Silicon nitride deposition

Abstract

Methods and apparatus are provided for depositing silicon nitride in a variety of applications. Embodiments include depositing silicon nitride directly onto a silicon or silicon oxide surface using a controlled dose-to-conversion-time ratio in thermal atomic layer deposition. Embodiments include exposing the silicon oxide surface to a nitrogen-containing plasma treatment prior to depositing the silicon nitride, and depositing the silicon nitride by thermal atomic layer deposition.

Description

Incorporation by Reference

[0001] A PCT application is being filed contemporaneously herewith as a part of this application, and each application identified in that contemporaneously filed PCT application to which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes. [Background technology]

[0002] Semiconductor device fabrication may involve the deposition of silicon nitride films. Silicon nitride thin films have unique physical, chemical, and mechanical properties and are therefore used in a variety of applications. For example, silicon nitride films may be used as diffusion barriers, gate insulators, sidewall spacers, encapsulation layers, strain membranes, etc. in transistors.

[0003] The background description provided herein is intended to provide a general overview of the contents of the present disclosure. Work by the currently named inventors within the scope of what is described in this Background section, as well as aspects of the description that may not otherwise be regarded as prior art at the time of filing, are not admitted, expressly or impliedly, as prior art against the present disclosure. Summary of the Invention

[0004] One embodiment involves a method for processing a substrate, the method including providing a semiconductor substrate having an exposed surface to a process chamber, performing a pretreatment on the semiconductor substrate by (1) heating the semiconductor substrate to a first temperature and / or (2) exposing the semiconductor substrate to a nitrogen-containing plasma, introducing a flow of a halosilane gas into the process chamber using a dosage time, purging the process chamber for a first purge time after stopping the flow of the halosilane gas, introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride by thermal atomic layer deposition, and purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas.

[0005] In various embodiments, the exposed surface comprises silicon oxide.

[0006] In various embodiments, the nitrogen-containing plasma is formed by igniting a second nitrogen-containing gas, which may be, for example, any one of nitrogen, ammonia, nitrous oxide, and combinations thereof.

[0007] In various embodiments, the first temperature is less than about 800°C.

[0008] In various embodiments, the first temperature and the second temperature are the same.

[0009] In various embodiments, the halosilane gas includes chlorine.

[0010] Another aspect involves a method for processing a substrate, the method including providing a semiconductor substrate having an exposed surface to a process chamber, heating the semiconductor substrate to a first temperature, performing a pretreatment on the semiconductor substrate by exposing the semiconductor substrate to a nitrogen-containing plasma, heating the semiconductor substrate to a second temperature after performing the pretreatment, introducing a flow of a halosilane gas into the process chamber in a plasma-free environment using a dosage time after heating the semiconductor substrate to the second temperature, purging the process chamber for a first purge time after stopping the flow of the halosilane gas, introducing a flow of a first nitrogen-containing gas into the process chamber in a plasma-free environment using a conversion time to form silicon nitride, and purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas.

[0011] In various embodiments, the exposed surface comprises silicon oxide.

[0012] In various embodiments, the nitrogen-containing plasma is formed by igniting a second nitrogen-containing gas, which may be, for example, any one of nitrogen, ammonia, nitrous oxide, and combinations thereof.

[0013] In various embodiments, the first temperature is less than about 800°C.

[0014] In various embodiments, the first temperature and the second temperature are the same.

[0015] In various embodiments, the halosilane gas includes chlorine.

[0016] Another aspect involves a method for processing a substrate including providing a semiconductor substrate having an exposed surface to a process chamber; exposing the exposed surface to a nitrogen-containing plasma; introducing a flow of a silicon-containing gas into the process chamber using a dosage time; purging the process chamber for a first purge time after stopping the flow of the silicon-containing gas; introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride by thermal atomic layer deposition; and purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas, wherein a ratio of dosage time to conversion time is from about 1:1 to about 10:4.

[0017] In various embodiments, the silicon nitride has an atomic ratio of silicon to nitrogen of at least about 0.69.

[0018] In various embodiments, the silicon nitride has an atomic ratio of silicon to nitrogen of at least about one.

[0019] In various embodiments, the silicon-containing gas comprises chlorine.

[0020] In various embodiments, the silicon-containing gas is a halosilane.

[0021] In various embodiments, the exposed surface comprises silicon, hi some embodiments, the exposed surface further comprises oxygen.

[0022] Another aspect involves a method for processing a substrate comprising providing a semiconductor substrate having an exposed surface to a process chamber; exposing the exposed surface to a nitrogen-containing plasma; introducing a flow of a silicon-containing gas into the process chamber in a plasma-free environment using a dose time; purging the process chamber for a first purge time after stopping the flow of the silicon-containing gas; introducing a flow of a first nitrogen-containing gas into the process chamber in a plasma-free environment using a conversion time to form silicon nitride; and purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas, whereby a ratio of dose time to conversion time is from about 1x:3x to about 10x:12x, where x is from about 0.2 seconds to about 10 seconds.

[0023] In various embodiments, the silicon nitride has an atomic ratio of silicon to nitrogen of at least about 0.69.

[0024] In various embodiments, the silicon nitride has an atomic ratio of silicon to nitrogen of at least about one.

[0025] In various embodiments, the silicon-containing gas comprises chlorine.

[0026] In various embodiments, the silicon-containing gas is a halosilane.

[0027] In various embodiments, the exposed surface comprises silicon, hi some embodiments, the exposed surface further comprises oxygen.

[0028] Another aspect involves an apparatus for processing a substrate, the apparatus including one or more process chambers, each process chamber including a chuck, one or more gas inlets to the process chambers and associated flow control hardware, and a controller having at least one processor and a memory, the at least one processor and the memory communicatively connected to each other, the at least one processor at least operatively connected to the flow control hardware, and the memory storing computer executable instructions for controlling the at least one processor to at least provide a substrate to one of the one or more process chambers, generate a plasma using a nitrogen-containing gas to generate nitrogen plasma species, expose the substrate to the nitrogen plasma species in the one or more process chambers, introduce a silicon-containing precursor to the one or more process chambers, and introduce a nitrogen-containing reactant to convert the silicon-containing precursor to silicon nitride in a plasma-free environment.

[0029] Another aspect involves an apparatus for processing a substrate, the apparatus including one or more process chambers, each process chamber including a chuck, one or more gas inlets to the process chambers and associated flow control hardware, and a controller having at least one processor and a memory, the at least one processor and the memory communicatively coupled to each other, the at least one processor at least operatively coupled to the flow control hardware, the memory storing computer executable instructions for controlling the at least one processor to control the flow control hardware to at least provide a substrate to one of the one or more process chambers, introduce a halosilane precursor to the one or more process chambers for a dosage time, and introduce a nitrogen-containing reactant for a conversion time to convert the halosilane precursor to silicon nitride in a plasma-free environment, whereby a ratio of dosage time to conversion time is between about 1x:3x and about 10x:12x, where x is between about 0.2 seconds and about 10 seconds is used.

[0030] These and other aspects are further described below with reference to the drawings. [Brief description of the drawings]

[0031] [Figure 1A] FIG. 1A is a process flow diagram illustrating operations performed in accordance with certain disclosed embodiments.

[0032] [Figure 1B] FIG. 1B is a process flow diagram illustrating operations performed in accordance with certain disclosed embodiments.

[0033] [Diagram 2] FIG. 2 is a timing schematic illustrating gas flow and plasma on and off phases for various operations that may be performed in accordance with certain disclosed embodiments.

[0034] [Diagram 3] FIG. 3 is a schematic diagram of an exemplary process chamber for practicing certain disclosed embodiments.

[0035] [Figure 4] FIG. 4 is a schematic diagram of an exemplary process tool for practicing certain disclosed embodiments.

[0036] [Diagram 5] FIG. 5 is a graph of experimental results showing growth rate per cycle for silicon nitride deposition on various substrates.

[0037] [Figure 6] FIG. 6 is a graph of experimental results showing the relative nitrogen content for silicon nitride films deposited on oxide and silicon substrates.

[0038] [Figure 7] FIG. 7 is a graph of experimental results showing growth rate per cycle for silicon nitride deposition on various substrates.

[0039] [Figure 8] FIG. 8 is a graph of experimental results showing sidewall growth rate per cycle for various depths of features on various substrates.

[0040] [Figure 9A] FIG. 9A is a diagram illustrating the silicon content of silicon nitride films. [Figure 9B] FIG. 9B is a diagram illustrating the silicon content of silicon nitride films.

[0041] [Figure 10A] FIG. 10A is a graph of experimental results showing sidewall thickness of a silicon nitride film deposited on a feature of a substrate versus feature depth. [Figure 10B] FIG. 10B is a graph of experimental results showing sidewall thickness of a silicon nitride film deposited on a feature of a substrate versus feature depth. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with specific embodiments, it will be understood that the specific embodiments are not intended to limit the disclosed embodiments.

[0043] Semiconductor fabrication processes involve the deposition of silicon nitride. Certain fabrication processes may involve forming silicon nitride on and in various structures. The structures may have various topographies and compositions, and it may be difficult to deposit silicon nitride in or on such structures. For example, it may be difficult to deposit silicon nitride on silicon oxide surfaces, and it may be difficult to deposit silicon nitride on high aspect ratio features, and some applications may utilize silicon nitride with variable Si:N atomic ratios. Although certain methods may be used to deposit silicon nitride in general, such methods have drawbacks such as the use of very high temperatures, longer process times, reduced tunability range, and increased nucleation delay.

[0044] Provided herein are methods for depositing silicon nitride using pretreatments involving either a nitrogen-containing plasma or thermal treatments prior to depositing silicon nitride by thermal ALD that use tunable process conditions, including relative dose and conversion times during atomic layer deposition (ALD), to achieve a variety of advantageous characteristics, including, but not limited to, conformality in high aspect ratio features, silicon-rich silicon nitride films, and reduced nucleation lag.

[0045] Figures 1A and 1B are process flow diagrams illustrating operations that may be performed in methods according to certain disclosed embodiments. Further examples are described below with respect to the timing diagram of Figure 2. It should be noted that while Figure 2 shows a particular sequence of operations performed in one embodiment, other variations, including or excluding plasma treatment, including or excluding thermal treatment, and including or excluding adjustment of dose, conversion, and purge times, may be performed depending on the desired properties of the deposited silicon nitride.

[0046] Certain disclosed embodiments are directed to ALD processes. ALD is a technique that uses sequential self-limiting reactions to deposit thin layers of materials. Typically, an ALD cycle includes operations 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 sub-layer of a film. As an example, a silicon nitride deposition cycle can include the following operations: (i) delivery / adsorption of a silicon-containing precursor, (ii) purging the silicon precursor from the chamber, (iii) delivery of a nitrogen-containing reactant or nitrogen-containing gas, and (iv) purging the nitrogen-containing reactant and additional reaction by-products from the chamber.

[0047] Unlike chemical vapor deposition (CVD) techniques, ALD processes use surface-mediated deposition reactions to deposit films layer by layer. In one example of an ALD process, a substrate surface containing a population of surface active sites is exposed to a gas-phase distribution of a first precursor, such as a silicon-containing precursor, in a dose provided to a chamber housing the substrate. Molecules of this first precursor are adsorbed to the substrate surface, including chemisorbed species and / or physisorbed molecules of the first precursor. It should be understood that when a compound is adsorbed to a substrate surface as described herein, the adsorbed layer may include the compound as well as derivatives of the compound. For example, an adsorbed layer of a silicon-containing precursor may include the silicon-containing precursor as well as derivatives of the silicon-containing precursor. After the dose of the first precursor, the chamber is evacuated to remove most or all of the first precursor remaining in the gas phase, leaving most or only the adsorbed species. In some embodiments, 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 mitigate reaction. A second reactant, such as a nitrogen-containing reactant, is introduced into the chamber, causing some of these molecules to react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed first precursor. The chamber can then be evacuated again to remove unbound second reactant molecules. As mentioned above, in some embodiments, the chamber may not be fully evacuated. Additional ALD cycles can also be used to build up the film thickness.

[0048] In certain embodiments, the dose of the first precursor of the ALD partially saturates the substrate surface. In some embodiments, the dose phase of the ALD cycle is terminated before the precursor contacts the substrate and uniformly saturates the surface. Typically, the precursor flow is stopped or redirected at this point, and only the purge gas flows. By operating in this subsaturated region, the ALD process shortens cycle time and increases throughput. However, because the adsorption of the precursor is not limited to saturation, the concentration of the adsorbed precursor may vary slightly across the substrate surface. An example of an ALD process operating in the subsaturated region is provided in U.S. Patent Application No. 14 / 061,587, entitled “SUB SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION,” filed on October 23, 2013 (now U.S. Patent No. 9,355,839), the disclosure of which is incorporated herein by reference in its entirety.

[0049] As described, in some embodiments, the ALD process includes plasma activation. As described herein, the ALD process and apparatus described herein may be a conformal film deposition (CFD) process, which is generally described in U.S. Patent Application No. 13 / 084,399, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," filed April 11, 2011 (now U.S. Patent No. 8,728,956), and U.S. Patent Application No. 13 / 084,305, entitled "SILICON NITRIDE FILMS AND METHODS," filed April 11, 2011, the disclosures of which are incorporated herein by reference in their entireties.

[0050] In operation 102 of Figure 1A, a substrate is provided to a process chamber. The substrate may be a silicon wafer, e.g., a 200 mm wafer, or a 300 mm wafer, including wafers having one or more layers of materials, such as dielectric, conductive, or semiconductive materials, deposited thereon. Non-limiting examples of underlayers include dielectric and conductive layers, e.g., silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0051] In some embodiments, the process chamber is a single wafer chamber. In some embodiments, the process chamber is a single wafer station in a multi-station chamber, such as a four-station chamber. In some embodiments, the process chamber is a furnace chamber. An example of a process chamber is further described below with reference to FIG.

[0052] In some embodiments, the operations of FIG. 1A are performed at the same chamber pressure, for example, from about 0.5 Torr to about 50 Torr, or from about 5 Torr to about 25 Torr. In some embodiments, the operations of FIG. 1A are performed at equal pressures. In some embodiments, the operations of FIG. 1A are performed in different chambers or at different pressures. In some embodiments, a multi-station chamber is used such that each station is set to a different pressure, and the substrate can be shuttled between stations during processing such that one or more operations are performed at different stations.

[0053] In some embodiments, the operations of FIG. 1A are performed at different temperatures. In some embodiments, the operations of FIG. 1A are performed at the same temperature or isothermally. Exemplary deposition temperatures may be about 500° C. to about 700° C., or less than about 850° C., or less than about 700° C., or less than about 650° C., or about 650° C. The temperature may refer to a pedestal temperature or a substrate temperature, which is understood to be the temperature at which the pedestal is set to heat or cool the substrate to a set temperature. In some embodiments, the operations of FIG. 1A are performed in different chambers having different pedestal temperatures or at different temperatures. In some embodiments, a multi-station chamber is used such that each station is set to a different temperature, and the substrate can shuttle between stations during processing such that one or more operations are performed at different stations.

[0054] In operation 104, the substrate is heated to a desired temperature. In various embodiments, the temperature may be between about 500° C. and about 700° C., or less than about 850° C., or less than about 700° C., or less than about 650° C., or about 650° C., or less than about 500° C., or less than about 400° C., or less than about 300° C., or less than about 200° C.

[0055] In operation 106, the surface of the substrate is optionally treated with a nitrogen-containing plasma. In some embodiments, both operations 104 and 106 may be performed. In some embodiments, only one of operations 104 and 106 is performed. In some embodiments, heating the substrate in operation 104 is selected to enable deposition of a silicon-rich film using a halosilane precursor. In some embodiments, treating the substrate in operation 106 may be performed to reduce nucleation delay on the substrate surface. For example, when depositing silicon nitride on a silicon oxide surface, the silicon oxide surface of the substrate may be treated in operation 106 before depositing silicon nitride, since it may be difficult for the silicon nitride deposition precursor to nucleate on the silicon oxide surface. In various embodiments, operation 106 may be performed before operations 108-114, or after operation 104, or both.

[0056] The treatment with nitrogen-containing plasma in operation 106 may be performed by flowing or introducing nitrogen-containing plasma species generated or ignited using a nitrogen-containing gas at an upstream location or a remote chamber, or by flowing or introducing a nitrogen-containing gas into the chamber and igniting the gas in situ. The nitrogen-containing gas may be any suitable nitrogen-containing gas, such as, but not limited to, nitrogen, ammonia, deuterated ammonia (ND3), NH2D, NHD2, and combinations thereof. In various embodiments, a gas containing both nitrogen and hydrogen may be used. In various embodiments, a mixture of nitrogen-containing gases may be used, such as, but not limited to, a mixture of nitrogen and ammonia. The plasma species used to perform the treatment may be ion-free. The plasma species used to perform the treatment may be radical-based. In various embodiments, the plasma species passes through a showerhead such that the substrate surface is primarily exposed to the radicals. Radicals that may be used for plasma treatment include, but are not limited to, nitrogen radicals and hydrogen radicals. In some embodiments, the radicals include NH radicals. In some embodiments, the plasma is an inductively coupled plasma. In some embodiments, the plasma is a capacitively coupled plasma. In some embodiments, the plasma is a radical-assisted plasma. In some embodiments, the plasma is an ion-free plasma. The more radicals the substrate is exposed to, the more reduced the nucleation delay in the subsequent silicon nitride deposition.

[0057] The plasma may be generated using a plasma power of about 500W to about 10,000W, or about 500W to about 4,000W, or about 1,000W to about 4,000W, or about 2,000W to about 4,000W for a single station chamber. The flow rate of the nitrogen-containing gas depends on the nitrogen-containing gas selected and the mixture of gases used. For example, in a mixture of nitrogen gas and ammonia, the percentage of nitrogen gas may be about 0% to about 100%, the percentage of ammonia gas may be about 0% to about 100%, and the sum of the percentages of nitrogen gas and ammonia gas relative to the total flow rate of the nitrogen-containing gas is 100%. For example, in one non-limiting example, a mixture of 40% nitrogen gas and 60% ammonia gas is used. The relative flow rates of nitrogen gas and ammonia gas may be about 1:10 to about 200:1.

[0058] In some embodiments, the nitrogen gas, either as a mixture or alone, may be flowed into the single station chamber at a flow rate of about 1 slm to about 50 slm, or about 10 slm to about 30 slm. In some embodiments, the ammonia gas, either as a mixture or alone, may be flowed into the single station chamber at a flow rate of about 100 sccm to about 10,000 sccm, or about 4,000 sccm to about 5,000 sccm.

[0059] The duration of the plasma treatment depends on various factors, including the material being deposited, the surface on which the material is deposited, the precursors used for material deposition, and other process conditions. In various embodiments, the plasma treatment may be performed for a duration of about 30 seconds to about 30 minutes, or about 1 minute to about 30 minutes, or about 10 minutes to about 30 minutes. In various embodiments, operation 106 is performed only once before silicon nitride is deposited. In some embodiments, operation 106 is performed on the exposed silicon oxide surface one before silicon nitride is deposited.

[0060] In operation 108, the halosilane precursor is introduced into the process chamber under a controlled dosage time. In various embodiments, the halosilane precursor is introduced without the use of a plasma. In various embodiments, the halosilane precursor is introduced into the process chamber in a plasma-free environment.

[0061] Operation 108 may be performed in various embodiments to form silicon-rich films. That is, in some embodiments, the use of halosilane precursors in combination with specific dose times can form silicon-rich films. Exemplary dose times include, but are not limited to, about 0.1 seconds to about 100 seconds. A dose time can refer to the duration during which a flow of a precursor used during dosing is introduced into a process chamber. For example, a dose time for dichlorosilane can be the duration during which dichlorosilane is introduced into a process chamber.

[0062] Any halosilane precursor can be used in operation 108. A halosilane precursor is also referred to as a halogen-containing silane precursor, or a halogen-containing silicon precursor, or a halogen-containing silane gas. In some embodiments, a halogen-containing silane can be used such that the silane contains at least one hydrogen atom. Such silanes include, for example, SiX a H y where y>0 and X is a halogen. For example, dichlorosilane (H2SiCl2) may be used in some embodiments. In some embodiments, the silane is Si a X b where a≧0, and b≧0 (i.e., b=a+4). In such embodiments, the silanes may include tetrachlorosilane and HCDS.

[0063] In some embodiments, a halogen-containing silane precursor may be used such that the silane contains at least one hydrogen atom. Such silanes include, for example, SiX a H ywhere y>1. In some embodiments, the halogen-containing silane may be a dihalosilane or trihalosilane, or may contain more than three silicon atoms. In some embodiments, for example, dichlorosilane (H2SiCl2) may be used in some embodiments. Another example of the chemical formula of the halogen-containing silane is Si n X y H z where X is a halogen, H is hydrogen, n is an integer equal to or greater than 1 and equal to the number of Si atoms in the molecule, and in some embodiments, y is from about 1 to about 4, and z is 4-y. In some embodiments, the halogen-containing silane is n X y where n is any integer equal to or greater than 1, and y is 2n+2. Additional examples include, but are not limited to, SiHCl3, SiH2Cl2, SiH3Cl, and Si2Cl6. Another example of the formula for a halogen-containing silane is Si n H 2n+1 X, n is an integer equal to or greater than 1, and X is a halogen. Examples of halosilanes are iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like.

[0064] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is an organosilicon-containing precursor.

[0065] In some embodiments, the halosilane precursor comprises at least one optionally substituted C 1-2 Non-limiting examples of haloaliphatic groups include -CX y H 3-y, y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I);-CX z H 2-z CX y H 3-y , z is 0, 1, or 2, y is 0, 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; or -CHCX y H 3-y , y is 1, 2, or 3, and each X is independently halo (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), chloro ...Cl), chlorofluoromethyl (-CHCl), chlorofluoromethyl (-CHBr), bromomethyl (-CHBr), dibromomethyl (-CHBr), tribromomethyl (-CHBr), tribromomethyl (-CBr), iodomethyl (-CH2I), diiodomethyl 2-fluoroethyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CHCHF), 2-chloroethyl (-CHCHCl), 2-bromoethyl (-CHCHBr), 2-iodoethyl (-CHCHI), 2,2-difluoroethyl (-CHCHF), 2,2-dichloroethyl (-CHCHCl), 2,2-dibromoethyl (-CHCHBr), 2,2-diiodoethyl (-CHCHI), 2,2-fluoroiodoethyl (-CHCHFI), and the like. In certain embodiments, C 1-2 Haloalkyl includes β-halo substituted ethyl. Further haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 Haloalkynyl is mentioned.

[0066] The flow rate of the halosilane depends on the size of the chamber, the chamber pressure, the precursors used, and various other features. In various embodiments, the flow rate of the halosilane for a single station chamber is about 100 sccm to about 2000 sccm, or about 300 sccm to about 1500 sccm, or about 500 sccm to about 1500 sccm. In some embodiments, nitrogen gas may also be introduced to dilute the precursor. For example, in some embodiments, the flow rate of the nitrogen gas for a single station chamber may be about 1000 sccm to about 40000 sccm, or about 500 sccm to about 2000 sccm.

[0067] The chamber pressure during operation 106 may be between about 1 Torr and about 25 Torr, or between about 1 Torr and about 10 Torr, or between about 3 Torr and about 10 Torr, or between about 5 Torr and about 10 Torr.

[0068] The dose time in operation 108 can be adjusted to modify the properties of the deposited silicon nitride film. For example, in some embodiments, to form a silicon-rich silicon nitride film, the dose time for operation 108 can be from about 0.1 seconds to about 100 seconds, or from about 1 second to about 100 seconds, or from about 40 seconds to about 60 seconds.

[0069] In operation 110, the process chamber may be purged. Purging the chamber may involve flowing a purge or sweep gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Exemplary purge gases include argon, hydrogen, nitrogen, and helium. In various embodiments, the purge gas is an inert gas. The purge gas may include one or more gases. In some embodiments, operation 110 may include one or more evacuation sub-stages to evacuate the process chamber. Alternatively, it will be understood that in some embodiments, operation 110 may be omitted. Operation 110 may have any suitable duration, such as from about 0 seconds to about 60 seconds, for example, about 0.01 seconds. In some embodiments, increasing the flow rate of one or more purge gases may decrease the duration of operation 110. For example, the purge gas flow rate may be adjusted according to the thermodynamic and / or geometric properties of various reactants of the process chamber and / or the process chamber piping to modify the duration of operation 110. In one non-limiting example, the duration of the purge step may be adjusted by adjusting the purge gas flow rate. This may shorten the deposition cycle time and improve substrate throughput. After purging, the silicon-containing precursor molecules remain adsorbed on the substrate surface. In some embodiments, the silicon-containing precursor is flowed into the chamber housing the substrate at a flow rate of about 1000 sccm to about 5000 sccm.

[0070] In operation 112, a nitrogen-containing reactant is introduced into the process chamber and reacts with the adsorbed silicon-containing precursor to form silicon nitride. In various embodiments, the nitrogen-containing reactant reacts with the silicon-containing precursor in a thermal reaction. In various embodiments, the nitrogen-containing reactant reacts with the silicon-containing precursor in a plasma-free reaction. In various embodiments, the nitrogen-containing reactant is introduced into the process chamber in a plasma-free environment. The nitrogen-containing reactant may be introduced in a plasma-free environment. The nitrogen-containing reactant may thermally react with the silicon nitride deposition precursor to form silicon nitride. In various embodiments, the nitrogen-containing reactant reacts with the silicon nitride deposition precursor to undergo a thermal ALD process.

[0071] In various embodiments, one or more process conditions used during operation 112 can be adjusted to modify the silicon content of the deposited silicon nitride. For example, the conversion time of operation 112 can be adjusted to form a silicon-rich film. Other process conditions can also be adjusted to form silicon-rich silicon nitride. One way to form silicon-rich silicon nitride is by adjusting the exposure time of operation 112. For example, the nitrogen-containing reactant can be introduced for a time period from about 1 second to about 120 seconds. The ratio of dose time to conversion time can be from about 1:1 to about 10:4.

[0072] Other process conditions that may be adjusted include reactant flow rates, chamber pressure, temperature, and dilution. In some embodiments, the flow rate of the nitrogen-containing reactant may be between about 2000 sccm and about 10000 sccm, for example, for a single station chamber, ammonia gas may be flowed using a flow rate of between about 2000 sccm and about 10000 sccm. In some embodiments, a hydrogen-containing gas is flowed along with the nitrogen-containing reactant. For example, one hydrogen-containing gas that may be used includes hydrogen gas. Hydrogen gas may be flowed using a flow rate of between about 0 sccm and about 5000 sccm for a single station chamber. During operation 112, the chamber pressure may be between about 5 Torr and about 25 Torr. In some embodiments, nitrogen gas is also flowed along with the ammonia and optionally the hydrogen gas. For example, nitrogen gas may be flowed at a flow rate of between about 500 sccm and about 2000 sccm to dilute the nitrogen-containing gas. In some embodiments, nitrogen gas is used instead of ammonia.

[0073] In operation 114, the chamber may be purged again. In some embodiments, this operation is performed before operation 112, or after operation 112, or both before and after operation 112. The process conditions and techniques used in operation 114 may be the same or similar to those of operation 110.

[0074] In various embodiments, operations 108-114 may be repeated multiple times. Each repetition of operations 108-114 may constitute a cycle. The cycle may be repeated until the desired silicon nitride film is deposited.

[0075] In some embodiments, the formation of the silicon-rich silicon nitride film may involve cycles of operations 102, 104, 108, 110, 112, and 114, and operations 108-114. In some embodiments, the formation of the silicon-rich silicon nitride film involves operations 108-114 without thermal or plasma pretreatment, and the duration of operations 108 and 112 is adjusted to allow the silicon-rich film to form. For example, the ratio of the duration of operation 108 to operation 112 may be about 5:1 to about 5:4. In some embodiments, the ratio of the duration of operation 108 to the duration of operation 112 is about 1x:3x to about 10x:12x, where x is about 0.2 seconds to about 10 seconds, or about 5 seconds to about 10 seconds. In various embodiments, the silicon nitride has a silicon to nitrogen atomic ratio of at least about 0.69, or at least about 1.

[0076] In various embodiments, the step coverage of the silicon nitride film using certain disclosed embodiments is at least about 80%, or at least about 90%, or about 100%. The silicon to nitrogen content of the silicon nitride film deposited using certain disclosed embodiments can be tuned from about 0.69 to about 1.10. The hydrogen content of the deposited silicon nitride can also be controlled by adjusting the process conditions of operations 108 and 112, such as exposure time, dosage time, or conversion time.

[0077] 1B shows another process flow diagram illustrating operations that may be performed according to certain disclosed embodiments. In operation 142, a substrate having silicon oxide is provided to a process chamber. The substrate may be a silicon wafer, e.g., a 200 mm wafer, or a 300 mm wafer, including wafers having one or more layers of materials, such as dielectric, conductive, or semiconductive materials, deposited thereon. Non-limiting examples of underlayers include dielectric and conductive layers, e.g., silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0078] In some embodiments, the process chamber is a single wafer chamber. In some embodiments, the process chamber is a single wafer station in a multi-station chamber, such as a four-station chamber. In some embodiments, the process chamber is a furnace chamber. An example of a process chamber is further described below with reference to FIG.

[0079] In some embodiments, the operations of FIG. 1B are performed at the same chamber pressure, for example, about 0.5 Torr to about 50 Torr. In some embodiments, the operations of FIG. 1B are performed in different chambers or at different pressures. In some embodiments, a multi-station chamber is used such that each station is set to a different pressure, and the substrate can be shuttled between stations during processing such that one or more operations are performed at different stations.

[0080] In some embodiments, the operations of FIG. 1B are performed at the same temperature, for example, about 500° C. to about 650° C., or less than about 850° C., or less than about 700° C., or less than about 650° C., or about 650° C. The temperature can refer to the pedestal temperature or the substrate temperature, which is understood to be the temperature at which the pedestal is set to heat or cool the substrate to a set temperature. In some embodiments, the operations of FIG. 1B are performed in different chambers having different pedestal temperatures or at different temperatures. In some embodiments, a multi-station chamber is used such that each station is set to a different temperature, and the substrate can be shuttled between stations during processing such that one or more operations are performed at different stations.

[0081] The silicon oxide surface is treated with a nitrogen-containing plasma in operation 146. The use of a nitrogen-containing plasma may be performed to reduce nucleation delay of silicon nitride deposition on the silicon oxide surface.

[0082] The treatment may be any of the treatments described above with respect to operation 106 of FIG. 1A. In some embodiments, the treatment is a nitrogen-containing plasma treatment. The plasma may be generated using a plasma power of about 500 W to about 10,000 W, or about 500 W to about 4,000 W, or about 1,000 W to about 4,000 W, or about 2,000 W to about 4,000 W for a single station chamber. The plasma may be generated by any suitable technique.

[0083] The flow rate of the nitrogen-containing gas depends on the nitrogen-containing gas selected and the mixture of gases used. For example, in a mixture of nitrogen gas and ammonia, the percentage of nitrogen gas may be about 0% to about 100%, the percentage of ammonia gas may be about 0% to about 100%, and the sum of the percentages of nitrogen gas and ammonia gas to the total flow rate of the nitrogen-containing gas is 100%. For example, in one non-limiting example, a mixture of 40% nitrogen gas and 60% ammonia gas is used. The relative flow rates of nitrogen gas and ammonia gas may be about 1:10 to about 200:1.

[0084] In some embodiments, the nitrogen gas, either as a mixture or alone, may be flowed into the single station chamber at a flow rate of about 1 slm to about 50 slm, or about 10 slm to about 30 slm. In some embodiments, the ammonia gas, either as a mixture or alone, may be flowed into the single station chamber at a flow rate of about 100 sccm to about 10,000 sccm, or about 4,000 sccm to about 5,000 sccm.

[0085] The duration of the plasma treatment depends on various factors, including the material being deposited, the surface on which the material is deposited, the precursors used for material deposition, and other process conditions. In various embodiments, the plasma treatment may be performed for a duration of about 30 seconds to about 30 minutes, or about 1 minute to about 30 minutes, or about 10 minutes to about 30 minutes. In various embodiments, operation 106 is performed only once before silicon nitride is deposited. In some embodiments, operation 106 is performed on the exposed silicon oxide surface one before silicon nitride is deposited.

[0086] The treatment with nitrogen-containing plasma in operation 106 may be performed by flowing or introducing nitrogen-containing plasma species generated or ignited using a nitrogen-containing gas at an upstream location or a remote chamber, or by flowing or introducing a nitrogen-containing gas into the chamber and igniting the gas in situ. The nitrogen-containing gas may be any suitable nitrogen-containing gas, such as, but not limited to, nitrogen, ammonia, nitrous oxide, and combinations thereof. In various embodiments, a gas containing both nitrogen and hydrogen may be used. In various embodiments, a mixture of nitrogen-containing gases may be used, such as, but not limited to, a mixture of nitrogen and ammonia. The plasma species used to perform the treatment may be ion-free. The plasma species used to perform the treatment may be radical-based. In various embodiments, the plasma species passes through a showerhead such that the substrate surface is primarily exposed to radicals. Radicals that may be used for plasma treatment include, but are not limited to, nitrogen radicals and hydrogen radicals. In some embodiments, the plasma is an inductively coupled plasma. In some embodiments, the plasma is a capacitively coupled plasma. In some embodiments, the plasma is a radical-assisted plasma. In some embodiments, the plasma is an ion-free plasma. The more radicals the substrate is exposed to, the more the nucleation delay in the subsequent silicon nitride deposition is reduced.

[0087] In operation 148, a silicon nitride deposition precursor is introduced into the process chamber. This operation can use any of the precursors and process conditions described above with respect to operation 108 of FIG. 1A. In various embodiments, a precursor containing silicon and chlorine is used. In some embodiments, dichlorosilane is introduced into the process chamber. In some embodiments, the silicon nitride precursor is trichlorosilane (SiHCl3). In some embodiments, the silicon nitride precursor is hexachlorodisilane (HCDS). In some embodiments, the silicon nitride precursor is tetrachlorosilane (SiCl4).

[0088] The deposition precursor may be any group IV-containing precursor, such as a silicon-containing precursor. In some embodiments, the deposition precursor may be a germanium-containing precursor. In some embodiments, hydrogen gas is simultaneously flowed into the chamber in addition to the deposition precursor and reactant. In various embodiments, the deposition precursor is an aminosilane.

[0089] The deposition precursor is selected based on the material to be deposited. For example, for the deposition of silicon oxide, a silicon-containing precursor can be selected. An exemplary silicon-containing precursor has the following structure: [ka] a silicon-containing precursor having

[0090] R1, R2, and R3 may be the same or different substituents and may include silane, amine, halide, hydrogen, or organic groups such as alkylamines, alkoxy, alkyl, alkenyl, alkynyl, and aromatic groups.

[0091] Exemplary silicon-containing precursors include polysilanes (H3Si-(SiH2) n —SiH3), where n≧1, such as silane, disilane, trisilane, tetrasilane, and trisilylamine: [ka]

[0092] In some embodiments, the silicon-containing precursor is an alkoxysilane. Alkoxysilanes that can be used include, but are not limited to, the following:

[0093] H x -Si-(OR) y , x=1 to 3, x+y=4, R is a substituted or unsubstituted alkyl group, and

[0094] H x (RO) y -Si-Si-(OR) y H x , x=1 to 2, x+y=3, and R is a substituted or unsubstituted alkyl group.

[0095] Examples of silicon-containing precursors include tetraethyl orthosilicate (TEOS), TMOS (tetramethoxysilane), octamethylcyclotetrasiloxane (OMCTS), methylsilane, trimethylsilane (3MS), ethylsilane, butasilane, pentasilane, octasilane, heptasilane, hexasilane, cyclobutasilane, cycloheptasilane, cyclohexasilane, cyclooctasilane, cyclopentasilane, 1,4-dioxa-2,3,5,6-tetrasilacyclohexane, diethoxymethylsilane (DEMS), diethoxymethylsilane (DEMS), cyclopentasilane, cyclohex ... Examples of suitable silanes include but are not limited to butoxysilane (DES), dimethoxymethylsilane, dimethoxysilane (DMOS), methyl-diethoxysilane (MDES), methyl-dimethoxysilane (MDMS), octamethoxydodecasiloxane (OMODDS), tert-butoxydisilane, tetramethylcyclotetrasiloxane (TMCTS), tetraoxymethylcyclotetrasiloxane (TOMCTS), triethoxysilane (TES), triethoxysiloxane (TRIES), and trimethoxysilane (TMS or TriMOS).

[0096] As mentioned above, in some embodiments, the silicon-containing precursor may be an aminosilane having a hydrogen atom, such as bisdiethylaminosilane, diisopropylaminosilane (DIPAS), tert-butylaminosilane (BTBAS), tris(dimethylamino)silane (3DMAS), or 1-dimethylamino-1,1,5,5,5-pentamethyldisiloxane, or di-sec-butylaminosilane (DSBAS). Aminosilane precursors include, but are not limited to, the following: H x -Si-(NR) y , x=1 to 3, x+y=4, and R is an organic group or a hydride group.

[0097] In some embodiments, the silicon nitride deposition precursor is a halosilane, such as any of those described above with respect to operation 108 in FIG.

[0098] In one example, the silicon nitride deposition precursor is flowed at a flow rate of about 100 sccm to about 2000 sccm for a single station chamber. The duration of operation 148 in a single dose or exposure can be about 0.1 seconds to about 10 seconds. The chamber pressure is about 5 Torr to about 25 Torr. In some embodiments, nitrogen gas is introduced with the silicon nitride deposition precursor for dilution or is co-flowed with the silicon nitride deposition precursor. In some embodiments, the nitrogen gas is flowed for a duration of about 500 sccm to about 2000 sccm. In some embodiments, operation 148 is performed in a plasma-free environment.

[0099] In operation 150, the process chamber is optionally purged. Purging can be performed using any of the process conditions or techniques described above with respect to operation 110 of FIG. 1A. In some embodiments, purging is performed by flowing a purge gas, such as nitrogen gas. The purge gas may be flowed at a flow rate of about 1000 sccm to about 40000 sccm for a single station chamber. The purge operation can 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. In some embodiments, a lower pressure, such as less than about 0.1 Torr, can be used to more effectively purge.

[0100] In operation 152, a nitrogen-containing reactant is introduced into the process chamber to form silicon nitride on the substrate surface. The nitrogen-containing reactant may be introduced in a plasma-free environment. The nitrogen-containing reactant may thermally react with the silicon nitride deposition precursor to form silicon nitride. In various embodiments, the nitrogen-containing reactant reacts with the silicon nitride deposition precursor to undergo a thermal ALD process.

[0101] The nitrogen-containing reactant may be any nitrogen-containing reactant, such as nitrogen gas, ammonia gas, or a combination thereof. In some embodiments, the nitrogen-containing gas includes hydrogen. In some embodiments, the nitrogen-containing gas is introduced with hydrogen gas. The process chemistries and process conditions for operation 152 may be any of those described above with respect to operation 112 of FIG. 1A.

[0102] In one example, operation 152 involves flowing ammonia gas using a flow rate between about 2000 sccm and about 10000 sccm, and hydrogen gas using a flow rate between about 0 sccm and about 5000 sccm, for a single station chamber for a duration between about 1 second and about 30 seconds, using a chamber pressure between about 5 Torr and about 25 Torr. In some embodiments, nitrogen gas is also flowed for dilution using a flow rate between about 500 sccm and about 2000 sccm.

[0103] In operation 154, the process chamber may be optionally purged again. Purging may be performed using any of the process conditions or techniques described above with respect to operation 110 of FIG. 1A. In some embodiments, purging is performed by flowing a purge gas, such as nitrogen gas. The purge gas may be flowed at a flow rate of about 1000 sccm to about 40000 sccm for a single station chamber. The purge operation 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. In some embodiments, a lower pressure, such as less than about 0.1 Torr, may be used to more effectively purge.

[0104] Operations 148-154 may be repeated in one or more cycles. Each repetition of operations 148-154 may constitute a cycle. The cycle may be repeated until the desired silicon nitride film is deposited. In some embodiments, the cycle includes only operations 148 and 152. In some embodiments, the cycle includes operations 148, 150, and 152. In some embodiments, the cycle includes operations 150, 152, and 154. In some embodiments, the cycle includes operations 148, 150, 152, and 154.

[0105] FIG. 2 shows an exemplary timing diagram for the stages over time that may be performed in one embodiment of a particular disclosed embodiment. FIG. 2 shows a process 200 having a pretreatment stage 206A before two deposition cycles 200A and 200B. For each stage, it is illustrated whether an inert gas, a treatment gas, a silicon precursor gas, and a second reactant gas are flowed, and whether the plasma is turned on or off. During the pretreatment stage 206A, an inert gas can be flowed with the treatment gas, while the flow of the silicon precursor gas and the second reactant gas is off and the plasma is turned on. The pretreatment stage 206A may correspond to operation 106 of FIG. 1A or operation 146 of FIG. 1B. The pretreatment may be performed before silicon nitride is deposited on the substrate. In some embodiments, the pretreatment is performed on the exposed silicon oxide surface on the substrate.

[0106] The deposition cycle 200A includes a precursor stage 208A, a purge stage 210A, a conversion stage 212A, and a purge stage 214A. Although the deposition cycle 200A includes a purge stage, it will be understood that in certain embodiments, one or more purge stages may not be performed. During the precursor stage 208A, the flow of the silicon precursor is turned on while the flow of the process gas is turned off, the inert gas can continue to flow (as a carrier gas, a dilution gas, a delivery gas, or any of the above), but the flow of the second reactant remains off, and the plasma is turned off. The precursor stage 208A may correspond to operation 108 of FIG. 1A or operation 148 of FIG. 1B. Returning to FIG. 2, following the precursor stage 208A, a purge stage 210A is performed. During the purge stage 210A, the inert gas, such as a purge gas, can continue to flow while the process gas and the second reactant gas remain off. During the purge stage 210A, the silicon precursor gas is turned off and the plasma remains off. The purge stage 210A may correspond to operation 110 of FIG. 1A or operation 150 of FIG. 1B. Returning to FIG. 2, following the purge stage 210A, a conversion stage 212A may be performed. During the conversion stage 212A, the inert gas may continue to flow and the second reactant gas is turned on. An exemplary second reactant gas may be ammonia. The second reactant gas may include one or more gases. During the conversion stage 212A, the flow of the process gas remains off, the flow of the silicon precursor gas remains off, and the plasma remains off. The conversion stage 212A may correspond to operation 112 of FIG. 1A or operation 152 of FIG. 1B. Returning to FIG. 2, following the conversion stage 212A, a purge stage 214A may be performed. During the purge stage 214A, the inert gas, such as a purge gas, can continue to flow while the flow of the process gas remains off and the flow of the silicon precursor gas remains off. The flow of the second reactant is turned off and the plasma remains off. The purge stage 214A may correspond to operation 114 of FIG. 1A or operation 154 of FIG. 1B. Returning to FIG. 2, the deposition cycle 200A may be followed by a second deposition cycle 200B that repeats certain operations. The deposition cycle 200B includes a precursor stage 206B, a purge stage 210B, a conversion stage 212B, and a purge stage 214B.Although only two deposition cycles are illustrated in FIG. 2, it will be understood that in some embodiments, fewer or more cycles may be performed to deposit a desired thickness of silicon nitride. During precursor phase 208B, the flow of silicon precursor is turned on while the flow of process gas remains off, the inert gas can continue to flow (as a carrier gas, diluent gas, delivery gas, or any of the above), but the flow of the second reactant remains off, and the plasma remains off. Precursor phase 208B may correspond to iteration 108 of FIG. 1A or iteration 148 of FIG. 1B. Returning to FIG. 2, following precursor phase 208B, purge phase 210B is performed. During purge phase 210B, the inert gas, such as purge gas, can continue to flow while the process gas and second reactant gas remain off. During purge phase 210B, silicon precursor gas is turned off and the plasma remains off. The purge stage 210B may correspond to the iteration 110 of FIG. 1A or the iteration 150 of FIG. 1B. Returning to FIG. 2, following the purge stage 210B, the conversion stage 212B may be performed. During the conversion stage 212B, the inert gas may continue to flow and the second reactant gas is turned on. An exemplary second reactant gas may be ammonia. The second reactant gas may include one or more gases. During the conversion stage 212B, the flow of the process gas remains off, the flow of the silicon precursor gas remains off, and the plasma remains off. The conversion stage 212B may correspond to the iteration 112 of FIG. 1A or the iteration 152 of FIG. 1B.

[0107] Certain disclosed embodiments may be used to form silicon-rich silicon nitride films. Silicon-rich silicon nitride films may have more silicon dangling bonds, which allows for better density control to form high energy traps used in silicon nitride charge trapping layers. Silicon-rich silicon nitride films have reduced hydrogen content by about 50% to about 90% compared to stoichiometric silicon nitride films. In various embodiments, silicon-rich silicon nitride films deposited using certain disclosed embodiments may achieve at least about 80%, or at least about 90%, or about 100%, or 100% conformality. For example, silicon-rich silicon nitride films may be formed by adjusting the dosing time and / or conversion time. In various embodiments, the density of the silicon nitride film may be about 2.5 g / cc to about 3.0 g / cc. In various embodiments, the wet etch rate of silicon nitride in 100:1 dilute hydrofluoric acid is about 2 Å / min to about 3 Å / min. In various embodiments, the refractive index of silicon nitride is about 2 Å / min to about 3 Å / min. The deposition rate may be about 0.4 Å / cycle to about 6 Å / cycle.

[0108] Certain disclosed embodiments can be used to reduce nucleation delay to form silicon nitride on silicon oxide surfaces. For example, plasma treatment can be used to reduce nucleation delay before depositing silicon nitride. The plasma treatment can involve flowing ammonia gas, nitrogen gas, or both, and igniting a plasma. Under the same process conditions, the thickness of the deposited silicon nitride increases with plasma treatment, and silicon nitride deposited after ammonia treatment has a greater thickness than silicon nitride deposited after nitrogen plasma treatment, which has a greater thickness than silicon nitride deposited without plasma treatment. Silicon nitride deposition using plasma treatment remains more selective on silicon surfaces than silicon oxide surfaces. When plasma treatment is performed before silicon nitride deposition, the pattern loading effect is reduced.

[0109] Device 3 illustrates a schematic diagram of one embodiment of an atomic layer deposition (ALD) process station 300 having a process chamber body 302 for maintaining a low pressure environment. Multiple ALD process stations 300 may be included in a common low pressure process tool environment. For example, FIG. 5 illustrates one embodiment of a multi-station processing tool 300. In some embodiments, one or more hardware parameters of the ALD process station 300 (including those described in more detail below) can be programmatically adjusted by one or more computer controllers 350.

[0110] The ALD process station 300 is in fluid communication with a reactant delivery system 301 for delivering process gases to a showerhead 306. The reactant delivery system 301 includes a mixing vessel 304 for blending and / or conditioning process gases, such as a silicon-containing precursor gas or a nitrogen-containing gas, 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 gases to the showerhead 306.

[0111] As an example, the embodiment of FIG. 3 includes a vaporization point 303 for vaporizing liquid reactants that are fed to the mixing vessel 304. In some embodiments, the vaporization point 303 may be a heated vaporizer. Saturated reactant vapors generated from such vaporizers may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactants may generate small particles. These small particles may clog the piping, interfere with valve operation, or contaminate the substrate. Some approaches to address these issues involve purging and / or evacuating the delivery piping to remove residual reactants. However, purging the delivery piping may increase process station cycle times and reduce process station throughput. Thus, in some embodiments, the delivery piping downstream of the vaporization point 303 may be heat traced. In some examples, the mixing vessel 304 may also be heat traced. In one non-limiting example, the piping downstream of the vaporization point 303 has an elevated temperature profile ranging from about 40° C. to about 55° C., or from about 60° C. to about 65° C. at the mixing vessel 304 .

[0112] In some embodiments, the liquid precursor or liquid reactant can be vaporized in a liquid injector. For example, the liquid injector can inject pulses of liquid reactant into the carrier gas stream upstream of the mixing vessel. In one embodiment, the liquid injector can vaporize the reactant by flashing the liquid from high pressure to low pressure. In another example, the liquid injector can atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. Small droplets can vaporize faster than large droplets, reducing the delay between liquid injection and full vaporization. The faster the vaporization, the shorter the length of piping downstream from the vaporization point 303 can be. In one scenario, the liquid injector can be attached directly to the mixing vessel 304. In another scenario, the liquid injector can be attached directly to the showerhead 306.

[0113] In some embodiments, a liquid flow controller (LFC) can be provided upstream of the vaporization point 303 to control the mass flow rate of the liquid vaporized and delivered to the ALD process station 300. For example, the LFC can include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC can then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take more than a second to stabilize the liquid flow using feedback control. This may extend the dosing time of the liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this can be implemented by disabling the sensing tube and the PID controller of the LFC.

[0114] The showerhead 306 distributes process gases toward the substrate 312. In the embodiment illustrated in Figure 3, the substrate 312 is shown positioned below the showerhead 306 and resting on a pedestal 308. The showerhead 306 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 312.

[0115] In some embodiments, the pedestal 308 can be raised or lowered to expose the substrate 312 to the volume 307 between the substrate 312 and the showerhead 306. It will be appreciated that in some embodiments, the height of the pedestal can be programmatically adjusted by a suitable computer controller 350.

[0116] In another scenario, adjusting the height of the pedestal 308 may allow the plasma density to be varied during plasma activation of the process in embodiments where a plasma is ignited. At the end of the process step, the pedestal 308 may be lowered to allow removal of the substrate 312 from the pedestal 308 during another substrate transfer step.

[0117] In some embodiments, the pedestal 308 may be temperature controlled via heater 310. In some embodiments, the pedestal 308 may be heated to a temperature of about 25° C. to about 800° C., or about 200° C. to about 700° C., during deposition of a silicon nitride film as described in the disclosed embodiments. In some embodiments, the pedestal is set to a temperature of about 25° C. to about 800° C., or about 200° C. to about 300° C.

[0118] Additionally, in some embodiments, pressure control for the ALD process station 300 may be provided by a butterfly valve 318. As shown in the embodiment of FIG. 3, the butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the ALD process station 300 may also be adjusted by varying the flow rates of one or more gases introduced to the ALD process station 300.

[0119] In some embodiments, the position of the showerhead 306 can be adjusted relative to the pedestal 308 to change the volume between the substrate 312 and the showerhead 306. Further, it will be understood that the vertical position of the pedestal 308 and / or the showerhead 306 may be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 308 may include a rotation axis for rotating the orientation of the substrate 312. It will be understood that in some embodiments, one or more of these exemplary adjustments can be implemented programmatically by one or more suitable computer controllers 350.

[0120] In some embodiments, where a plasma may be used as described above, the showerhead 306 and pedestal 308 are in electrical communication with a radio frequency (RF) power source 314 and matching network 316 to power the plasma. For example, the plasma may be used to treat a silicon oxide surface prior to depositing silicon nitride. In some embodiments, the plasma energy can be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 314 and matching network 316 can be operated at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is from about 150 W to about 6000 W for a single station chamber. For a four station chamber, the plasma power can include four generators, each powered up to about 6000 W, for a total of about 24000 W. To treat a silicon oxide surface, the substrate may be exposed to a nitrogen-containing gas, or a mixture of a nitrogen-containing gas and an optional inert gas, while a plasma is ignited using the RF power source 314 and matching network 316.

[0121] In some embodiments, the substrate may be exposed to a nitrogen-containing gas while igniting a plasma to treat the silicon oxide surface using a plasma power such as about 500 W to about 6000 W per surface area of ​​a 300 mm wafer. The plasma may be generated remotely (such as with a remote plasma generator) or directly in the chamber housing the substrate (i.e., in situ). The RF power source 314 may provide RF power at any suitable frequency. In some embodiments, the RF power source 314 may be configured to control high and low frequency RF power sources independently of each other. Exemplary low frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz, or up to about 2 MHz. Exemplary high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or frequencies greater than about 13.56 MHz, or frequencies greater than 27 MHz, or frequencies greater than 30 MHz, or frequencies greater than 60 MHz. It will be appreciated that any suitable parameters may be discretely or continuously adjusted to provide plasma energy for the surface reactions.

[0122] In some embodiments, the plasma can be monitored in-situ by one or more plasma monitors. In one scenario, the plasma power can be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, the plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters can be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, OES sensors can be used in a feedback loop to provide programmatic control of the plasma power. It will be appreciated that in some embodiments, other monitors can be used to monitor the plasma and other process characteristics. Such monitors can include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0123] 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 step may be included in a corresponding recipe step of a process recipe. In some cases, the process recipe steps may be arranged in sequence such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a first recipe step may include instructions for setting a flow rate of a process gas, such as a nitrogen-containing gas, instructions for setting a flow rate of a carrier gas (such as argon), and a time delay instruction for the first recipe step. A second recipe step may include instructions for setting a flow rate of an inert gas and / or a silicon-containing precursor gas, instructions for setting a flow rate of a carrier gas (such as argon), and a time delay instruction for the second recipe step. A third subsequent recipe step may include instructions for adjusting or stopping the flow rate of an inert gas and / or a reactant gas, instructions for adjusting the flow rate of a carrier gas or a purge gas, and a time delay instruction for the third recipe step. The fourth recipe step may include instructions to adjust the flow rate of the nitrogen-containing gas, instructions to adjust the flow rate of the carrier gas or purge gas, and a time delay instruction for the fourth recipe step. The fifth subsequent recipe step may include instructions to adjust or stop the flow rate of the inert gas and / or reactant gas, instructions to adjust the flow rate of the carrier gas or purge gas, and a time delay instruction for the fifth recipe step. It will be understood that these recipe steps may be further subdivided and / or repeated in any suitable manner within the scope of the disclosed embodiments. In some embodiments, the controller 350 may include any of the features described below with respect to the system controller 450 of FIG. 4.

[0124] As mentioned above, one or more process stations may be included in a multi-station processing tool. FIG. 4 illustrates an exemplary processing apparatus according to disclosed embodiments. The tool 400 includes a first processing chamber 402 and a second processing chamber 404. The first processing chamber 402 includes multiple processing stations, namely, four stations 480A-D, each capable of processing a wafer. The first processing chamber 402 is configured to perform a plasma processing operation on the wafer. The second processing chamber 404 is configured to perform deposition on the wafer and may be considered a deposition chamber. The second processing chamber 404 also includes multiple processing stations, namely, four stations 482A-D, each capable of processing a wafer and may be controlled by a controller 490, which may be integrated with the system controller 429. The first and second processing chambers 402 and 404 may be considered a multi-station processing chamber.

[0125] The tool 400 also includes a wafer transfer unit configured to transport one or more wafers within the tool 400. Additional features of the tool 400 are described in more detail below, where various features are described with respect to some of the described techniques. In the illustrated example, the wafer transfer unit includes a first robot arm unit 408 in a first wafer transfer module 410 and a second robot arm unit 412 in a second wafer transfer module 414, which may be considered as front-end equipment modules (EFEMs) configured to receive containers for wafers, such as a front-opening unified pod (FOUP) 418. The first robot arm unit 408 is configured to transport wafers between the first processing chamber 402 and the second processing chamber 404, and between the second robot arm unit 412. The second robot arm unit 412 is configured to transport wafers between the FOUP and the first robot arm unit 408. After the wafer is processed in the first processing chamber 402, a wafer transfer unit can transfer the wafer from the first processing chamber 402 to a second processing chamber 404, where one or more layers of encapsulating material can be deposited on the wafer or wafers.

[0126] Similar to above, the first wafer transfer module 410 may be a vacuum transfer module (VTM). An airlock 420, also known as a loadlock, is shown and may be individually optimized to perform various fabrication processes. The tool 400 also includes a FOUP 418 configured to reduce the pressure of the tool 400 to a vacuum or low pressure, for example, about 1 mTorr to about 10 Torr, and maintain the tool 400 at this pressure. This includes maintaining the first and second processing chambers 402 and 404, as well as the first wafer transfer module 410, at a vacuum or low pressure. The second wafer transfer module 414 may be at a different pressure, such as atmospheric pressure. Thus, as the wafer is transferred throughout the tool 400, the wafer is maintained at a vacuum or low pressure. For example, as the wafer is transferred from the first processing chamber 402 to the first wafer transfer module 410 and then to the second processing chamber 404, the wafer is maintained at a vacuum or low pressure and is not exposed to atmospheric pressure.

[0127] In a further example, a substrate is placed in one of the FOUPs 418, and the second robot arm unit 412 or front-end robot transfers the substrate from the FOUP 418 to an aligner, which allows the substrate to be properly centered before being etched, deposited on, or otherwise processed. After being aligned, the substrate is moved by the second robot arm unit 412 to the airlock 420. The airlock module has the ability to accommodate the environment between the ATM and the VTM, so the substrate can move between the two pressure environments without being damaged. From the airlock 420, the substrate is moved by the first robot arm unit 408 through the first wafer transfer module 410 or VTM 410 to the first processing chamber 402. To accomplish this substrate movement, the first robot arm unit 408 uses end effectors on each of its arms.

[0128] 4 also illustrates one embodiment of a system controller 429 used to control the process conditions and hardware states of the tool 400. The system controller 429 can 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 can include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc.

[0129] In some embodiments, the system controller 429 controls all of the activity of the tool 400. The system controller 429 executes system control software that is stored in a mass storage device, loaded into a memory device, and executed on a processor. Alternatively, the control logic may be hard-coded into the system controller 429. 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 description, 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, mixture of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor positions, and parameters of a particular process performed by the tool 400. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components used to perform the various process tool processes. The system control software may be coded in any suitable computer-readable programming language.

[0130] In some embodiments, the system control software may include input / output control (IOC) sequence instructions for controlling the various parameters described above. In some embodiments, other computer software and / or programs stored on mass storage and / or memory devices associated with the system controller 429 may be used. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0131] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal and control the spacing between the substrate and other parts of the tool 400 .

[0132] The process gas control program may include code for controlling gas composition (e.g., silicon-containing precursor gases described herein, nitrogen-containing gases, carrier gases, inert gases, and / or purge gases) and flow rates to stabilize the pressure of the process station, and optionally code for flowing gases to one or more process stations prior to deposition. The pressure control program may include code for controlling the pressure of the process station, for example, by adjusting a throttle valve in the exhaust system of the process station, gas flow to the process station, etc.

[0133] The heater control program may include code for controlling the current to a heating unit used to heat the substrate, or the heater control program may control the delivery of a heat transfer gas (such as helium or nitrogen) to the substrate.

[0134] The plasma control program can include code for setting RF power levels applied to process electrodes in one or more process stations in accordance with embodiments herein.

[0135] The pressure control program can include code for maintaining pressure in the reaction chamber according to embodiments herein.

[0136] In some embodiments, there may be a user interface associated with the system controller 429. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0137] In some embodiments, the parameters adjusted by the system controller 429 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), etc. These parameters may be provided to a user in the form of a recipe and may be entered utilizing a user interface.

[0138] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 429 from various process tool sensors. Signals for controlling the process can be output at analog and digital output connections of the tool 400. Non-limiting examples of process tool sensors that can be monitored include mass flow controllers, pressure sensors (such as pressure gauges), thermocouples, etc. Appropriately programmed feedback and control algorithms can be used with data from these sensors to maintain process conditions.

[0139] The system controller 429 can provide program instructions for carrying out the deposition processes described above. The program instructions can control various process parameters such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions can control the parameters that operate the in-situ deposition of a film stack according to various embodiments described herein.

[0140] The system controller 429 typically includes one or more memory devices and one or more processors configured to execute instructions such that the apparatus performs methods according to the disclosed embodiments. Machine-readable media containing instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 429.

[0141] In some implementations, the system controller 429 is part of a system, such a system may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling system operations before, during, and after processing of a semiconductor wafer or substrate. Such electronics may be referred to as a "controller" and may control various components or subparts of one or more systems. The system controller 429 may be programmed to control any of the processes disclosed herein depending on the processing conditions and / or type of system. Such processes may include 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 motion settings, wafer loading and unloading to and from tools and other transfer tools connected or interlocked with the particular system, and / or wafer loading and unloading to and from load locks.

[0142] Broadly, the system controller 429 may be defined as electronic equipment 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 chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, i.e., microcontrollers that execute program instructions (e.g., software). The program instructions may be instructions communicated to the system controller 429 in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps in the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0143] The system controller 429 may be part of, coupled to, or a combination of a computer that is integrated or coupled with the system or otherwise networked to the system in some embodiments. For example, the system controller 429 may be in the "cloud" or may be all or part of a fab host computer system. This allows for remote access of wafer processing. The computer may allow remote access to the system to monitor the current progress of a fabrication operation, review the history of past fabrication operations, review trends or performance criteria from multiple fabrication operations, modify parameters of a current process, set processing steps following a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network. Such a network may include a local network or the Internet. The remote computer may include a user interface that allows entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the system controller 429 receives instructions in the form of data. Such data identifies parameters for each processing step performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the system controller 429 is configured to interface with or control. Thus, as described above, the system controller 429 may be distributed, for example, by including one or more individual controllers that are networked together and cooperate toward a common purpose (such as the processes and controls described herein).An example of a distributed controller for such purposes would include one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) and coupled to control the process in the chamber.

[0144] Exemplary systems may include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a tracking chamber or module, and any other semiconductor processing system that may be associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0145] As described above, depending on the process step or steps being performed by the tool, the system controller 429 may communicate with one or more other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used for material transport to and from tool locations and / or load ports within the semiconductor manufacturing factory.

[0146] Suitable apparatus for carrying out the methods disclosed herein are further discussed and illustrated in U.S. patent application Ser. No. 13 / 084,399, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," filed Apr. 11, 2011 (now U.S. Patent No. 8,728,956), and U.S. patent application Ser. No. 13 / 084,305, entitled "SILICON NITRIDE FILMS AND METHODS," filed Apr. 11, 2011, the disclosures of each of the above being incorporated herein in their entirety.

[0147] The apparatus / processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, solar panels, and the like. Typically, but not necessarily, such tools / processes are used or performed together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following operations, each of which is enabled by a number of available tools: (1) applying photoresist to a workpiece (i.e., substrate) using a spin-on or spray-on tool; (2) curing the photoresist using a hotplate or furnace or UV curing tool; (3) exposing the photoresist to visible or UV or X-ray light using a tool such as a wafer stepper; (4) developing the resist to selectively remove the resist, thereby patterning the resist, using a tool such as a wet bench; (5) transferring the resist pattern to an underlying film or workpiece by using a dry etching tool or a plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0148] experiment Experiment 1 Experiments were performed on multiple substrates. On the first substrate, silicon nitride was deposited on the untreated silicon oxide surface using 10 cycles of atomic layer deposition (ALD). On the second substrate, silicon nitride was deposited on the untreated bare silicon surface using 10 cycles of ALD. On the third substrate, the untreated silicon oxide surface was exposed to a nitrogen plasma treatment, and then silicon nitride was deposited on the treated silicon oxide surface using 10 cycles of ALD. On the fourth substrate, the untreated silicon surface was exposed to a nitrogen plasma treatment, and then silicon nitride was deposited on the treated silicon surface using 10 cycles of ALD. On the fifth substrate, the untreated silicon oxide surface was exposed to an ammonia plasma treatment, and then silicon nitride was deposited on the treated silicon oxide surface using 10 cycles of ALD. On a sixth substrate, the untreated silicon surface was exposed to an ammonia plasma treatment, after which silicon nitride was deposited on the silicon surface using 10 cycles of ALD, each cycle including a 5 second dose of a silicon-containing precursor, a 10 second purge, a 15 second ammonia exposure, and a 10 second purge.

[0149] The thickness and growth per cycle of silicon nitride deposited on the second, fourth, and sixth substrates are shown in Table 1. The growth per cycle is also illustrated in FIG. [Table 1]

[0150] The resulting nitrogen content for each substrate is shown in Table 2. The variation in nitrogen content for each substrate and for each plasma treated and untreated type is illustrated in FIG. [Table 2]

[0151] Experiment 2 Experiments were performed on substrates. On the first substrate, silicon nitride was deposited on an untreated blanket silicon surface using ALD. On the second substrate, the untreated blanket silicon surface was exposed to a nitrogen plasma treatment, and then silicon nitride was deposited on the treated silicon surface using ALD. The growth per cycle was measured and is graphed in Figure 7. The silicon nitride deposited with a nitrogen plasma treatment prior to silicon nitride deposition showed greater growth per cycle, especially in the initial cycles of ALD.

[0152] On a third substrate, silicon nitride was deposited using ALD on features having a 30:1 aspect ratio and an untreated silicon surface. On a fourth substrate, features having a 30:1 aspect ratio and an untreated silicon surface were exposed to a nitrogen plasma treatment, after which silicon nitride was deposited on the treated silicon surface using ALD. The growth of silicon nitride on the sidewalls of the two substrates was measured and is graphed in FIG. 8. The conformality of the growth of silicon nitride deposited after the nitrogen plasma was improved and the nucleation delay was reduced as thicker growth per cycle was observed.

[0153] Experiment 3 Experiments were performed on patterned substrates with feature aspect ratios of approximately 180:1. Each substrate was patterned with features having an initial diameter D1. If the resulting diameter after deposition is D2, then the sidewall deposition can be determined by subtracting D2 from D1 and dividing by 2 according to the following equation, where X is the amount of sidewall deposition:

number

[0154] Pattern loading is measured by dividing the deposition on the patterned wafer by the deposition on the unpatterned wafer. Silicon nitride was deposited on the first patterned substrate using ALD without plasma pretreatment. Silicon nitride was deposited on the second patterned substrate using nitrogen plasma pretreatment at 3 Torr chamber pressure, 20 slm of nitrogen gas ignited using 3000 W plasma power for a single wafer for 20 minutes, followed by ALD. Silicon nitride was deposited on the third patterned substrate using ammonia plasma pretreatment at 3 Torr chamber pressure, 4.5 slm of ammonia gas ignited using 3000 W plasma power for a single wafer for 20 minutes, followed by ALD. The amount of deposited material was measured by critical dimension scanning electron microscopy (CDSEM). Pattern loading was measured using Equation 2:

number

[0155] The resulting pattern loadings shown on each of these substrates are shown in Table 3. [Table 3]

[0156] Experiment 4 Experiments were conducted to measure silicon content by XPS for silicon nitride deposited using a dose time to conversion time ratio of 1:1 and for silicon nitride deposited using a dose time to conversion time ratio of about 10:4. XPS scans of silicon (top) and nitrogen (bottom) for a dose time to conversion time ratio of 1:1 are shown in FIG. 9A. XPS scans of silicon (top) and nitrogen (bottom) for a dose time to conversion time ratio of 10:4 are shown in FIG. 9B. Results are also illustrated in Table 4. The nitrogen to silicon atomic content ratio can be adjusted from about 0.69 to about 1.10. [Table 4]

[0157] Experiment 5 Experiments were conducted by depositing silicon nitride using adjusted dose time to conversion time ratios on features with an aspect ratio of 180:1. Sidewall thicknesses were measured at various depths into the features. Sidewall thicknesses and depths of silicon nitride deposited using a dose time to conversion time ratio of about 1:1 are shown in FIG. 10A. Conformity of silicon nitride films deposited using a dose time to conversion time ratio of about 1:1 was about 90% to about 110%. Sidewall thicknesses and depths of silicon nitride deposited using a dose time to conversion time ratio of about 10:4 are shown in FIG. 10B. Conformity of silicon nitride films deposited using a dose time to conversion time ratio of about 10:4 was about 100%.

[0158] definition The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to hydrogen or groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of a 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. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0159] "Alkanoyloxy" means an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, an alkanoyloxy group is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0160] "Aliphatic" means a group consisting of at least 1 carbon atom and at least 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, as well as straight-chain and branched-chain arrangements, and all stereoisomers and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups described herein. For example, aliphatic groups can be substituted with one or more of the substituents described herein for alkyl.

[0161] "Aliphatic-carbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0162] "Aliphatic-carbonyloxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0163] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the aliphatic-oxy ​​group is -OR, where R is an optionally substituted aliphatic group as defined herein.

[0164] "Aliphatic-oxycarbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted aliphatic group as defined herein.

[0165] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" refer to an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, that is coupled (or bonded) or can be coupled (or bonded) to a parent molecular group via an aryl group, as defined herein. The alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted with one or more of the substituents described herein for alkyl and / or aryl. Exemplary unsubstituted alkyl-aryl groups are alkyl groups having 7 to 16 carbons (C 7-16 alkyl-aryl), as well as alkyl groups having 1 to 6 carbons and aryl groups having 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkenyl-aryl), as well as alkenyl groups having 2 to 6 carbons and aryl groups having 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups are those having 7 to 16 carbons (C 7-16 alkynyl-aryl), as well as alkynyl groups having 2 to 6 carbons and aryl groups having 4 to 18 carbons (i.e., C 2-6 Alkynyl-C4-18 In some embodiments, the alkyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkynyl group as defined herein.

[0166] "Alkenyl" means an alkyl group having at least 2 carbon atoms and at least 50 carbon atoms (C 2-50 ), e.g., 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, which can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. Alkenyl groups can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C 2-24 Alkyl groups include alkyl groups. Alkenyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (VI), 1-butenyl, 2-butenyl, and the like.

[0167] "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, t-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 of the substituents described herein for alkyl. 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 Examples of the alkyl group include alkoxy groups.

[0168] "Alkoxyalkyl" means an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include those having 2 to 12 carbons (C 2-12 alkoxyalkyl), as well as alkyl groups having 1 to 6 carbons and alkoxy groups having 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl group is -LOR, where each of L and R is independently an alkyl group, as defined herein.

[0169] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as defined herein. In certain embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more of the substituents described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 An example of such a group is an alkoxycarbonyl group.

[0170] "Alkyl" means an alkyl group having at least 1 carbon atom and at least 50 carbon atoms (C 1-50 ), e.g., 1 to 25 carbon atoms (C 1-25 ), or 1 to 10 carbon atoms (C 1-10 ), which can be derived from the removal of one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). An alkyl group can be branched, straight chain, or cyclic (e.g., cycloalkyl). Exemplary alkyls include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. Alkyl groups can also be substituted or unsubstituted. An alkyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group can be substituted with 1, 2, 3, or, in the case of an alkyl group of 2 or more carbons, 4 substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, R is C 1-6 (2) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C1-6 (4) amino (e.g., -NR 1 R 2 , R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 can be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group as defined herein), (5) aryl, (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl), (7) aryloyl (e.g., -C(O)-R, where R is aryl), (8) azido (e.g., -N), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11) C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein), (15) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO), (19) oxo (e.g., =O), (20) C 1-6 Thioalkoxy (e.g., -SR, where R is alkyl), (21) thiol (e.g., -SH), (22) -COR 1 , R 1 is (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 (23) -C(O)NR aryl 1 R 2 , R 1 and R2 each of which is independently (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 (24) -SO2R 1 , R 1 (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 (25)-SONR 1 R 2 , R 1 and R 2 each of which is independently (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 (26)-NR 1 R 2 , R 1 and R 2 each of which is independently (a) hydrogen, (b) an N-protecting group, (c) 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 (h) C 3-8 cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C1-6 alkyl and R is C 3-8 In one embodiment, there are no more than two groups attached to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl groups can be primary, secondary, or tertiary alkyl groups substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl groups are selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0171] "Alkylene," "alkenylene," or "alkynylene" refers to the 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, an alkylene group is a 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 another embodiment, the alkylene group is 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24It is an alkenylene group or an alkynylene group. The alkylene group, the alkenylene group, or the alkynylene group can be branched or unbranched. The alkylene group, the alkenylene group, or the alkynylene group can also be substituted or unsubstituted. For example, the alkylene group, the alkenylene group, or the alkynylene group can be substituted with one or more of the substituents described herein for alkyl.

[0172] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is 1-6 or C 1-12 In another embodiment, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0173] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is 2-12 or C 2-24 Alkyl sulfinyl alkyl groups (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In another embodiment, the alkylsulfinylalkyl group is -LS(O)-R, where each of L and R is independently an alkyl group, as defined herein.

[0174] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO- group. In some embodiments, an unsubstituted alkylsulfonyl group is 1-6 or C 1-12 In other embodiments, the alkylsulfonyl group is -SO-R, where R is an optionally substituted alkyl (e.g., an optionally substituted C alkyl group as described herein).1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0175] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is 2-12 or C 2-24 Alkylsulfonylalkyl groups (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In another embodiment, the alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group, as defined herein.

[0176] "Alkynyl" means an alkyl group having at least 2 carbon atoms and at least 50 carbon atoms (C 2-50 ), e.g., 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, which can be derived from removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight chain, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include optionally substituted C 2-24 Examples of such groups include alkyl groups. Alkynyl groups can be cyclic or non-cyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0177] 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.

[0178] "Amide" means -C(O)NR 1 R 2 or -NHCOR 1 means R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 can be taken together with the nitrogen atom to which they are each attached to form a heterocyclyl group, as defined herein.

[0179] "Amino" means -NR 1 R 2 means 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, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 can be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group, as defined herein. In certain embodiments, R 1 and R 2 Each of R 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 silyloxy. In certain embodiments, R 1 and R 2 can be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0180] "Aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 where L is an alkyl group as defined herein and R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group, as defined herein. In other embodiments, an aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, or aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group as defined herein; R 3 and R 4 Each of is independently H or alkyl as defined herein.

[0181] "Aminoxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 and R 1 and R 2each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 can be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group, as defined herein. In certain embodiments, R 1 and R 2 Each of 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 silyloxy.

[0182] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5-15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., 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 Hückel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted, for example, by functional groups described herein. For example, aromatic groups can be substituted with one or more of the substituents described herein for alkyl and / or aryl.

[0183] "Aromatic-carbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl group is -C(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0184] "Aromatic-carbonyloxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0185] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled through an oxy group (-O-). In some embodiments, the aromatic-oxy ​​group is -OR, where R is an optionally substituted aromatic group as defined herein.

[0186] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic-carbonyl group is -C(O)OR, where R is an optionally substituted aromatic group as defined herein.

[0187] "Aryl" refers to an aryl group having a single ring or multiple condensed rings and at least 5 carbon atoms to 15 carbon atoms (C 5-15 ), e.g., 5 to 10 carbon atoms (C 5-10), the fused ring 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, heteroaliphatic, aromatic, 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, which is defined as a group that contains an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 (2) C 1-6 Alkyl, (3) C 1-6 Alkoxy (e.g., -OR, R is C 1-6 (4) C 1-6 Alkoxy-C 1-6 alkyl (e.g., -LOR, each of L and R is independently C 1-6 (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (6) C 1-6 Alkylsulfinyl-C 1-6 alkyl (e.g., -LS(O)-R, each of L and R is independently C 1-6 (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, each of L and R is independently C 1-6(9) aryl; (10) amino (e.g., -NR 1 R 2 , R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which each is attached to form a heterocyclyl 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 , L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 is alkyl, R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which each is attached to form a heterocyclyl group as defined herein; R 3 and R 4 each independently is H or C 1-6 (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) aryloyl (e.g., -C(O)-R, where R is aryl), (15) azido (e.g., -N), (16) cyano (e.g., -CN), (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6(18) aldehyde (e.g., —C(O)H), (19) aldehyde-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 (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 (22) halo, (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 alkyl, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 each independently is H or C 1-6 (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (25) heterocyclyloxy (e.g., -OR, where R is heterocyclyl, as defined herein), (26) heterocyclyloyl (e.g., -C(O)-R, where R is 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 , L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein. 1-6 (29) nitro, (30) C 1-6 Nitroalkyl (e.g., -L1 -NO or -L 2 -C(NO)(R 1 )-R 2 , L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein. 1-6 (31) N-protected amino, (32) N-protected amino-C 1-6 Alkyl, (33) oxo (e.g., =O), (34) C 1-6 Thioalkoxy (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, each of L and R is independently C 1-6 (36)-(CH2) r CO2R 1 , r is an integer from 0 to 4, R 1 is (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 (37)-(CH2) r CONR 1 R 2 , r is an integer from 0 to 4, and each R 1 and R 2 is (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 (38)-(CH2) r SO2R 1 , r is an integer from 0 to 4, R1 (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 (39)-(CH2) r SO2NR 1 R 2 , r is an integer from 0 to 4, R 1 and R 2 each of which is independently (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), (40)-(CH2) r NR 1 R 2 , r is an integer from 0 to 4, R 1 and R 2 each of which is independently (a) hydrogen, (b) an N-protecting group, (c) 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) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2)n CF3, n is an integer of 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, n is an integer from 0 to 10), (44) aryloxy (e.g., -OR, R is aryl), (45) cycloalkoxy (e.g., -OR, R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -OLR, L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -OLR, L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl 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 It is an aryl group.

[0188] "Aryl-alkyl", "aryl-alkenyl", and "aryl-alkynyl" refer to an aryl group, as defined herein, that is coupled (or bonded) or can be coupled (or bonded) to a parent molecular group via an alkyl group, an alkenyl group, or an alkynyl group, as defined herein, respectively. The aryl-alkyl group, the aryl-alkenyl group, and / or the aryl-alkynyl group can be substituted or unsubstituted. For example, the aryl-alkyl group, the aryl-alkenyl group, and / or the aryl-alkynyl group can be substituted with one or more of the substituents described herein for the aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups are aryl groups having 7 to 16 carbons (C 7-16 aryl-alkyl), as well as those with aryl groups having 4 to 18 carbons and alkyl groups having 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Exemplary unsubstituted aryl-alkenyl groups are those having 7 to 16 carbons (C 7-16aryl-alkenyl), as well as aryl groups having 4 to 18 carbons and alkenyl groups having 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups are those having 7 to 16 carbons (C 7-16 aryl-alkynyl), as well as aryl groups having 4 to 18 carbons and alkynyl groups having 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, where L is an alkyl or alkylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkenyl group is -LR, where L is an alkenyl or alkenylene group as defined herein, and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -LR, where L is an alkynyl or alkynylene group as defined herein, and R is an aryl group as defined herein.

[0189] "Arylene" refers to a polyvalent (e.g., divalent) form of the aryl groups described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, acenaphthenylene, anthrylene, or phenanthrylene. 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 It is an arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more of the substituents described herein for aryl.

[0190] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0191] "Aryloxy" refers to -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is 4-18 or C 6-18 In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0192] "Aryloxycarbonyl" refers to an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is 5-19 In another embodiment, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group as defined herein.

[0193] "Aryloyl" refers to an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is 7-11 Aryloyl or C 5-19 In another embodiment, the aryloyl group is -C(O)-R, where R is an aryl group, as defined herein.

[0194] "Aryloyloxy" refers to an aryloyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, an unsubstituted aryloyloxy group is 5-19 In another embodiment, an aryloyloxy group is -OC(O)-R, where R is an aryl group, as defined herein.

[0195] "Azido" refers to the group --N3.

[0196] "Azidoalkyl" means an azido group attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group, as defined herein.

[0197] "Azo" means the -N=N- group.

[0198] "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 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, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 can be taken together with the nitrogen atom to which they are each attached to form a heterocyclyl group, as defined herein.

[0199] "Carbamoyloxy" refers to a carbamoyl group, as defined herein, attached to the parent molecular group through an n-oxy group, as defined herein. In some embodiments, carbamoyl is -OC(O)NR 1 R 2 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, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R1 and R 2 can be taken together with the nitrogen atom to which they are each attached to form a heterocyclyl group, as defined herein.

[0200] "Carbonimidoyl" 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 silyloxy, or any combination thereof, as defined herein.

[0201] "Carbonyl" refers to the group -C(O)-, which also can be represented as >C=O.

[0202] "Carboxyl" means the -CO2H group or its anion.

[0203] By "catalyst," as would be readily understood by one of ordinary skill in the art, is meant a compound capable of catalyzing a synthetic reaction, usually present in small amounts relative to the reactants. In some embodiments, the catalyst may include a transition metal coordination complex.

[0204] "Cyanato" refers to the group -OCN.

[0205] "Cyano" refers to the radical -CN.

[0206] "Alicyclic" means an aliphatic group, as defined herein, that is cyclic.

[0207] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group, as defined herein.

[0208] "Cycloalkylalkoxy" means a -OLR group where L is an alkyl or alkylene group as defined herein and R is a cycloalkyl group as defined herein.

[0209] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of 3 to 8 carbons, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyl groups can be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those described herein for alkyl. Additionally, cycloalkyl groups can include one or more double and / or triple bonds.

[0210] "Cycloheteroaliphatic" means a heteroaliphatic group, as defined herein, that is cyclic.

[0211] "Disilanyl" refers to a group that contains a Si-Si bond. In some embodiments, the disilanyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - group, and R S1 , R S2 , R S3 , R S4 , and R S5 Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0212] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0213] By "electron donating group" is meant a functional group capable of donating, such as by resonance, at least a portion of its electron density to the ring to which the electron donating group is directly attached.

[0214] By "electron-withdrawing group" is meant a functional group capable of accepting electron density, such as by inductive electron withdrawal, from the ring to which the electron-withdrawing group is directly attached.

[0215] "Halo" means F, Cl, Br, or I.

[0216] "Haloaliphatic" means an aliphatic group, as defined herein, in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0217] "Haloalkyl" means an alkyl group, as defined herein, in which one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, the haloalkyl can be a -CX group, where each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -LX, where L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -LC(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0218] "Haloheteroaliphatic" means heteroaliphatic, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced by a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0219] "Heteroaliphatic" means an aliphatic group, as defined herein, containing at least one heteroatom to 20 heteroatoms, e.g., 1-15 heteroatoms, or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. Heteroaliphatic groups are unsubstituted or substituted, e.g., with functional groups as described herein. For example, heteroaliphatic groups can be substituted with one or more substituents as described herein for alkyl.

[0220] "Heteroaliphatic-carbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0221] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0222] "Heteroaliphatic-oxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0223] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0224] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" mean an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, which may be branched, straight-chained, or cyclic, and which contain at least one heteroatom and up to 20 heteroatoms, e.g., 1-15 heteroatoms, or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group.

[0225] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to the polyvalent (eg, divalent) forms of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein.

[0226] "Heteroaromatic" means an aromatic group, as defined herein, containing at least one heteroatom to 20 heteroatoms, e.g., 1-15 heteroatoms, or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. Heteroaromatic groups are unsubstituted or substituted, e.g., by functional groups as described herein. For example, heteroaromatic groups can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0227] "Heteroaromatic-carbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0228] "Heteroaromatic-carbonyloxy" means a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0229] "Heteroaromatic-oxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​group is -OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0230] "Heteroaromatic-oxycarbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0231] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms, e.g., one to four heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms in the ring. Such heteroaryl groups may have a single ring or multiple fused rings, which may or may not be aromatic and / or may contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryls include the subset of heterocyclyl groups defined herein that are aromatic, i.e., contain 4n+2 pi-electrons in a monocyclic or polycyclic ring system.

[0232] "Heteroarylene" means a multivalent (eg, divalent) form of a heteroaryl group described herein.

[0233] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, such as where valence constraints are not permitted, heteroatoms do not include halogen atoms.

[0234] "Heterocyclyl" means, unless otherwise specified, a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Five-membered rings have 0-2 double bonds, and 6- and 7-membered rings have 0-3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups, in which any of the above heterocycles 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 heterocycle such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolidinyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, nyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, urisyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0235] "Heterocyclyloxy" means a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group, as defined herein.

[0236] "Heterocyclyl" means a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group, as defined herein.

[0237] "Hydrazino" means -NR 1 -NR 2 R 3 means R 1 , R 2 , and R 3 each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted silyloxy, or any combination thereof, as defined herein, or R 1 and R 2 combination of, or R 2 and R 3 can be combined with the nitrogen atom to which each is attached to form a heterocyclyl group, as defined herein. 1 , R 2 , or R 3 Each of R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In certain embodiments, R 2 and R 3 can be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0238] "Hydroxyl" means --OH.

[0239] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, with the proviso that not more than one hydroxyl group can be attached to a single carbon atom of the alkyl group, as exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, the hydroxyalkyl group is -L-OH, where L is an alkyl group, as defined herein. In other embodiments, the hydroxyalkyl group is -LC(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0240] "Imidoyl" refers to a moiety that contains a carbonimidoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2 and 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, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein. In other embodiments, the imidoyl group is -C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar and R 1is 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 silyloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic, R Ar is an optionally substituted aryl or an optionally substituted aromatic.

[0241] "Imino" refers to the group -NR-. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In certain 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.

[0242] "Isocyanato" refers to a -NCO group.

[0243] "Isocyano" refers to the group -NC.

[0244] By "ketone" is meant a compound containing -C(O)R or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. An example of a ketone is a compound containing -C(O)R or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. 1 C(O)R, R and R 1 Each of is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0245] "Nitro" refers to the -NO2 group.

[0246] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group, as defined herein. In other embodiments, the nitroalkyl group is -LC(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0247] "Oxo" means the group ═O.

[0248] "Oxy" means --O--.

[0249] "Perfluoroalkyl" refers to an alkyl group, as defined herein, having each hydrogen atom replaced with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, a perfluoroalkyl group is -(CF2) n CF3, and n is an integer from 0 to 10.

[0250] "Perfluoroalkoxy" means an alkoxy group, as defined herein, having each hydrogen atom replaced with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group, as defined herein.

[0251] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein), including cationic or anionic compounds that form electrically neutral compounds or structures. 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. PHStahl and CG Wermuth). Salts can be prepared in-situ during the final isolation and purification of the compounds of the present invention, or separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or the acid group with a suitable metal or organic acid salt (thereby producing a cationic salt).Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, Examples of the salts include laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, 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, acetate, succinate, sulfate, tannate, tartrate, theophylline, thiocyanate, triethiodide, toluenesulfonate, undecanoate, and valerate. Representative cationic salts include metal salts, such as alkali or alkaline earth 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.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, 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 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 azepinium, optionally substituted indolium , optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prenium.

[0252] "Silyl" means -SiR 1 R 2 R 3 or -SiR 1 R2 In some embodiments, R 1 , R 2 , and R 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3 Each of 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, the silyl group is -Si(R) a (OR) b (NR2) c and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0253] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 and R 1 , R 2 , and R 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3Each of 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, the silyloxy group 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, and each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0254] "Sulfinyl" refers to the group -S(O)-.

[0255] "Sulfo" refers to the group -S(O)2OH.

[0256] "Sulfonyl" or "sulfonate" means a -S(O)- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0257] "Thioalkyl" means an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include, 1-6 In some embodiments, the thioalkyl group is -SR, where R is an alkyl group as defined herein.

[0258] "Thiol" refers to a -SH group.

[0259] Those skilled in the art will recognize that the above definitions are not intended to include impermissible substitution patterns (such as, for example, methyl substituted with five different groups). Such impermissible substitution patterns are readily recognized by those skilled in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise indicated.

[0260] As used herein, the term "about" means ±10% of the recited value. As used herein, the term modifies a recited value, a range of values, or one or more of the endpoints of a range.

[0261] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. Use of these terms does not indicate or require that a particular structure must be located in a particular location within the apparatus.

[0262] Other features and advantages of the disclosed embodiments will become apparent from the following description and from the claims.

[0263] conclusion Although the foregoing embodiments have been described in some detail for clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Thus, the present embodiments should be considered as illustrative rather than restrictive, and the embodiments should not be limited to the details set forth herein.

Claims

1. 1. A method for processing a substrate, comprising: Providing a semiconductor substrate having an exposed surface in a process chamber; (1) heating the semiconductor substrate to a first temperature; and / or (2) pretreating the semiconductor substrate by exposing the semiconductor substrate to a nitrogen-containing plasma; introducing a flow of halosilane gas into said process chamber using a dose time; purging the process chamber for a first purge time after stopping the flow of the halosilane gas; introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride by thermal atomic layer deposition; purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas. A method comprising:

2. 1. A method for processing a substrate, comprising: Providing a semiconductor substrate having an exposed surface in a process chamber; heating the semiconductor substrate to a first temperature; pretreating the semiconductor substrate by exposing the semiconductor substrate to a nitrogen-containing plasma; After performing the pretreatment, the semiconductor substrate is heated to a second temperature; introducing a flow of halosilane gas into the process chamber in a plasma-free environment using a dose time after heating the semiconductor substrate to the second temperature; purging the process chamber for a first purge time after stopping the flow of the halosilane gas; introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride in a plasma-free environment; purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas. A method comprising:

3. The method according to claim 1 or 2, further comprising: the exposed surface comprises silicon oxide.

4. 3. The method according to claim 1 or 2, The method wherein the nitrogen-containing plasma is formed by igniting a second nitrogen-containing gas.

5. 3. The method according to claim 1 or 2, The method, wherein the first temperature and the second temperature are the same.

6. 3. The method according to claim 1 or 2, The method according to claim 1, wherein the halosilane gas comprises chlorine.

7. 1. A method for processing a substrate, comprising: Providing a semiconductor substrate having an exposed surface in a process chamber; exposing the exposed surface to a nitrogen-containing plasma; introducing a flow of silicon-containing gas into said process chamber using a dose time; purging the process chamber for a first purge time after stopping the flow of the silicon-containing gas; introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride by thermal atomic layer deposition; purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas. Equipped with the ratio of said administration time to said conversion time is from about 1:1 to about 10:4; method.

8. 1. A method for processing a substrate, comprising: Providing a semiconductor substrate having an exposed surface in a process chamber; exposing the exposed surface to a nitrogen-containing plasma; introducing a flow of a silicon-containing gas into the process chamber in a plasma-free environment using a dose time; purging the process chamber for a first purge time after stopping the flow of the silicon-containing gas; introducing a flow of a first nitrogen-containing gas into the process chamber using a conversion time to form silicon nitride in a plasma-free environment; purging the process chamber for a second purge time after stopping the flow of the first nitrogen-containing gas. Equipped with the ratio of the administration time to the conversion time is from about 1x:3x to about 10x:12x, where x is from about 0.2 seconds to about 10 seconds; method.

9. 1. An apparatus for processing a substrate, comprising: one or more process chambers, each process chamber comprising a chuck; one or more gas inlets and associated flow control hardware to the process chamber; a controller having at least one processor and a memory; Equipped with the at least one processor and the memory are communicatively coupled to each other; the at least one processor is at least operatively connected to the flow control hardware; The memory controls the at least one processor and includes at least providing a substrate to one of the one or more process chambers; generating a plasma using a nitrogen-containing gas to generate nitrogen plasma species; exposing the substrate to the nitrogen plasma species in the one or more process chambers; introducing a silicon-containing precursor into the one or more process chambers; Introducing a nitrogen-containing reactant to convert the silicon-containing precursor to silicon nitride in a plasma-free environment. storing computer executable instructions for controlling the flow control hardware such that Device.

10. 1. An apparatus for processing a substrate, comprising: one or more process chambers, each process chamber comprising a chuck; one or more gas inlets and associated flow control hardware to the process chamber; a controller having at least one processor and a memory; Equipped with the at least one processor and the memory are communicatively coupled to each other; the at least one processor is at least operatively connected to the flow control hardware; The memory controls the at least one processor and includes at least providing a substrate to one of the one or more process chambers; introducing a halosilane precursor into the one or more process chambers for a dosage time; A nitrogen-containing reactant is introduced over a conversion period to convert the halosilane precursor to silicon nitride in a plasma-free environment. storing computer executable instructions for controlling the flow control hardware such that A ratio of administration time to conversion time of about 1x:3x to about 10x:12x, where x is about 0.2 seconds to about 10 seconds, is used; Device.

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