for 1 second, followed by a 3 second purge, and then flowing 20 slm of nitrogen at 3 Torr and igniting the plasma at 6000 W for 5 seconds (then 10 seconds, then 15 seconds, then 20 seconds to evaluate variable times), followed by a 3 second purge. Fig.11A The trend of growth per cycle versus plasma time is shown. Fig. 11B The growth per cycle and the trend of the refractive index are shown. Refractive index saturation is observed at about 20 seconds. Experiment 9

[0292] The growth of undercoat films deposited as blanket films was evaluated. The films were deposited at 650°C using 100 atomic layer deposition cycles, where each cycle involved flowing 100 seem of diisopropylaminosilane at 3 Torr for a variable time (seconds), followed by a 3 second purge, and then flowing 20 slm of nitrogen at 3 Torr and igniting the plasma at 6000 W for 5 seconds, followed by a 3 second purge. Fig. 12A Trends in growth per cycle versus dosing time are shown. Fig. 12B The growth and refractive index trends per cycle are shown. The sub-saturation time of the dosing occurs in about 1.5 seconds. Experiment 10

[0293] The growth of undercoat films deposited as blanket films was evaluated. The films were deposited at 650°C using 100 atomic layer deposition cycles, where each cycle involved flowing 100 seem of diisopropylaminosilane at variable pressure for 1 second, followed by a 3 second purge, and then flowing 20 slm of nitrogen at variable pressure and igniting the plasma at 6000 W for 5 seconds, followed by a 3 second purge. Fig.13A The trend of growth and pressure per cycle is shown. Fig. 13B The growth and refractive index trends for each cycle are shown. As the pressure increases, the growth and refractive index also increase. Overall, approximately of growth per cycle and a refractive index of about 2.05. Experiment 11

[0294] Fourier transform infrared spectroscopy (FTIR) spectra of the non-graded SiON film and the FTIR spectra of the silicon oxide film were obtained. The refractive index of the silicon oxide film was 1.46. The refractive index of the SiON film was 1.63. The shift of the FTIR peak to a lower wave number indicates an increase in the nitrogen content in the film.

[0295] FTIR spectra of non-graded silicon nitride film, graded silicon nitride film in-situ oxidized for 10 minutes, and graded silicon nitride film in-situ oxidized for 15 minutes were obtained. Fig.14 Middle: The bottom image shows a non-graded silicon nitride film, the middle image shows a graded silicon nitride film that was in-situ oxidized for 10 minutes, and the top image shows a graded silicon nitride film that was in-situ oxidized for 15 minutes. The peaks show the bending mode of the Si-O bonds. For the graded SiON film, both SiN and SiO peaks are visible. Longer in-situ oxidation increases the Si-O peak, indicating that more oxygen is incorporated and more Si-O-Si bonds are formed, which means that the SiN film has a deeper oxidation. These results show that the amount of oxidation and the depth of oxidation can be controlled using certain disclosed embodiments. Experiment 12

[0296] Experiments were conducted to measure the sidewall thickness compared to the depth within the features of silicon oxynitride deposited using certain disclosed embodiments. The step coverage achieved was from about 90% to about 102%, as shown in FIG. Fig.15 shown. Definition and Precursors definition

[0297] The terms "acyl" or "alkanoyl" used interchangeably herein refer to a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms or hydrogen in straight chain, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent molecular group through a carbonyl group as defined herein. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, wherein R is hydrogen, an aliphatic group or an aromatic group, as defined herein.

[0298] "Alkanoyloxy" refers to an alkanoyl group, as defined herein, attached to a parent molecular group through an oxy group, as defined herein. Such a group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, alkanoyloxy is -OC(O)-R, wherein R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0299] "Aliphatic" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), and hydrocarbon groups including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and also including straight chain and branched arrangements, as well as all stereo and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0300] "Aliphatic-carbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0301] "Aliphatic-carbonyloxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, aliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0302] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, aliphatic-oxy ​​is -OR, wherein R is an optionally substituted aliphatic group as defined herein.

[0303] "Aliphatic-oxycarbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, aliphatic-oxycarbonyl is -C(O)OR, wherein R is an optionally substituted aliphatic group as defined herein.

[0304] "Alkyl-aryl", "alkenyl-aryl" and "alkynyl-aryl" mean an alkyl, alkenyl or alkynyl, respectively, as defined herein, coupled (or linked) or capable of being coupled (or linked) to a parent molecular group through an aryl, as defined herein. Alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted with one or more substituents, as described herein for alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon (C 2+) atoms. 7-16 alkyl-aryl), and those having an alkyl group containing 1 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkenyl-aryl), and those having an alkenyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbon (C 7-16 alkynyl-aryl), and those having an alkynyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, alkyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkynyl as defined herein.

[0305] "Alkenyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50), for example, 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent olefin. The alkenyl group can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 Alkyl. Alkenyl can be monovalent or multivalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecular group or a suitable connection between the parent molecular group and another substituent. Alkenyl can also be substituted or unsubstituted. For example, alkenyl can be substituted with one or more substituents, as described herein for alkyl. Non-limiting alkenyl includes allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, etc.

[0306] "Alkoxy" refers to -OR, where R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 Alkoxy.

[0307] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups contain 2 to 12 carbon (C 2-12 alkoxyalkyl), and those having an alkyl group containing 1 to 6 carbons and an alkoxy group containing 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl is -LOR, wherein L and R are each independently alkyl as defined herein.

[0308] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In specific embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group may be substituted or unsubstituted. For example, the alkoxycarbonyl group may be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 Alkoxycarbonyl.

[0309] "Alkyl" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, straight or cyclic (e.g., a cycloalkyl group). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can also be substituted or unsubstituted. The alkyl group may be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to the parent molecular group or between the parent molecular group and another substituent. For example, the alkyl group may be substituted with one, two, three, or in the case of an alkyl group of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (2) C 1-6 Alkylsulfinyl (e.g., C 1-6 , wherein R is a C1-6 alkyl group); (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (4) amino (e.g., -NR 1 R2 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein, or R 1 and R 2 (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C(O)-R; (12) C(O)-R; (13) C(O)-R; (14) C(O)-R; (15) C(O)-R; (16) C(O)-R; (17) C(O)-R; (18) C(O)-R; (19) C(O)-R; (20) C(O)-R; (21) C(O)-R; (22) C(O)-R; (23) C(O)-R; (24) C(O)-R; (25) C(O)-R; (26) C(O)-R; (27) C(O) 3-8 Cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -OR, wherein R is heterocyclyl, as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is heterocyclyl, as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 , where R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (23)-C(O)NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 alkyl.

[0310] "Alkylene", "alkenylene" or "alkynylene" refers to a polyvalent (e.g., divalent) form of an alkyl, alkenyl or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, alkylene is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 The alkylene, alkenylene or alkynylene groups may be branched or unbranched. The alkylene, alkenylene or alkynylene groups may also be substituted or unsubstituted. For example, the alkylene, alkenylene or alkynylene groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0311] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -S(O)- group. In some embodiments, unsubstituted alkylsulfinyl is C 1-6 or C 1-12 In other embodiments, alkylsulfinyl is -S(O)-R, wherein R is alkyl as defined herein.

[0312] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, unsubstituted alkylsulfinylalkyl is C 2-12 or C 2-24 Alkylsulfinylalkyl (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In other embodiments, alkylsulfinylalkyl is -LS(O)-R, wherein L and R are each independently alkyl as defined herein.

[0313] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO2- group. In some embodiments, unsubstituted alkylsulfonyl is C1-6 or C 1-12 In other embodiments, alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., as described herein, comprising optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0314] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24 Alkylsulfonylalkyl (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In other embodiments, alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0315] "Alkynyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent alkyne. The alkynyl group can be branched, straight chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include optionally substituted C 2-24 Alkyl. Alkyl groups can be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or an appropriate bond between the parent molecular group and another substituent. Alkyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl.

[0316] By "ambient temperature" is meant a temperature in the range of 16°C to 26°C, for example 19°C to 25°C or 20°C to 25°C.

[0317] "Amide" refers to -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, an aromatic group as defined herein, or any combination thereof, or wherein R 1 and R 2Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0318] "Amino" refers to -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted siloxy. In specific embodiments, R 1 and R 2 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0319] "Aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminoalkyl is -L-NR 1 R 2 , wherein L is alkyl as defined herein, and R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. In other embodiments, aminoalkyl is -LC(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each is independently H or alkyl as defined herein.

[0320] "Aminooxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminooxy is -O-NR 1 R 2 , where R 1 and R 2 R is each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl or optionally substituted siloxy.

[0321] Unless otherwise indicated, "aromatic group" refers to a cyclic conjugated group or moiety having 5 to 15 ring atoms of a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous delocalized π electron system. Typically, the number of out-of-plane π electrons corresponds to the Huckel rule (4n+2). The point of connection to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aromatic groups may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

[0322] "Aromatic-carbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0323] "Aromatic-carbonyloxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0324] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, aromatic-oxy ​​is -OR, wherein R is an optionally substituted aromatic group as defined herein.

[0325] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted aromatic group as defined herein.

[0326] "Aryl" refers to a group comprising at least 5 carbon atoms and up to 15 carbon atoms (C 5-15 ), such as 5 to 10 carbon atoms (C 5-10 ), an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic groups, heteroaliphatic groups, aromatic groups, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl groups, which are defined as groups containing aromatic groups having at least one heteroatom bound to the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl is also included in the term aryl, which is defined as a group containing aromatic groups without heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 Alkyl); (2) C 1-6 Alkyl; (3)C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, wherein L and R are each independently C 1-6 Alkyl); (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 Alkyl); (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, wherein L and R are each independently C 1-6Alkyl); (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 Alkyl); (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein); (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 Alkyl; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each independently is H or C 1-6 alkyl); (12) heteroaryl; (13) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (14) aroyl (e.g., C(O)-R, wherein R is an aryl group); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehydes (e.g., -C(O)H); (19) aldehydes-C 1-6Alkyl (e.g., -LC(O)H, where L is C 1-6 Alkyl); (20)C 3-8 Cycloalkyl; (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 Cycloalkyl); (22) halo; (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each independently is H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -OR, wherein R is a heterocyclyl, as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, wherein R is a heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (29) nitro; (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C 1-6Alkyl; (33) Oxo (eg, =O); (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, wherein L and R are each independently C 1-6 Alkyl); (36)-(CH2) r CO2R 1 , where r is an integer from 0 to 4, and R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (37)-(CH2) r CONR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 and R 2 are each independently selected from: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (38)-(CH2) r S02R 1 , where r is an integer from 0 to 4, and where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C 4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 (41) thiols (e.g., -SH); (42) perfluoroalkyls (e.g., -(CF2) n CF3, wherein n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, wherein n is an integer from 0 to 10); (44) aryloxy (e.g., -OR, wherein R is aryl); (45) cycloalkoxy (e.g., -OR, wherein R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, wherein L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl). In specific embodiments, the unsubstituted aryl is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Aryl.

[0327] "Aryl-alkyl", "aryl-alkenyl" and "aryl-alkynyl" refer to an aryl group, as defined herein, coupled (or linked) to a parent molecular group through an alkyl, alkenyl or alkynyl group, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted with one or more substituents, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbon atoms (C 7-16 aryl-alkyl), and those having an aryl group of 4 to 18 carbons and an alkyl group of 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbon (C 7-16 aryl-alkenyl), and those having an aryl group containing 4 to 18 carbons and an alkenyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbon (C 7-16 aryl-alkynyl), and those having an aryl group containing 4 to 18 carbons and an alkynyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, wherein L is alkyl or alkylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkenyl group is -LR, wherein L is alkenyl or alkenylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkynyl group is -LR, wherein L is alkynyl or alkynylene as defined herein, and R is aryl as defined herein.

[0328] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthracene, or phenanthrenyl. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Arylene. Arylene can be branched or unbranched. Arylene can also be substituted or unsubstituted. For example, arylene can be substituted with one or more substituents, as described herein for aryl.

[0329] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, arylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is aryl, as defined herein.

[0330] "Aryloxy" refers to -OR, where R is an optionally substituted aryl as described herein. In some embodiments, unsubstituted aryloxy is C 4-18 or C 6-18 In other embodiments, R is aryl optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0331] "Aryloxycarbonyl" refers to an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aryloxycarbonyl is C 5-19 Aryloxycarbonyl. In other embodiments, aryloxycarbonyl is -C(O)OR, wherein R is aryl as defined herein.

[0332] "Aroyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aroyl is C 7-11 Aroyl or C 5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

[0333] "Aroyloxy" refers to an aroyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, unsubstituted aroyloxy is C 5-19 In other embodiments, aroyloxy is -OC(O)-R, wherein R is aryl as defined herein.

[0334] "Azide" refers to a -N3 group.

[0335] "Azidoalkyl" refers to an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, azidoalkyl is -L-N3, wherein L is an alkyl group as defined herein.

[0336] "Azo" refers to the group -N=N-.

[0337] "Carbamoyl" refers to an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 Group, where R 1 and R 2are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0338] "Carbamoyloxy" refers to a carbamoyl group, as defined herein, appended to the parent molecular group through n oxy groups, as defined herein. In some embodiments, the carbamoyl group is -OC(O)NR 1 R 2 Group, where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0339] "Carboimidoyl" refers to a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof.

[0340] "Carbonyl" refers to a -C(O)- group, which may also be represented as >C=O.

[0341] "Carboxyl" refers to a -CO2H group or its anion.

[0342] "Catalyst" refers to a compound capable of catalyzing a synthesis reaction, typically present in a small amount relative to the reactants, as readily understood by one of ordinary skill in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0343] "Cyanato" refers to an -OCN group.

[0344] "Cyano" refers to a -CN group.

[0345] "Cycloaliphatic" means a cyclic aliphatic radical as defined herein.

[0346] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, cycloalkoxy is -OR, wherein R is a cycloalkyl group, as defined herein.

[0347] "Cycloalkylalkoxy" means a -OLR group where L is alkyl or alkylene as defined herein and R is cycloalkyl as defined herein.

[0348] Unless otherwise indicated, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 8 carbons, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyls may also be substituted or unsubstituted. For example, cycloalkyls may be substituted with one or more groups, including those described herein for alkyls. In addition, cycloalkyls may include one or more double bonds and / or triple bonds.

[0349] "Cycloheteroaliphatic" refers to a heteroaliphatic group as defined herein that is cyclic.

[0350] "Disilyl" refers to a group containing a Si-Si bond. In some embodiments, the disilyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 Or-SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 and R S5 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0351] "Disulfide" means -SSR, wherein R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0352] An "electron donating group" refers to a functional group that is capable of donating at least a portion of its electron density to the ring to which it is directly attached, such as by resonance.

[0353] "Electron withdrawing group" refers to a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

[0354] "Halo" refers to F, Cl, Br or I.

[0355] "Haloaliphatic" means an aliphatic group as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0356] "Haloalkyl" refers to an alkyl group as defined herein, wherein one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently replaced by halogen atoms, e.g., fluorine, bromine, chlorine, or iodine. In independent embodiments, haloalkyl can be a -CX3 group, wherein each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, haloalkyl is -LX, wherein L is an alkyl group as defined herein, and X is fluorine, bromine, chlorine, or iodine. In other embodiments, haloalkyl is -LC(X)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0357] "Haloheteroaliphatic" refers to a heteroaliphatic group as defined herein wherein one or more hydrogen atoms, eg, 1 to 10 hydrogen atoms, are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0358] "Heteroaliphatic" refers to an aliphatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaliphatic groups may be substituted with one or more substituents, such as described herein for alkyl groups.

[0359] "Heteroaliphatic-carbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0360] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0361] "Heteroaliphatic-oxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0362] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, heteroaliphatic-oxycarbonyl is -C(O)OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0363] "Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" refer to an alkyl, alkenyl or alkynyl group (which may be branched, straight chain or cyclic) as defined herein, respectively, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms, which heteroatoms may be selected from but are not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and oxidized forms thereof.

[0364] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to polyvalent (eg, divalent) forms of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0365] "Heteroaromatic" refers to an aromatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups may be substituted with one or more substituents, such as described herein for alkyl and / or aryl groups.

[0366] By "heteroaromatic-carbonyl" is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0367] "Heteroaromatic-carbonyloxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0368] "Heteroaromatic-oxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​is -OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0369] "Heteroaromatic-oxycarbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0370] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms (e.g., one to four heteroatoms) in the ring, wherein the heteroatoms are selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups may have a monocyclic or multiple condensed rings, wherein the condensed rings may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of an aromatic heteroaryl group. Heteroaryl groups may be substituted by one or more groups that are not hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n+2 π electrons in a monocyclic or polycyclic ring system.

[0371] "Heteroarylene" refers to a polyvalent (eg, divalent) form of a heteroaryl group as described herein.

[0372] "Heteroatom" refers to an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, heteroatoms do not include halogen atoms, such as when valence restrictions do not permit.

[0373] Unless otherwise indicated, "heterocyclyl" refers to a 5-, 6- or 7-membered ring containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur or halide). The 5-membered ring has 0 to 2 double bonds, and the 6-membered and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic and tetracyclic groups, wherein any of the above heterocyclic rings are fused to one, two or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothienyl, etc. The heterocyclic group includes thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, zinyl), pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl,thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, etc.

[0374] "Heterocyclyloxy" refers to a heterocyclyl, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -OR, wherein R is heterocyclyl, as defined herein.

[0375] "Heterocycloacyl" means a heterocyclyl, as defined herein, attached to the parent molecular moiety through a carbonyl group. In some embodiments, heterocycloacyl is -C(O)-R, wherein R is a heterocyclyl, as defined herein.

[0376] "Hydrazino" refers to -NR 1 -NR 2 R 3 , where R 1 , R 2 and R 3 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 A combination of or2 and R 3 The combination of together with the nitrogen atom to which they are attached may form a heterocyclic group as defined herein. 1 , R 2 or R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl. In specific embodiments, R 2 and R 3 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0377] "Hydroxyl" refers to -OH.

[0378] "Hydroxyalkyl" refers to an alkyl group as defined herein substituted with 1 to 3 hydroxy groups, provided that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, hydroxyalkyl is -L-OH, wherein L is an alkyl group as defined herein. In other embodiments, hydroxyalkyl is -LC(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0379] "Imino" refers to a moiety comprising a carbon imino group. In some embodiments, the imino group is C(NR 1 )R 2 , where R 1 and R 2 Each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof. In other embodiments, the imino group is -C(NR 1 )H、-C(NR 1 )R Ak or -C(NR N1 )R Ar , where R 1 R is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, or optionally substituted siloxy; RAk is optionally substituted alkyl or optionally substituted aliphatic; and R Ar is an optionally substituted aryl group or an optionally substituted aromatic group.

[0380] "Imino" refers to a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0381] "Isocyanato" refers to a -NCO group.

[0382] "Isocyano" refers to a -NC group.

[0383] "Ketone" refers to -C(O)R or a compound containing this group, wherein R is selected from aliphatic, heteroaliphatic, aromatic or any combination thereof as defined herein. Examples of ketones may include R 1 C(O)R, where R and R 1 Each is independently selected from aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0384] "Nitro" refers to a -NO2 group.

[0385] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with 1 to 3 nitro groups. In some embodiments, nitroalkyl is -L-NO, wherein L is an alkyl group, as defined herein. In other embodiments, nitroalkyl is -LC(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0386] "Oxo" refers to a =0 group.

[0387] "Oxy" refers to -O-.

[0388] "Perfluoroalkyl" refers to an alkyl group as defined herein in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, wherein n is an integer from 0 to 10.

[0389] "Perfluoroalkoxy" refers to an alkoxy group as defined herein wherein each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, wherein R is a perfluoroalkyl group as defined herein.

[0390] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that contains a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in: Berge SM et al., "Pharmaceutical salts," J. Pharm. Sci. 1977 January; 66 (1): 1-19; and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. PHStahland C G Wermuth. Salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or separately by reacting the free base groups with suitable organic acids (thereby producing anionic salts) or by reacting the acid groups with suitable metals or organic salts (thereby producing cationic salts). Representative anionic salts include acetates, adipates, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphor sulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrobromide, hydrochloride, hydroiodide, isethionate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, methanesulfonate (m esylate), methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophylline Representative cationic salts include metal salts, such as alkali metal or alkaline earth metal salts, for example, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron and zinc; and non-toxic ammonium, quaternary ammonium and amino cations, including but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc.Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine and procaine. Other salts include ammonium, sulfonium, sulfoxonium, phosphorus, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepi nium), optionally substituted indolium, optionally substituted isoindolinium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0391] "Silyl" refers to -SiR 1 R 2 R 3 Or-SiR 1 R 2 - group. In some embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyl is -Si(R) a (OR)b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0392] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, silyloxy is -O-SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyloxy is —O—Si(R) a (OR) b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0393] "Sulfinyl" refers to a -S(O)- group.

[0394] "Sulfo" refers to a -S(O)2OH group.

[0395] "Sulfonyl" or "sulfonate" refers to a -S(O)2- group or -SO2R, where R is selected from hydrogen, an aliphatic, a heteroaliphatic, a haloaliphatic, a haloheteroaliphatic, an aromatic group as defined herein, or any combination thereof.

[0396] "Thioalkyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 In some embodiments, the thioalkyl group is -SR, wherein R is alkyl as defined herein.

[0397] "Thiol" refers to a -SH group.

[0398] One of ordinary skill in the art will recognize that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such impermissible substitution patterns are readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

[0399] As used herein, the term "about" refers to a difference of ±10% from any stated value. As used herein, the term modifies any stated value, range of values, or endpoints of one or more ranges.

[0400] As used herein, the terms "top", "bottom", "lower", "above", and "below" are used to provide relative relationships between multiple structures. The use of these terms does not indicate or require that a particular structure must be located at a particular position in the device.

[0401] Other features and advantages of the invention will become apparent from the following description and from the claims. Silicon-containing precursor

[0402] In various embodiments, the silicon-containing precursor is a silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In specific embodiments, the silicon-containing precursor comprises a halosilane precursor. In specific embodiments, the silicon-containing precursor comprises an aminosilane precursor.

[0403] Aminosilanes contain at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), and substituted mono-, di-, tri-, and tetra-aminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilylamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2(BTBAS), tert-butylsilylcarbamate, Si(NH2)4, and tert-butylsilylaminosilane. H(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), etc. Another example of aminosilane is trisilylamine (N(SiH3)3). In one example, the silicon-containing precursor is DIPAS. In another example, the silicon-containing precursor is BTBAS.

[0404] The silicon-containing precursor may contain one or more optionally substituted amino groups, thereby providing non-limiting aminosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(NR"2) x ,in: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and Each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0405] In another embodiment, the precursor has the formula (R"2N) x (R') 3-x Si-L-Si(R') 3-x (NR"2) x ,in: Each x is independently 0, 1, 2 or 3; L is a linking group such as a covalent bond, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an oxy group (—O—), an imino group or a silyl group; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and Each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0406] In specific embodiments, L is an optionally substituted imino group, such as -NR-, wherein R is H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group. In other embodiments, L is an optionally substituted silyl group, such as -SiR2-, wherein each R is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group.

[0407] In one case, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0; and / or L comprises an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (—O—), an imino, or a silyl group.

[0408] In specific embodiments, at least one R' or R" is not H. The precursor can have any useful combination of R' groups and amino groups (NR"2) attached to one or more silicon atoms.

[0409] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy ​​(e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic-oxy-silyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic groups (e.g., aryl), aromatic-oxy ​​groups (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), etc. In specific embodiments, each R is independently H, optionally substituted aliphatic groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted aryl groups, and optionally substituted heteroaromatic groups; a≥0; b≥1; and a+b=3. In some embodiments, two R groups may form an optionally substituted heterocyclic group together with the nitrogen atom to which they are attached. In other embodiments, each R is independently H, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, or optionally substituted aryl groups.

[0410] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted siloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiR3, -Si(R') a (OR) b 、-Si(R) a (OR) b 、-Si(R') a (NR2) b 、-Si(R) a (NR2) b 、-Si(R') a (OR)b (NR2) c 、-Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b 、-O-Si(R) a (OR) b 、-O-Si(R') a (NR2) b 、-O-Si(R) a (NR2) b 、-O-Si(R') a (OR) b (NR2) c or -O-Si(R) a (OR) b (NR2) c , wherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic or optionally substituted heteroaromatic; a, b and c are each ≥ 0; and a+b+c=3 or a+b=3 (if c is absent). In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl.

[0411] The precursor may comprise at least one R' group attached to a silicon atom. In one embodiment, the precursor has the formula (R')(H) 3-x Si(NR"2) x , wherein R' and R" can be any of those described herein, and wherein x is 1, 2 or 3. In another embodiment, the precursor has the formula (R')(H)2Si(NR"2), wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')(H)Si(NR"2)2, wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R')2(H)Si(NR"2), wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R')2Si(NR"2)2, wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')3Si(NR"2), wherein R' and R" can be any of those described herein.

[0412] The precursor may have no R' groups attached to the silicon atom. In one embodiment, the precursor has the formula (H) 4- x Si(NR"2) x , wherein each R" can independently be any of those described herein, and wherein x is 1, 2, 3 or 4. In another embodiment, the precursor has the formula Si(NR"2) x , wherein each R" can independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0413] The precursor may contain one or more hydrogen atoms attached to a silicon atom. In one embodiment, the precursor has the formula (H)3Si(NR"2) or (H)2Si(NR"2)2 or (H)Si(NR"2)3, wherein each R" may independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, wherein any of these groups may be optionally substituted.

[0414] The precursor may contain a heterocyclic group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, wherein Het is an optionally substituted heterocyclic group containing at least one nitrogen atom. In a specific embodiment, the precursor has the formula wherein the heterocyclyl group may be optionally substituted (e.g., substituted with any substituent described herein as substituted with an alkyl group), and wherein n is 1, 2, 3, 4, or 5. In one embodiment, the formula is of the formula R'3Si-Het, wherein Het is an optionally substituted heterocyclyl group comprising at least one nitrogen atom, and each R' may independently be any of those described herein. In a specific embodiment, the precursor is of the formula wherein the heterocyclyl group can be optionally substituted (eg, with any substituent described herein as substituted with alkyl); each R′ can independently be any of those described herein; and wherein n is 1, 2, 3, 4, or 5.

[0415] In some cases, the precursor may have two or more silicon atoms, wherein the precursor may contain Si-Si bonds. In a specific embodiment, the precursor has the formula (R"2N): x (R') 3-x Si-Si(R') 3-x (NR"2) x, wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R"2N)(R')2Si-Si(R')2(NR"2), wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R"2N)2(R')Si-Si(R')(NR"2)2, wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R"2N)3Si-Si(NR"2)3, wherein each R" can independently be any of those described herein.

[0416] The precursor may include different groups attached to the silicon atom. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-SiH3, wherein R' and R" can be any of those described herein.

[0417] The linking group may be present between two silicon atoms. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-NR-Si(R') 3-x (NR"2) x , wherein R' and R" can be any of those described herein, and wherein R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another instance, the precursor has the formula (R"2N) x (H) 3-x Si-NR-Si(H) 3-x (NR"2) x , wherein R, R' and R" can be any of those described herein.

[0418] The precursor may comprise a combination of an R' group and a linker having a heteroatom. In one instance, the precursor has the formula (R')3Si-NR-Si(R')3, wherein R and R' may be any of those described herein. In another instance, the precursor has the formula (R')3Si-L-Si(R')3, wherein L and R' may be any of those described herein. In a specific embodiment, L is an oxy group (-O-), an optionally substituted imino group (e.g., -NR-), or an optionally substituted silyl group (e.g., -SiR2-).

[0419] The precursor may include any useful combination of R' and NR"2 groups in combination with two silicon atoms. In one instance, the precursor has the formula (R"2N)(R')2Si-L-Si(R')2(NR"2) x , wherein L, R' and R" can be any of those described herein.

[0420] The precursor may contain a heterocyclic group containing silicon and nitrogen atoms. In one embodiment, the precursor has the formula wherein R' and R" can be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0421] In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein each R" can independently be any of those described herein; and wherein n is 1, 2, 3 or 4. In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein R" can independently be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0422] In any of the precursors herein, two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclic group.

[0423] The precursor may comprise any of the following, for example, (R Ak )Si(NH2)(NR Ak 2)2、(R Ak )Si(NR Ak 2)3、(R Ak )2Si(NHR Ak 2)2、(R Ak )(H)Si(NHR Ak )2、(R Ak )3Si(NR Ak 2) (R Ak )3Si(NHR Ak )、H2Si(NHR Ak 2)2、(R Ak )(H)Si(NR Ak 2)2、HSi(NH2)(NR Ak 2) 2、HSi(NR Ak 2)3、Si(NR Ak 2)4, (R')(H)Si(NR"2)2, (R')2Si(NR Ak 2)2、 (R')2Si(N[SiH3]2)2, (R')2Si(N[SiR"3]2)2 or (R')3Si(NHR AkIn some embodiments, R' and R" can each independently be any of those described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. Ak It is methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu) and the like.

[0424] Non-limiting examples of precursors include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]); dimethylaminodimethylsilane (SiMe2H[NMe2]); dimethylaminotrimethylsilane (SiMe3[NMe2]); dimethylaminodiethylsilane (SiHEt2[NMe2]); dimethylaminotriethylsilane (SiEt3[NMe2]); ethylmethylaminodimethylsilane (SiHMe2[NMeEt]); ethylmethylaminotrimethylsilane (SiMe3[NMeEt]); ethylmethylaminodiethylsilane (SiHEt2[NMeEt]); ethylmethylaminotriethylsilane (SiEt3[NMeEt]); diethylaminomethylsilane (SiH2Me[NEt2]); diethylaminoethylsilane (SiH 2Et[NEt2]); ethylaminotrimethylsilane (SiMe3[NHEt]); diethylaminodimethylsilane (SiHMe2[NEt2]); diethylaminodiethylsilane (SiHEt2[NEt2]); diethylaminotrimethylsilane (SiMe3[NEt2]); diethylaminotriethylsilane (SiEt3[NEt2]); isopropylaminodimethylsilane (SiHMe2[NHiPr]); isopropylaminotrimethylsilane (SiMe3[NHiPr]); isopropylaminodiethylsilane (SiHEt2[NHiPr]); isopropylaminotriethylsilane (SiEt3[NHiPr]); diisopropylaminotrimethylsilane (SiMe3[NiPr2]); diisopropylaminosilane (SiH3[NiPr2], C6H 17NSi or DIPAS); diisopropylaminomethylsilane (SiH2Me[NiPr2]); diisopropylaminodimethylsilane (SiHMe2[NiPr2]); diisopropylaminodiethylsilane (SiHEt2[NiPr2]); diisopropylaminotriethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]) ; tert-butylaminodimethylsilane (SiHMe2[NHtBu]); tert-butylaminotrimethylsilane (SiMe3[NHtBu]); tert-butylaminodiethylsilane (SiHEt2[NHtBu]); tert-butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl); N-propylisopropylaminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N-ethylcyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], where Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], where Py is pyrrolyl); pyrrolidinyltrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolidinyl); piperidinyltrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], where Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm] , wherein Im is an imidazolyl group); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino)methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2);Bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); Bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2); Bis(diethylamino)silane (SiH2[NEt2]2, C8H; 22 N2Si or BDEAS); bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(isopropylamino)dimethylsilane (SiMe2[NHiPr]2); bis(isopropylamino)diethylsilane (SiEt2[NHiPr]2); bis(isopropylamino)methylvinylsilane (SiMeVi[NHiPr]2 ); bis(diisopropylamino)silane (SiH2[NiPr2]2); bis(diisopropylamino)dimethylsilane (SiMe2[NiPr2]2); bis(diisopropylamino)diethylsilane (SiEt2[NiPr2]2); bis(diisopropylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec-butylamino)methylsilane (SiHMe [NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS); bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2); bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); bis(1-imidazolyl)dimethylsilane (SiMe2[Im]2, where I m is imidazolyl); tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS); tris(dimethylamino)phenylsilane (SiPh[NMe2]3); tris(dimethylamino)methylsilane (SiMe[NMe2]3); tris(dimethylamino)ethylsilane (SiEt[NMe2]3); tris(ethylmethylamino)silane (SiH[NEtMe]3); tris(diethylamino)silane (SiH[NEt2]3); tris(isopropylamino)silane (SiH[NHiPr]3, C9H 25N3Si or TIPAS); tris(dimethylamino)silylamide (Si[NMe2]3[NH2]); tetrakis(dimethylamino)silane (Si[NMe2]4); tetrakis(ethylmethylamino)silane (Si[NEtMe]4); tetrakis(diethylamino)silane (Si[NEt2]4); 1,2-diethyl-tetrakis(diethylamino)disilane ([Et2N]2EtSi-SiEt[NEt2]2); 1,2-dimethyl-tetrakis(dimethylamino)disilane ([ Hexa(methylamino)disilane ([MeHN]3Si-Si[NHMe]3); Hexa(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3); Hexa(dimethylamino)disilazane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), etc.

[0425] In some embodiments, the silane precursor is a halosilane precursor. A halosilane precursor is defined as a precursor having at least one halogen-containing atom and at least one silicon atom. Halogens include chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane precursor comprises a structure of formula (I): Si(X)4, At least one of X comprises a halogen atom.

[0426] For example, a monohalosilane is tetrachlorosilane or silicon tetrachloride (SiCl4). Another example of a chemical formula of a halosilane is Si n X y H z , wherein X is a halogen and H is hydrogen; n is an integer greater than or equal to 1 and equal to the number of Si atoms in the molecule; in some embodiments, y is from about 1 to about 4, and z is 4-y. Additional examples include, but are not limited to, SiHCl3, SiH2Cl2, and SiH3Cl.

[0427] Examples of halosilanes are iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane (DCS), monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert-butylchlorosilane, di-tert-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, tert-butyldimethylchlorosilane, tert-hexyldimethylchlorosilane, hexachlorodisilane (HCDS), and the like.

[0428] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is an organic silicon-containing precursor.

[0429] In some embodiments, the halosilane precursor (eg, in formula (I)) has at least one optionally substituted C 1-2 Non-limiting examples of haloaliphatic groups include -CX y H 3-y , wherein y is 1, 2, or 3, and wherein each X is independently halogen (F, Cl, Br, or I); -CX z H 2-z CX y H 3-y , wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is independently a halogen (F, Cl, Br, or I), wherein at least one of z or y is not 0; or -CH2CX y H 3-y , wherein y is 1, 2, or 3, and wherein each X is independently halogen (F, Cl, Br, or I). Still other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHF Cl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI), and the like. In certain embodiments, C 1-2 Haloalkyl groups include β-halo-substituted ethyl groups. Still other haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Halogenated alkenyl, and C 2-4 Haloalkynyl. Summarize

[0430] Although the foregoing embodiments have been described in some detail for the purpose of clarity of understanding, it is apparent that certain changes and modifications may be implemented within the scope of the appended claims. It should be noted that there are many alternative ways to implement the processes, systems and devices of the present embodiments. Therefore, the embodiments presented are considered to be illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method for processing a substrate, the method comprising: providing a substrate having features thereon; exposing the substrate to a silicon-containing precursor in a vapor phase for a duration sufficient to cause at least some of the silicon-containing precursor to adsorb on a surface of the substrate to form an adsorbed silicon-containing precursor; exposing the substrate to a first nitrogen-containing gas in a plasma-free environment; as well as The substrate is exposed to a plasma generated by igniting a second nitrogen-containing gas to form silicon nitride on the surface of the substrate.

2. The method of claim 1, wherein the plasma comprises radical species selected from the group consisting of nitrogen radicals, hydrogen radicals, and nitrogen-hydrogen radicals.

3. The method of claim 1 , wherein at least one of exposing the substrate to the first nitrogen-containing gas in the plasma-free environment and exposing the substrate to the plasma generated by igniting the second nitrogen-containing gas further comprises exposing the substrate to hydrogen gas. The method of claim 1 , wherein the second nitrogen-containing gas comprises two or more gases. The method of claim 1 , wherein the silicon-containing precursor is a halogen-containing precursor. The method of claim 1 , wherein the plasma is remotely generated.

7. The method of claim 1, further comprising exposing the formed silicon nitride to an in-situ nitridation or oxidation process to combine nitrogen or oxygen to form a second silicon-containing film.

8. The method of claim 1 further comprising setting a temperature of one or more chamber components of a processing chamber for housing a substrate to at least about 650° C. before providing the substrate having the features thereon; introducing a halogen-free aminosilane precursor to the processing chamber after setting the temperature to at least about 650° C.; and introducing a nitrogen-containing reactant and igniting a plasma to form a silicon nitride undercoat on at least one of the one or more chamber components.

9. A method of processing a processing chamber without a substrate therein, the method comprising: setting a temperature of one or more chamber components of the process chamber to at least about 650° C.; After setting the temperature to at least about 650° C., introducing a halogen-free aminosilane precursor into the processing chamber; and A nitrogen-containing reactant is introduced and a plasma is ignited to form a silicon nitride base coating on at least one of the one or more chamber components.

10. A method for processing a substrate, the method comprising: introducing a substrate having features; exposing the substrate to a silicon-containing precursor for a duration sufficient to cause at least some of the silicon-containing precursor to adsorb on a surface of the substrate; exposing the substrate to a reactant species to form a first silicon-containing film; as well as The first silicon-containing film is exposed to an in-situ nitridation or oxidation process to incorporate nitrogen or oxygen to form a second silicon-containing film.

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