Low-k dielectric protection during plasma deposition of silicon nitride

Abstract

Methods and apparatus are provided for using a plasma to deposit silicon nitride over a low-k dielectric material while protecting the low-k dielectric material. The method includes: providing a substrate having a dielectric material deposited thereon; depositing a protective layer on the dielectric material in a plasma-free environment; and after depositing the protective layer, exposing the substrate to a first plasma to deposit a first silicon nitride while converting at least a portion of the protective layer to a second silicon nitride.

Description

Incorporated by Reference

[0001] The PCT application form is filed concurrently with this specification as a part of this application. Each application identified in the concurrently filed PCT application form to which this application claims the benefit or priority is incorporated herein by reference in its entirety and for all purposes. Background Art

[0002] Semiconductor manufacturing processes involve depositing silicon-containing materials, including silicon nitride materials, on low-k dielectric materials. When forming high-quality silicon nitride, it is challenging to reduce damage to the low-k dielectric during the deposition of the silicon nitride.

[0003] The background description provided here is for the purpose of generally presenting the context of the present disclosure. The work of the presently designated inventors is neither explicitly nor implicitly admitted to be prior art against the present disclosure to the extent that it is described in this background section and to aspects of the specification that could not be determined as prior art at the time of filing the application. Summary of the invention

[0004] One aspect relates to a method for processing a substrate, the method comprising: providing a substrate having a dielectric material deposited thereon; depositing a protective layer on the dielectric material in a plasma-free environment; and after depositing the protective layer, exposing the substrate to a first plasma to deposit a first silicon nitride while converting at least a portion of the protective layer to a second silicon nitride.

[0005] In various embodiments, the protective layer is deposited by thermally decomposing a deposition precursor on the surface of the substrate.

[0006] In various embodiments, the protective layer is deposited by: exposing the substrate to a deposition precursor; and heating the substrate to a temperature sufficient to decompose the deposition precursor onto the surface of the substrate.

[0007] In various embodiments, the protective layer is deposited by time-alternating pulses of: exposing the substrate to a deposition precursor; and exposing the substrate to an inert gas. In some embodiments, the substrate is heated to a temperature of at least about 500°C.

[0008] In various embodiments, exposing the substrate to the first plasma includes using one or more nitrogen-containing gases to generate the first plasma. In some embodiments, the nitrogen-containing gas is one of nitrogen, ammonia, and a combination thereof. In some embodiments, for a single wafer chamber, the first plasma is generated using a plasma power of about 500W to about 6000kW. In some embodiments, the second silicon nitride is deposited by performing one or more deposition cycles. For example, in some embodiments, one of the one or more deposition cycles includes using time-alternating pulses of exposure to a silicon-containing precursor and exposure to a nitrogen-containing plasma. In some embodiments, one of the one or more deposition cycles includes using pulses separated in time by exposure to a silicon-containing precursor, exposure to the first plasma generated by igniting nitrogen, and exposure to a third plasma generated by igniting a mixture of ammonia and nitrogen.

[0009] In various embodiments and any of the above embodiments, during deposition of the protective layer, less than about of dielectric material.

[0010] In various embodiments and any of the embodiments above, the dielectric material is silicon oxycarbide.

[0011] In various embodiments and any of the embodiments described above, the protective layer is deposited directly on the dielectric material.

[0012] In various embodiments and any of the embodiments described above, the entire protective layer is converted to the second silicon nitride.

[0013] In various embodiments, the protective layer is deposited by decomposing a deposition precursor on the surface of the substrate to form a decomposed film; and exposing the decomposed film to a second plasma to form a protective layer. In some embodiments, the second plasma is generated by igniting an inert gas, and the protective layer is densified. In some embodiments, the second plasma is generated by igniting an oxygen-containing or nitrogen-containing gas, and the protective layer is an oxide or a nitride. In some embodiments, exposing the decomposed film to the second plasma includes exposing the decomposed film to an inert gas plasma and then exposing the decomposed film to an oxygen-containing or nitrogen-containing plasma. In some embodiments, the method further includes repeatedly decomposing the deposition precursor and exposing the decomposed film to an inert gas plasma and an oxygen-containing or nitrogen-containing plasma.

[0014] In various embodiments, the deposition precursor is diisopropylaminosilane.

[0015] In various embodiments, the deposition precursor is bis(tert-butylamino)silane.

[0016] Another aspect relates to a method for processing a substrate, the method comprising: providing a substrate having a silicon oxynitride material deposited thereon to a processing chamber; introducing a first silicon-containing precursor to the processing chamber, the processing chamber being under process conditions sufficient to decompose the first silicon-containing precursor in a plasma-free environment and form the decomposed first silicon-containing precursor on a surface of the substrate to form a protective layer containing the decomposed first silicon-containing precursor; after forming the protective layer, introducing a second silicon-containing precursor to the processing chamber to form an adsorption layer of the second silicon-containing precursor on the surface of the protective layer; and introducing a nitrogen-containing plasma to the processing chamber to convert the second silicon-containing precursor into silicon nitride and convert at least a portion of the protective layer into silicon nitride.

[0017] In various embodiments, at least one of the first and second silicon-containing precursors is diisopropylaminosilane.

[0018] In various embodiments, at least one of the first and second silicon-containing precursors is bis(tert-butylamino)silane.

[0019] In various embodiments, the first silicon-containing precursor is the same as the second silicon-containing precursor.

[0020] In various embodiments, the first silicon-containing precursor is different from the second silicon-containing precursor.

[0021] In various embodiments, the nitrogen-containing plasma is generated by igniting nitrogen gas, ammonia gas, or a mixture of nitrogen gas and ammonia gas.

[0022] Another aspect relates to an apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber comprising a chuck; one or more gas inlets leading to the processing chambers and associated flow control hardware; and a controller having a memory and at least one processor, wherein the memory and the at least one processor are communicatively coupled to each other, the at least one processor is operably coupled to at least the flow control hardware, and the memory stores computer executable instructions for controlling the at least one processor to control at least the flow control hardware to: cause a first silicon-containing precursor to be introduced into the one or more processing chambers for a duration sufficient to adsorb at least some of the first silicon-containing precursor to adsorb to a surface of the substrate without igniting a plasma; cause the chuck to be heated to decompose the first silicon-containing precursor and form a protective layer on the surface of the substrate; cause a second silicon-containing precursor to be introduced into the one or more processing chambers for a duration sufficient to adsorb at least some of the second silicon-containing precursor to adsorb to a surface of the protective layer without igniting a plasma; and use a nitrogen-containing gas to cause a plasma to be generated to convert the second silicon-containing precursor into silicon nitride and convert at least a portion of the protective layer into silicon nitride.

[0023] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figures 1A-1C A process flow diagram is provided to depict operations that may be performed in accordance with certain disclosed embodiments.

[0025] Figure 2A-2E-2 is a schematic diagram of a substrate being processed according to certain disclosed embodiments.

[0026] Figure 3 is a schematic diagram of an exemplary processing chamber for performing certain disclosed embodiments.

[0027] Figure 4 is a schematic diagram of an exemplary processing tool for performing certain disclosed embodiments.

[0028] Figure 5 is a schematic diagram of an exemplary processing tool for performing certain disclosed embodiments.

[0029] Figure 6-8 is a graph showing silicon oxynitride depletion for a number of experiments. DETAILED DESCRIPTION

[0030] In the following description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be implemented without some or all of these specific details. In other respects, well-known process operations are not described in detail in order not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that they are not intended to limit the disclosed embodiments.

[0031] Semiconductor manufacturing processes may involve depositing materials onto surfaces having dielectric materials. In some embodiments, low-k dielectric materials may be used to manufacture certain structures. Low-k dielectric materials may have a k value of about 4.4 to about 4.7. In some cases, low-k dielectric materials have low hardness or low modulus or both. The low modulus of low-density SiOC materials may have a modulus of about 10 GPa or less. The low modulus of high-density SiOC materials may have a modulus of about 150 GPa or less. For example, in some cases, low-k dielectric materials may be used as interconnect insulators to reduce resistance-capacitance (RC) delay. In some cases, it may be necessary to deposit high-quality materials on low-k dielectric materials. For example, it may be necessary to deposit high-quality silicon nitride (SiN) on silicon oxycarbide materials (SiOC). However, depositing SiN may involve exposing a semiconductor substrate to plasma. When the substrate is exposed to plasma, the exposed SiOC material may therefore be exposed to plasma, which may damage the surface of SiOC, which may be referred to as "SiOC loss". Plasma damage to SiOC can lead to increased device leakage current, reduced breakdown voltage, increased dielectric breakdown over time, and increased dielectric constant, all of which affect device performance.

[0032] While SiN can be deposited using thermal atomic layer deposition (ALD) in a furnace to prevent damage to the low-k dielectric material, furnace deposition has limitations in its ability to tune and control the properties of the deposited SiN film. Alternatively, plasma-based processes using remote plasma can be utilized, but the controllability of the film properties may also be limited, and in some cases, damage to the low-k dielectric material may still exist.

[0033] Methods and apparatus are provided herein for depositing SiN on low-k dielectric materials and minimizing or eliminating SiOC losses. Deposition using certain disclosed embodiments can still utilize in-situ or remote plasma processes for SiN deposition, which results in high quality SiN deposition with a wide tunable window, allowing for more controlled film deposition.

[0034] Certain disclosed embodiments involve depositing a protective layer on a low-k dielectric material using a thermal, plasma-free process, followed by depositing SiN on the protective layer using a plasma-based process that simultaneously deposits the SiN and converts at least a portion of the protective layer to SiN. The resulting substrate structure exhibits substantially indistinguishable properties between the converted SiN and the plasma-deposited SiN, as the two materials have similar film properties and are both high-quality films. Additionally, in some embodiments, a portion of the protective layer may be intentionally left at the low-k dielectric and SiN interface to control wet etch rates and other film properties.

[0035] Certain disclosed embodiments result in less than about or The SiOC loss may be reduced or no SiOC loss may be measured. Certain disclosed embodiments may be implemented in situ. In some embodiments, the deposition of the protective layer and SiN is performed without breaking vacuum, or in the same process chamber, or in the same tool, or any combination thereof. In some embodiments, the deposition of the protective layer and SiN is performed in a single process chamber. Certain disclosed embodiments may be performed in a single wafer chamber.

[0036] The technology described herein relates to thermal atomic layer deposition (ALD). That is, in various embodiments, the reaction between an aminosilane or a halosilane and a nitrogen-containing reactant to form silicon nitride is carried out without igniting a plasma. ALD is a technology that uses a continuous self-limiting reaction to deposit a thin layer of material. Generally, an ALD cycle includes the operation of delivering and adsorbing at least one reactant to a substrate surface, and then reacting the adsorbed reactant with one or more reactants to form a portion of a film layer. As another example, a silicon nitride deposition cycle may include the following operations: (i) delivering / adsorbing a silicon-containing precursor, (ii) purging the silicon-containing precursor from the chamber, (iii) delivering a nitrogen-containing gas, and (iv) purging the nitrogen-containing gas from the chamber. In various embodiments, the delivery / adsorption of the deposition precursor and the delivery of the reactant gas are delivered in the form of time-alternating pulses. Time-alternating pulses are defined as pulses introduced one after another at different times. For example, an on / off sequence of time-alternating pulses may include the following order of operations: (1) turn on the flow of a silicon-containing precursor, (2) turn off the flow of a silicon-containing precursor, (3) turn on the flow of a nitrogen-containing reactant, and (4) turn off the flow of a nitrogen-containing reactant. While this order is provided as an example, it should be understood that exposures may be performed in a different order in one or more cycles, that other gases besides silicon-containing precursors or nitrogen-containing reactants may be used, and that there may be pauses or sweeps or other intermediate exposures between time-alternating pulses.

[0037] Unlike chemical vapor deposition (CVD) techniques, the ALD process uses a surface-mediated deposition reaction to deposit films on a layer-by-layer basis. In one example of an ALD process, a substrate surface having a population of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, which is provided in a certain dosage to a chamber containing the substrate. Molecules of the first precursor are adsorbed onto the substrate surface, including chemically adsorbed species and / or physically adsorbed molecules of the first precursor. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound and derivatives of the compound. For example, the adsorption layer of a silicon-containing precursor may include a silicon-containing precursor and a derivative of the silicon-containing precursor. After the first precursor is dosed, the chamber is evacuated to remove most or all of the silicon-containing precursor remaining in the gas phase, so that most or only the adsorbed species remain. In some implementations, the chamber may not be completely evacuated. For example, the chamber may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant, such as a nitrogen-containing reactant, is introduced into the chamber so that some of these molecules react with the silicon-containing precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed silicon-containing precursor. The chamber can then be evacuated again to remove unbound silicon-containing reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

[0038] In some embodiments, the ALD first precursor dose partially saturates the substrate surface. In some embodiments, the dosing phase of the ALD cycle ends before the precursor contacts the substrate to saturate the surface evenly. Typically, at this time, the precursor flow is shut off or diverted, and only the sweep gas flows. By operating in this saturated state, the ALD process reduces cycle time and increases throughput. However, because precursor adsorption is not saturation-limited, the concentration of the adsorbed precursor may vary slightly across the substrate surface. An example of an ALD process operating in a subsaturated state is provided in U.S. Patent Application No. 14 / 061,587 (now U.S. Patent No. 9,355,839), filed on October 23, 2013, entitled "SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILMDEPOSITION," the entire contents of which are incorporated herein by reference.

[0039] In certain implementations, the ALD method may include plasma activation. However, in the thermal ALD process described herein, no plasma is ignited. As described herein, the ALD method and apparatus described herein may be a conformal film deposition (CFD) method generally described in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION” (now U.S. Patent No. 8,728,956), and described in U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled “SILICON NITRIDE FILMS AND METHODS,” the entire contents of which are incorporated herein by reference.

[0040] Figure 1A 1 is a flow chart depicting operations that may be performed according to certain disclosed embodiments. In operation 102, a substrate having a low-k dielectric material deposited thereon is provided to a processing chamber. In various embodiments, the processing chamber is a single wafer chamber. In some embodiments, the processing chamber is a station within a multi-station chamber. The process conditions described herein are applicable to a single wafer chamber.

[0041] The processing chamber can be set to a chamber pressure between about 5 mTorr and about 25 Torr or about 10 Torr and about 25 Torr. Such a chamber pressure can be used in all operations 104 to 108 as described herein. In some embodiments, the chamber pressure during different operations may be different. The chamber pressure may also depend on the chemistry selected for many of the operations described herein.

[0042] During operations 104 to 108, the substrate may be heated to a substrate temperature of about 25° C. to about 800° C., or about 500° C. to about 700° C., or at least about 650° C. It should be understood that substrate temperature as used herein refers to the temperature at which the pedestal holding the substrate is set, and in some embodiments, when the substrate is provided to the processing chamber pedestal, the substrate may be heated to a desired substrate temperature before processing the substrate. The substrate temperature may be the same in all operations 102 to 108 as described herein.

[0043] The substrate may be any suitable substrate. The substrate may be a silicon wafer, such as a 200-mm wafer, a 300-mm wafer, including a wafer having one or more material layers, such as dielectric, conductive, or semiconductor materials deposited thereon. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxide, metal nitride, metal carbide, and metal layers. In some embodiments, the substrate includes silicon oxide and silicon. In some embodiments, the substrate includes a portion of a fabricated 3D-NAND structure.

[0044] In some embodiments, the features may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or at least about 20:1, or at least about 50:1, or at least about 100:1, or at least about 150:1, or at least about 200:1 or more. The features may also have a size close to the opening, such as an opening diameter or line width between about 10nm and 500nm, such as between about 25nm and about 300nm. The disclosed method may be performed on a substrate with features having an opening less than about 150nm. A through hole, groove, or other recessed feature may be referred to as an unfilled feature or features. According to various embodiments, the feature profile may taper and / or include a protrusion at the feature opening. A concave profile is a profile that tapers from the bottom, closed end, or interior of the feature to the feature opening. The concave profile may result from asymmetric etch dynamics during patterning and / or protrusions resulting from non-conformal film step coverage in a previous film deposition, such as deposition of a diffusion barrier layer. In various examples, the width of the feature at its top opening may be less than the width of the feature bottom. One or more features may have a high aspect ratio, which is defined as having an aspect ratio greater than about 100:1, or greater than about 150:1, or greater than about 180:1.

[0045] In some embodiments, the substrate may be partially fabricated for forming a memory device. In some embodiments, the exposed area of ​​the substrate includes a silicon-containing surface, including but not limited to low-k dielectric materials, silicon oxides, silicon nitrides, silicon oxynitrides, silicon oxycarbides, carbon silicon nitrides, and silicon carbides. In some embodiments, the exposed area of ​​the substrate includes silicon oxynitrides.

[0046] In operation 104, a protective layer is deposited on the dielectric material in a plasma-free environment. In various embodiments, the dielectric material is a low-k material. In various embodiments, the protective layer is deposited on the dielectric material. In some embodiments, the protective layer is deposited directly on the dielectric material. In some embodiments, the protective layer is deposited directly on the dielectric material without any intervening layers between the protective layer and the dielectric material. During the deposition of the protective layer, the amount of low-k dielectric material consumed is less than about or about or The protective layer is deposited in a plasma-free environment to reduce and / or eliminate damage to the low-k dielectric material. The protective material may be a layer formed by a decomposition process or a cyclic process or a combination thereof.

[0047] An example of a method for depositing a protective material is shown in Figure 1B In. Figure 1B In the embodiment, operation 104 includes three operations, operation 104a, operation 104b, and operation 104c. Although this is provided as an example of depositing a protective layer in operation 104, it should be understood that other techniques or variations of operations 104a-104c may be used in some embodiments.

[0048] In operation 104a, a silicon-containing precursor is introduced into the processing chamber. In various embodiments, the silicon-containing precursor is a silane. Non-limiting examples of silanes that can be used include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. Additional exemplary silicon-containing precursors are further described elsewhere herein in the Definitions and Precursors section. In some embodiments, the silicon-containing precursor is diisopropylaminosilane (DIPAS).

[0049] The silicon-containing precursor is introduced at a flow rate of about 100 sccm to about 2000 sccm for use in a single wafer chamber. In some embodiments, a carrier gas or a driving gas also flows with the silicon-containing precursor. In some embodiments, the carrier gas or the driving gas may be nitrogen or argon. The carrier gas or the driving gas may flow at a flow rate of about 300 sccm to about 1500 sccm for use in a single wafer chamber. Operation 104a may be performed for a duration of about 0.1 seconds to about 10 seconds. In some embodiments, additional nitrogen may be introduced with the silicon-containing gas to serve as a diluent gas, for pressure stabilization, or both. In some embodiments, additional nitrogen flows at a flow rate of about 500 sccm to about 10000 sccm for use in a single wafer chamber. The pressure of the processing chamber during operation 104a may be about 5 Torr to about 25 Torr.

[0050] In one example, during operation 104a, an aminosilane precursor is introduced into a chamber having a pressure of about 22 Torr at a flow rate of about 600 sccm for an exposure time of about 1 second using a push gas at a flow rate of about 1500 sccm.

[0051] Operation 104a is performed without igniting a plasma. In some embodiments, operation 104a is performed in a plasma-free environment.

[0052] In operation 104b, the silicon-containing precursor is thermally decomposed to form a protective layer on the surface of the substrate. The protective layer includes the decomposed silicon-containing precursor. The thermal decomposition is performed so that the susceptor is set at a temperature that is at least the decomposition temperature of the precursor used during the decomposition or higher than the decomposition temperature. Operation 104b can be performed by heating the substrate when the silicon-containing precursor is introduced in operation 104a so that the silicon-containing precursor is decomposed onto the surface of the substrate. The heating substrate can be performed by setting the temperature of the susceptor holding the substrate to at least about 400°C, or at least about 500°C, or at least about 650°C, or at least about 750°C, or about 500°C to about 700°C, or about 650°C or higher, depending on the silicon-containing precursor used.

[0053] During or shortly after this operation, a sweep operation may be performed. In some embodiments, the silicon-containing precursor may continue to flow. In some embodiments, operation 104b involves stopping the flow of the silicon-containing precursor and introducing a flow of an inert gas or sweep gas to decompose silicon-containing precursor molecules adsorbed onto the surface of the substrate or silicon-containing precursor molecules in a gas phase in a processing region of the processing chamber above the substrate.

[0054] Exemplary inert or sweeping gases include, but are not limited to, nitrogen and argon. The flow rate of the inert or sweeping gas during operation 104b is about 1000 sccm to about 40000 sccm. The introduction of the inert or sweeping gas may be performed for a duration of about 0.1 seconds to about 10 seconds. During operation 104b, the chamber pressure may be about 0.5 Torr to about 22 Torr. In some embodiments, the chamber pressure during operation 104b is the same as the chamber pressure during operation 104a. In one example, argon is introduced at a flow rate of about 40000 sccm at a chamber pressure of about 22 Torr for about 2 seconds. In another example, nitrogen is introduced at a flow rate of about 10000 sccm at a chamber pressure of about 22 Torr for about 2 seconds. The flow rate, duration, and chamber pressure may depend on the morphology of the precursor used in operation 104a and the substrate on which the protective layer is to be deposited. Operation 104b is performed without igniting plasma. Operation 104b is performed in a plasma-free environment.

[0055] In some embodiments, operations 104a and 104b are performed in a plasma-free environment.

[0056] In some embodiments, plasma may be used. In some embodiments, plasma may be used to densify or modify the protective layer. During plasma exposure, one or more of the following gases may be used: an inert gas, an oxidizing gas, and a nitrogen-containing gas. Such a gas may be used to ignite a plasma to form an inert gas plasma, an oxidizing plasma, or a nitrogen-containing plasma. An inert gas plasma may be used to densify the decomposed material. Exemplary inert gases include hydrogen, helium, argon, and xenon. An inert gas plasma may be used to smooth the surface of the decomposed film, which may make the thickness of the entire surface uniform. In various embodiments, an inert gas plasma is performed on every approximately 1 nm of film deposited on the substrate surface. An oxidizing gas may be used to oxidize the decomposed material, such as to form silicon oxide. Exemplary oxidizing gases include oxygen, nitrous oxide, carbon dioxide, ozone, and peroxide. A nitrogen-containing gas may be used to form a nitride of the decomposed material, such as to form silicon nitride. Exemplary nitrogen-containing gases include nitrogen and ammonia. In various embodiments, an oxidizing or nitrogen-containing plasma may be used to deposit every approximately 5 nm or less of film on the substrate surface. During exposure to an oxidizing plasma or a nitrogen-containing plasma, one or more additional inert gases may also be used. In some embodiments, hydrogen may also be used. Hydrogen may also be used to help ashing the carbonaceous components of the decomposed film, for example if an organosilane is used during decomposition and the decomposed film has a large carbon content. In some embodiments, an oxygen-free, or nitrogen-free, or oxygen- and nitrogen-free plasma may be used. In some embodiments, the plasma is ignited only in a processing environment with an inert gas. In some embodiments, a gas mixture is used when igniting the plasma.

[0057] In operation 104c, it is determined whether the protective layer has been deposited to a sufficient thickness. The required thickness of the protective layer depends on several factors, including but not limited to the silicon-containing precursor used, the structure or morphology of the substrate provided in operation 102, the function that the protective layer will have when depositing silicon nitride in operation 108, the thickness of the silicon nitride to be deposited in operation 108, the process conditions to be used in operation 108, and whether a certain thickness of the protective layer is required after the silicon nitride is deposited in operation 108. In a non-limiting example, if a certain thickness is required after the silicon nitride is deposited in operation 108, a thicker protective layer can be deposited. However, a thin protective layer can also be deposited by switching the process conditions used in operation 108 and still maintaining the desired thickness after the silicon nitride is deposited. If the protective layer is not deposited to a sufficient thickness, operations 104a and 104b can be repeated until the desired thickness is reached.

[0058] In some embodiments, the protective layer is deposited to at least about or at least about or about to about or about to about or about to about In some embodiments, if the process conditions used in operation 108 involve high temperature or high power plasma or other harsher process conditions, the thickness of the protective layer can be increased to accommodate later exposure to plasma to deposit SiN, thereby fully protecting the underlying low-k dielectric. A non-limiting example of a high temperature is a temperature greater than 650° C. for a high power plasma process having at least about 6000 kW or at least about 10,000 kW plasma power per station. In contrast, silicon nitride can be deposited at a temperature as low as about 100° C. with an RF power of about 3000 kW to about 6000 kW.

[0059] The protective layer may have properties in some embodiments that enable it to withstand certain wet etching conditions. For example, the wet etching rate of the protective layer in 100:1 dilute hydrofluoric acid may be about / minute or less.

[0060] In certain embodiments, a purge may be performed between any or all operations, such as after decomposition but before inert plasma exposure, or after inert plasma exposure and before oxidation or nitrogen-containing plasma exposure, or after oxidation or nitrogen-containing plasma exposure and before repeating any, or any number of, or all of the above operations. The purge may be optional. In some embodiments, no purge is performed between operations 104a and 104b.

[0061] Certain disclosed embodiments may allow for faster deposition due to higher deposition rates. For example, cycles of precursor decomposition may form about to about Thick films can be obtained. Depending on the precursor used, the deposition rate may vary.

[0062] Certain disclosed embodiments may also be used to form films with a number of dopants, which may be introduced during any operation or by using specific deposition precursors in the gas phase in a plasma-free environment. Dopants include, but are not limited to, carbon (C), nitrogen (N), boron (B), and phosphorus (P). Such dopants may be incorporated by exposing the substrate to one or more of the following gases: CH and ammonia (NH). Certain disclosed embodiments may form films with silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, doped variants thereof, or combinations thereof.

[0063] return Figure 1AIn operation 106, the processing chamber may optionally be purged. The purge may be performed using any of the gases, flow rates, temperatures, pressures, and other process conditions described above with respect to operation 104b without evacuating the chamber. Purging the chamber may include flowing a purge gas or purge gas, which may be a carrier gas used for other operations or may be a different gas. In some embodiments, the purge may involve evacuating the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, the purge gas flows at about 1000 seem to about 40,000 seem for a period of time at a chamber pressure of about 0.5 Torr or about 22 Torr.

[0064] In some embodiments, operation 106 may include one or more evacuation sub-stages for evacuating the process chamber. Alternatively, it should be understood that operation 106 may be omitted in some embodiments. Operation 106 may have any suitable duration, such as between about 0 seconds and about 60 seconds, or about 0.1 seconds to about 10 seconds. In some embodiments, increasing the flow rate of one or more purge gases may reduce the duration of operation 106. For example, the purge gas flow rate may be adjusted according to a number of reactant thermodynamic properties and / or geometric properties of the process chamber and / or process chamber piping to modify the duration of operation 106. In a non-limiting example, the duration of the purge phase may be adjusted by adjusting the purge gas flow rate. This may reduce the deposition cycle time, thereby improving substrate yield.

[0065] In operation 108, silicon nitride is deposited over the protective layer and over the low-k dielectric material. During operation 108, at least a portion of the protective layer may be converted to SiN. During operation 108, at least a portion of a top layer of the protective layer may be converted to SiN. The deposition in operation 108 may involve igniting a plasma.

[0066] Figure 1C An example of a method for depositing silicon nitride in a plasma environment in operation 108 is provided. Figure 1C An example is shown, but it should be understood that other deposition techniques that may at least partially convert a portion of the protective layer to silicon nitride when depositing silicon nitride may also be used and the protective layer may still have the advantages described herein.

[0067] Figure 1C It is shown that operation 108 can be performed using operations 108a, 108b, 108c, 108d, and 108e. Operations 108b and 108d are optional. Operations 108a and 108c can constitute one deposition cycle. Operations 108a and 108c can constitute one ALD cycle.

[0068] In operation 108a, a silicon-containing precursor may be introduced into the processing chamber. The silicon-containing precursor may be any of the precursors described above with respect to operation 104a and described elsewhere herein. In some embodiments, the silicon-containing precursor includes or is the same as the silicon-containing precursor used in operation 104a. In some embodiments, the silicon-containing precursor does not include or is different from the silicon-containing precursor used in operation 104a.

[0069] In some embodiments, the silicon-containing precursor may flow at a flow rate of about 100 sccm to about 2000 sccm for a single wafer chamber. The silicon-containing precursor may flow with an inert push gas, such as nitrogen or argon or a mixture of nitrogen and argon. The flow rate of the inert push gas may be about 300 sccm to about 1500 sccm for a single wafer chamber. Operation 108a may be performed for a duration of about 0.1 seconds to about 10 seconds. During operation 108a, the processing chamber may have a chamber pressure of about 1 Torr to about 25 Torr. In some embodiments, additional nitrogen may be introduced with the silicon-containing precursor and / or the inert push gas for dilution, for pressure stability, or both. Additional nitrogen may flow at a flow rate of about 500 sccm to about 2000 sccm for a single wafer chamber. In an example, in a plasma-free environment, at a chamber pressure of about 18 Torr, DIPAS is introduced into a chamber containing a substrate having a protective layer thereon at a flow rate of about 200 sccm for about 2 seconds.

[0070] In operation 108b, the process chamber is optionally purged. Figure 1A The purge may be performed using any of the chemicals or process conditions described in operation 106 of the present invention. In some embodiments, a mixture of nitrogen and argon is used to purge the process chamber. Operation 108b may be performed for a duration of about 0.1 seconds to about 10 seconds. The chamber pressure during operation 108b may be about 0.5 Torr to about 25 Torr. In some embodiments, the chamber pressure during operation 108b is the same as during operation 108a.

[0071] In one example, nitrogen flows at a flow rate of about 20 slm and argon flows at a flow rate of about 20 slm for about 1 second for a single wafer chamber in the absence of plasma and at a chamber pressure of about 18 Torr.Purge may involve stopping the flow of the silicon-containing precursor and introducing a purge gas.

[0072] return Figure 1CIn operation 108c, the substrate is exposed to a nitrogen-containing plasma, which converts at least some of the adsorbed silicon-containing precursor into silicon nitride and reacts with at least a portion of the protective layer to convert the portion into silicon nitride. When the protective layer is exposed to the plasma in operation 108c, at least a portion of the protective layer is converted into silicon nitride. At the same time, additional silicon nitride may also grow above the protective layer. Extended exposure to the nitrogen-containing plasma or repeated operations or specific process conditions may convert more of the protective layer into silicon nitride until a specific penetration depth of the protective layer. Exposure to the nitrogen-containing plasma may also eventually convert all of the protective layer into silicon nitride. The resulting substrate has silicon nitride above the dielectric material, where the location of the previous deposition or formation of the protective layer cannot be distinguished. The quality of the silicon nitride formed by the plasma deposition and the conversion of the protective layer may also be indistinguishable.

[0073] Operation 108c may involve stopping the purge and / or stopping the flow of the purge gas and starting to introduce a nitrogen-containing plasma. In some embodiments, for an in-situ plasma, operation 108c includes stopping the purge or the introduction of the purge gas and flowing the nitrogen-containing gas into the processing chamber and igniting the plasma. In some embodiments, for a remote plasma, operation 108c involves stopping the purge or the introduction of the purge gas and introducing nitrogen-containing plasma species from a remote plasma generator into the processing chamber.

[0074] In various embodiments, the nitrogen-containing plasma is generated by igniting a nitrogen-containing gas, such as nitrogen (N2). The nitrogen-containing gas may flow at a flow rate of about 1000 sccm to about 5000 sccm for use in a single wafer chamber. In some embodiments, the nitrogen-containing plasma is generated by igniting a mixture of a nitrogen-containing gas and a hydrogen-containing gas, such as a mixture of nitrogen and hydrogen, a mixture of nitrogen and ammonia, a mixture of nitrogen, hydrogen and ammonia, and the like. In one example, the mixture of nitrogen and hydrogen may have a nitrogen flow rate of about 20 slm and a hydrogen flow rate of about 10 sccm to about 1000 sccm. An inert gas that may be used as a push gas or a carrier gas may also be flowed. In some embodiments, the inert gas may be argon. The inert gas may flow at a flow rate of about 10 slm to about 40 slm. Operation 108c may be performed for a duration of about 1 second to about 30 seconds. The chamber pressure during operation 108c may be about 15 Torr to about 25 Torr. In some embodiments, higher pressures (e.g., at least about 10 Torr) can be used to deposit conformal SiN. The plasma can be generated using a plasma power of about 500 W to about 6000 kW. In some embodiments, the chamber pressure during operation 108c is the same as during any one or more of operations 108a and 108b.

[0075] In one example, during operation 108c, after stopping the purge, nitrogen flows at a flow rate of about 2000 seem, argon flows at a flow rate of about 18 slm, and the plasma is ignited for a duration of about 5 seconds using a plasma power of about 2 kW in a chamber having a chamber pressure of about 18 Torr.

[0076] In some embodiments, operation 108c involves multiple operations, including exposing the substrate to a nitrogen-containing gas, optionally purging, and exposing the substrate to a nitrogen-containing plasma. This may be referred to as a "hybrid" deposition. In such embodiments, one cycle of depositing SiN in operation 108 involves introducing a silicon-containing precursor in operation 108a, optionally purging in operation 108b, introducing a nitrogen-containing gas without igniting a plasma or in a plasma-free environment, optionally purging, introducing a nitrogen-containing gas, and optionally purging in operation 108d.

[0077] In the case of using a hybrid deposition process to deposit SiN, the nitrogen-containing gas introduced without igniting plasma or the nitrogen-containing gas introduced in a plasma-free environment may be ammonia (NH3). In some embodiments, NH3 is introduced at a flow rate of about 1000sccm to about 4500sccm for a single wafer chamber. In some embodiments, NH3 is introduced with one or more diluent gases (e.g., nitrogen or argon or both). In some embodiments, during exposure to a nitrogen-containing gas without igniting plasma, nitrogen flows at a flow rate of about 1000sccm to about 5000sccm for a single wafer chamber. Argon can flow at a flow rate of about 10slm to about 40slm for a single wafer chamber. Exposure to a nitrogen-containing gas without igniting plasma can be performed for a duration of about 1 second to about 30 seconds. Exposure to a nitrogen-containing gas without igniting plasma can be performed at a chamber pressure of about 15Torr to about 25Torr. In one example, NH3 is introduced at a flow rate of about 4.5slm, and a mixture of nitrogen and argon is introduced at a flow rate of about 10slm. Introducing the nitrogen-containing gas without igniting a plasma may convert some of the silicon-containing precursor adsorbed onto the substrate surface in operation 108a into silicon nitride.

[0078] After exposure to the nitrogen-containing gas in the plasma-free environment, an optional sweep operation may be performed, which may be performed according to the above description of Figure 1A In some embodiments, the purge involves flowing nitrogen at a flow rate of about 20 slm. In some embodiments, the purge involves flowing argon at a flow rate of about 20 slm. In some embodiments, the purge is performed for a duration of about 0.1 seconds to about 10 seconds. In some embodiments, the purge is performed at a chamber pressure of about 0.5 Torr to about 25 Torr.

[0079] In the mixed SiN deposition process, a plasma operation can be performed using a nitrogen-containing plasma. In some embodiments, the operation includes flowing a nitrogen-containing gas, such as nitrogen. The nitrogen-containing gas can flow at a flow rate of about 1000 sccm to about 5000 sccm. In some embodiments, a variety of nitrogen-containing gases can be flowed. For example, in addition to nitrogen, ammonia can also be flowed. In some embodiments, in addition to nitrogen, hydrogen can also be flowed. In some embodiments, in addition to nitrogen, ammonia and hydrogen can also be flowed. Inert gases can also flow during this operation. For example, argon can be flowed. Inert gases can flow at a flow rate of about 10 slm to about 40 slm. The plasma operation can be performed for a duration of about 1 second to about 30 seconds. The chamber pressure during plasma exposure can be about 15 Torr to about 25 Torr. The plasma can be generated using a plasma power of about 500 W to about 6000 kW.

[0080] In one example, during plasma operation, about 2000 seem of nitrogen and about 125 seem of ammonia were flowed in about 18 slm of argon, where the nitrogen and ammonia were ignited using a plasma with about 2 kW power at a chamber pressure of about 18 Torr for a duration of about 5 seconds.

[0081] For this plasma operation and for any other plasma environment that may be used in operation 108 (e.g., in operation 108c), in various embodiments, the plasma may be an inductively coupled plasma or a capacitively coupled plasma. The inductively coupled plasma may be set at a plasma power between about 500W and about 6000kW. In some embodiments, a bias between about 0V and about 1000V may be applied. In some embodiments, no bias is applied.

[0082] Without being bound by a particular theory, it is believed that exposing the protective layer to the nitrogen-containing plasma at least partially converts a portion of the protective layer to SiN. For example, the plasma may provide sufficient energy to cleave certain bonds in the decomposed silicon-containing precursor in the protective layer and combine with nitrogen, thereby leaving SiN on the substrate surface. As the conversion occurs, some additional SiN may also be deposited on the substrate surface by converting silicon-containing precursors adsorbed to the substrate surface (e.g., any silicon-containing precursor adsorbed on the surface of the protective layer).

[0083] In operation 108d, the process chamber is optionally purged. Figure 1AThe purge is performed using any chemical substance or process condition described in operation 106 of . In some embodiments, the purge is performed using the same process conditions as during operation 108b. The purge can be performed using nitrogen, argon, or a mixture of the two, or any other inert gas. In some embodiments, nitrogen flows at a flow rate of about 20 slm. Argon can flow at a flow rate of about 20 slm. Each inert gas flowing during the purge can flow at a flow rate of about 20 slm. The purge can be performed for a duration of about 0.1 seconds to about 10 seconds. The purge can be performed for the same duration as the duration performed in operation 108b. The chamber pressure during operation 108d can be about 0.5 Torr to about 25 Torr. In some embodiments, the chamber pressure during operation 108d is the same as during any one or more of operations 108a, 108b, and 108c.

[0084] In operation 108e, it is determined whether the film has been deposited to a sufficient thickness. If not, operations 108a and 108c may be repeated. In some embodiments, operations 108a, 108b, 108c, and 108d may be repeated in a cycle. One cycle may consist of performing operations 108a and 108c at least once. One cycle may consist of performing each of operations 108a, 108b, 108c, and 108d once. In some embodiments, the operation may be repeated to convert all or at least about 90% of the protective layer into silicon nitride. In some embodiments, the operation may be repeated to leave a protective layer several angstroms thick between the dielectric material and the silicon nitride. The protective layer may have a robust wet etch rate and, depending on its application, may serve as an additional protective layer above the dielectric to support the entire stack. In Figure 2E-2 An example of retaining a portion of the protection layer between the low-k dielectric or SiOC layer and the SiN layer is provided in , which is further described below.

[0085] Figure 2A A low-k dielectric silicon oxycarbide substrate 200 is shown. This exemplary substrate may correspond to a Figure 1A In operation 102, a substrate is provided. Figure 2B A protective layer 202 is shown deposited thereon. Figure 1A Operation 104 or having Figure 1B The protective layer 202 is deposited by the exemplary process of operations 104a and 104b and optional 104c. Figure 2C It is shown that silicon nitride 204 begins to grow above the protective layer 202. This may correspond to Figure 1A Operation 108 and Figure 1C Optional operations 108a and 108c, or Figure 1C As deposition and exposure to the nitrogen-containing plasma occur, Figure 2D In some embodiments, more of the protective layer 202 is converted into silicon nitride, and silicon nitride 204 is further deposited on the protective layer 202. Figure 2E-1 In some embodiments, all of the protective layer is converted to silicon nitride 204, resulting in silicon nitride 204 being adjacent to and in direct contact with low-k dielectric silicon oxycarbide 200. Figure 2E-2 in Figure 2D Thereafter, a portion of the protection layer 202 remains unconverted between the silicon nitride 204 and the low-k dielectric silicon oxycarbide 200 , such that the protection layer 202 is in contact with and / or sandwiched between the silicon nitride 204 and the low-k dielectric silicon oxycarbide 200 . Device

[0086] Figure 3 A schematic diagram of an embodiment of an atomic layer deposition (ALD) processing station 300 is depicted, and the ALD processing station 300 has a processing chamber body 302. In various embodiments, in Figure 4 A single processing station 300 is implemented in the tool shown. In some embodiments, multiple ALD processing stations 300 may be included in a low pressure processing tool environment. For example, Figure 3 An embodiment of a multi-station processing tool 300 is depicted. In some embodiments, one or more hardware parameters of the ALD processing station 300 are programmably adjustable by one or more computer controllers 350, including those parameters discussed in detail below.

[0087] The ALD processing station 300 is in fluid communication with a reactant delivery system 301a to deliver process gases to the showerhead 306. The reactant delivery system 301a includes a mixing vessel 304 for mixing and / or regulating process gases, such as silicon-containing precursor gases or nitrogen-containing gases, for delivery to the showerhead 306. One or more mixing vessel inlet valves 320 can control the introduction of process gases to the mixing vessel 304. One or more valves 305 can control the introduction of process gases to the showerhead 306.

[0088] As an example, Figure 3Embodiments include a vaporization point 303 for vaporizing liquid reactants to be supplied to a mixing container 304. In some embodiments, the vaporization point 303 may be a heated vaporizer. The saturated reactant vapor produced from such a vaporizer may condense in the downstream transport pipeline. Exposure of incompatible gases to condensed reactants may produce small particles. These small particles may block the pipeline, hinder valve operation, contaminate substrates, etc. Some ways to deal with these problems involve cleaning and / or emptying the transport pipeline to remove residual reactants. However, cleaning the transport pipeline may increase the processing station cycle time and reduce the processing station productivity. Therefore, in some embodiments, the transport pipeline downstream of the vaporization point 303 may be heated. In some examples, the mixing container (not shown) may also be heated. In a non-limiting example, the pipeline downstream of the vaporization point 303 has a temperature increase curve extending from about 40°C to about 55°C at the mixing container or from about 60°C to about 65°C at the mixing container.

[0089] In some embodiments, a liquid precursor or liquid reactant can be vaporized at a liquid injector. For example, a liquid injector can inject a pulse of a liquid reactant into a carrier gas stream upstream of a mixing vessel. In one embodiment, a liquid injector can vaporize a reactant by flashing a liquid from a higher pressure to a lower pressure. In another example, a liquid injector can atomize a liquid into dispersed micro-droplets, which are then vaporized in a heated delivery line. Smaller droplets can vaporize faster than larger droplets and reduce the delay between liquid injection and complete vaporization. Faster vaporization can reduce the length of the pipeline downstream of the vaporization point 303. In one case, a liquid injector can be mounted directly to a mixing vessel. In another case, a liquid injector can be mounted directly to a spray head 306.

[0090] In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 303 may be provided to control the mass flow rate of the liquid used for vaporization and delivery to the ALD processing station 300. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-differential (PID) controller electrically connected to the MFM. However, it may take one second or more to stabilize the liquid flow using feedback control. This may extend the time for dosing the liquid reactants. Therefore, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be performed by deactivating the induction tube and PID controller of the LFC.

[0091] The showerhead 306 distributes process gases toward the substrate 312. Figure 3In the embodiment shown, substrate 312 is located below showerhead 306 and is shown disposed on pedestal 308. Showerhead 306 may have any suitable shape and may have any suitable number and arrangement of ports to distribute process gases to substrate 312.

[0092] In some embodiments, the pedestal 308 may be raised or lowered to expose the substrate 312 to the volume between the substrate 312 and the showerhead 306. It should be appreciated that in some embodiments, the pedestal height may be programmatically adjusted by a suitable computer controller 350.

[0093] In another case, adjusting the height of the pedestal 308 can allow the plasma density to be varied during plasma activation in a process in an embodiment of igniting a plasma. At the end of a process phase, the pedestal 308 can be lowered to allow the substrate 312 to be removed from the pedestal 308 during another substrate transfer phase.

[0094] In some embodiments, the susceptor 308 can be temperature controlled via a heater 310. In some embodiments, the susceptor 308 can be heated to a temperature of about 25° C. to about 800° C., or about 200° C. to about 700° C. during silicon oxide film deposition as described in the disclosed embodiments. In some embodiments, the susceptor is set at a temperature of about 45° C. to about 800° C., or about 500° C. to about 700° C. In some embodiments, the same susceptor 308 is used for multiple operations according to certain disclosed embodiments.

[0095] Additionally, in some embodiments, pressure control of the ALD processing station 300 may be provided by a butterfly valve 318. Figure 3 In the embodiment shown, butterfly valve 318 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of ALD process station 300 can also be adjusted by changing the flow rate of one or more gases introduced into ALD process station 300.

[0096] In some embodiments, the position of the showerhead 306 can be adjusted relative to the pedestal 308 to change the volume between the pedestal 312 and the showerhead 306. In addition, it should be understood that the vertical position of the pedestal 308 and / or the showerhead 306 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 308 can include a rotation axis for rotating the orientation of the substrate 312. It should be understood that in some embodiments, one or more of these exemplary adjustments can be performed programmatically by one or more appropriate computer controllers 350.

[0097] In some embodiments where plasma can be used as discussed above, the showerhead 306 and the pedestal 308 are electrically connected to a radio frequency (RF) power supply 314 and a matching network 316 for supplying energy to the plasma. For example, the plasma can be used to treat the silicon oxide surface before depositing silicon nitride. In some embodiments, the plasma energy can be controlled by controlling one or more of the processing station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse time. For example, the RF power supply 314 and the matching network 316 can be operated at any suitable power to form a plasma with a composition of desired free radical species. Examples of suitable powers for a single station chamber are about 150W to 10,000W or about 500W to about 6,000kW. For a 3-station chamber, the plasma power may include four generators, each generator supplying up to about 10,000W, for a total of about 30,000W. For annealed silicon oxide films, the substrate may be exposed to a nitrogen-containing gas, or a mixture of a nitrogen-containing gas and an optional inert gas, while the plasma is ignited using the RF power supply 314 and the matching network 316.

[0098] In some embodiments, the substrate may be exposed to a nitrogen-containing gas while the plasma is ignited to anneal silicon oxide using, for example, a plasma power between about 500 W and about 10,000 W per 300 mm wafer surface area. The plasma may be generated remotely (e.g., in a remote plasma generator) or directly in a chamber containing the substrate (i.e., in situ). The RF power supply 314 may provide RF power of any suitable frequency. In some embodiments, the RF power supply 314 may be configured to control high-frequency and low-frequency RF power sources independently of each other. Examples of low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Exemplary high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 3.45 GHz, or greater than about 13.56 MHz, or greater than about 27 MHz, or greater than about 30 MHz, or greater than about 60 MHz. It should be understood that any suitable parameter may be adjusted discretely or continuously to provide plasma energy for surface reactions.

[0099] In some embodiments, the plasma can be monitored in situ by one or more plasma monitors. In one case, the plasma power can be monitored by one or more voltage and current sensors (e.g., VI probes). In another case, the plasma density and / or the concentration of the process gas can be measured by one or more optical emission spectrometer sensors (OES). In some embodiments, one or more plasma parameters can be adjusted programmatically based on the measurement results from such in-situ plasma monitors. For example, an OES sensor can be used in a feedback loop to provide programmatic control of the plasma power. It should be understood that in some embodiments, other monitors can be used to monitor plasma and other processing characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure sensors.

[0100] In some embodiments, instructions for the controller 350 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for a process stage may be included in a corresponding recipe stage of a process recipe. In some cases, the process recipe stages may be configured sequentially so that all instructions for the process stage are executed synchronously with the process stage. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe stage. For example, a first recipe stage may include instructions for setting the flow rate of a silicon-containing precursor gas, instructions for setting the flow rate of a carrier gas (e.g., argon), and time delay instructions for the first recipe stage. A second recipe stage may include instructions for adjusting or stopping the flow rate of an inert and / or reactant gas, instructions for optional heating, instructions for setting the flow rate of a carrier gas (e.g., argon), and time delay instructions for the second recipe stage. A subsequent third recipe stage may include instructions for adjusting or stopping the flow rate of an inert and / or reactant gas, instructions for adjusting the flow rate of a second silicon-containing precursor, and time delay instructions for the third recipe stage. The fourth recipe stage may include instructions for adjusting or stopping the flow rate of the inert and / or reactant gases, instructions for adjusting the flow rate of the carrier gas or purge gas, and time delay instructions for the fourth recipe stage. The subsequent fifth recipe stage may include instructions for setting the flow rate of the nitrogen-containing gas, instructions for igniting the plasma, and instructions for adjusting the flow rate of the carrier gas or purge gas, and time delay instructions for the fifth recipe stage. The sixth recipe stage may include instructions for adjusting or stopping the flow rate of the inert and / or reactant gases, instructions for modulating the flow rate of the carrier gas or purge gas, and time delay instructions for the sixth recipe stage. It should be understood that these recipe stages may be further divided and / or repeated in any suitable manner within the scope of the present disclosure. In some embodiments, the controller 350 may include the following regarding Figure 4 The system controller 450 and Figure 3Any features described by the system controller 350.

[0101] The processing station may be included in e.g. Figure 4 In a single station chamber or single chamber tool as shown in . Figure 4 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 400 includes a processing chamber 414 having a processing station 490 that can process a wafer. Processing chamber 414 is configured to deposit silicon oxide, deposit silicon nitride, anneal a substrate using thermal annealing or plasma annealing, and the like.

[0102] The tool 400 also includes a wafer transfer unit configured to transfer wafers within the tool 400. Other features of the tool 400 will be discussed in more detail below, and various features related to certain of the described techniques are discussed herein. In the depicted figure, the wafer transfer unit includes a first robot unit 426 in a first wafer transfer module and a second robot unit 406 in a second wafer transfer module, which can be considered as an equipment front end module (EFEM) configured to receive a container of wafers, such as a front opening unified module (FOUP) 408. The first robot unit 426 is configured to transfer wafers between a processing chamber 414 and the second robot unit via a module 404, which can hold multiple wafers, such as shown in the module 402 with a substrate 412. The second robot unit 406 is configured to transfer wafers between a FOUP and a module 404, or from a module 402 to a FOUP. After the wafers are prepared in the module 404, the wafer transfer unit can transfer the wafers to the first processing chamber 414 for in-situ deposition and optional annealing.

[0103] Similar to the above, the first wafer transfer module can be a vacuum transfer module (VTM). An air lock or module 404, also known as a load lock, is shown and can be optimized individually to perform various manufacturing processes. Tool 400 also includes a FOUP 408 configured to reduce the pressure of tool 400 to a vacuum or a low pressure, such as between about 1 mTorr and about 10 Torr, and maintain tool 400 at this pressure. This includes maintaining the processing chamber 414 and the first wafer transfer module under vacuum or low pressure. The second wafer transfer module can be at a different pressure, such as atmospheric pressure. Since the wafers are transferred throughout the tool 400, the wafers are maintained under vacuum or low pressure.

[0104] In a further example, the substrate is placed in one of the FOUPs 408 and the second robot unit 406, or the front end robot transfers the substrate from the FOUP 418 to an aligner that allows the substrate to be properly centered before it is etched, deposited, or otherwise processed. After alignment, the substrate is moved into the airlock module 404 by the second robot unit 406. Because the airlock module has the ability to match environments between ATM and VTM, the substrate can be moved between the two pressure environments without damage. The substrate is moved from the airlock module 404 to the processing chamber 414 via the first wafer transfer module, or VTM, by the first robot unit 426. To achieve this substrate movement, the first robot unit 426 uses an end effector on each of its arms.

[0105] Figure 4 Also depicted is an embodiment of a system controller 450 for controlling process conditions and hardware states of the processing tool 400. The system controller 450 may include one or more memory devices 456, one or more mass storage devices 454, and one or more processors 452. The processor 452 may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc. In some embodiments, the system controller 450 includes a processor for performing, for example, the above-described Figure 5 And the following about Figure 5 Machine readable instructions for these operations described.

[0106] As described above, one or more processing stations may be included in a multi-station processing tool. Figure 5 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 500 includes a first processing chamber 502 and a second processing chamber 504. First processing chamber 502 includes a plurality of processing stations, four stations 580A to D, each of which can process one wafer. First processing chamber 502 is configured to perform plasma processing operations on a wafer. Second processing chamber 504 is configured to perform deposition on a wafer and can be considered a deposition chamber. Second processing chamber 504 also includes a plurality of processing stations, four stations 582A to D, each of which can process one wafer. First and second processing chambers 502 and 504 can be considered multi-station processing chambers.

[0107] The tool 500 also includes a wafer transfer unit configured to transfer one or more wafers within the tool 500. Other features of the tool 500 will be discussed in more detail below, and various features related to certain of the described techniques are discussed herein. In the depicted figure, the wafer transfer unit includes a first robot unit 508 in a first wafer transfer module 510 and a second robot unit 512 in a second wafer transfer module 514, which can be viewed as an equipment front end module (EFEM) configured to receive a container for wafers, such as a front opening unified module (FOUP) 516. The first robot unit 508 is configured to transfer wafers between the first processing chamber 502 and the second processing chamber 504, and between the second robot unit 512. The second robot unit 512 is configured to transfer wafers between the FOUP and the first robot unit 508. After the wafers have been processed in the first processing chamber 502, the wafer transfer unit can transfer the wafers from the first processing chamber 502 to the second processing chamber 504, where one or more layers of encapsulation material can be deposited on one or more wafers.

[0108] Similar to the above, the first wafer transfer module 510 can be a vacuum transfer module (VTM). An air lock 520, also referred to as a load lock or transfer module, is shown and can be optimized individually to perform various manufacturing processes. The tool 500 also includes a FOUP 516 configured to reduce the pressure of the tool 500 to a vacuum or a low pressure, such as between about 1mTorr and about 10Torr, and maintain the tool 500 at this pressure. This includes maintaining the first and second processing chambers 502 and 504, and the first wafer transfer module 510 at a vacuum or low pressure. The second wafer transfer module 514 can be at a different pressure, such as atmospheric pressure. Since the wafer is transferred throughout the tool 500, the wafer is maintained at a vacuum or low pressure. For example, since the wafer is transferred from the first processing chamber 502 into the first wafer transfer module 510 and arrives at the second processing chamber 504, the wafer is maintained at a vacuum or low pressure without being exposed to atmospheric pressure.

[0109] In a further example, the substrate is placed in one of the FOUP 518 and the second robot unit 512, or the front end robot transfers the substrate from the FOUP 518 to an aligner that allows the substrate to be properly centered before it is etched, deposited, or otherwise processed. After alignment, the substrate is moved into the airlock 520 by the second robot unit 512. Because the airlock module has the ability to match the environment between the ATM and the VTM, the substrate can be moved between the two pressure environments without damage. The substrate is moved from the airlock 520 via the first wafer transfer module 510, or the VTM510 into the first processing chamber 502 by the first robot unit 508. To achieve this substrate movement, the first robot unit 508 uses an end effector on each of its arms.

[0110] Figure 5 Also depicted is an embodiment of a system controller 529 for controlling process conditions and hardware states of the tool 500. The system controller 529 may include one or more memory devices (not shown), one or more mass storage devices (not shown), and one or more processors (not shown). The processor may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc.

[0111] In some embodiments, the system controller 529 controls all activities of the tool 500. The system controller 529 executes system control software stored in a mass storage device, loaded into a memory device, and executed on a processor. Alternatively, the control logic may be hard-coded in the system controller 529. Application-specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays, or FPGAs) and the like may be used for these purposes. In the following discussion, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software may include instructions for controlling the timing, mixing of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestals, chuck and / or sensor positions, and parameters of a particular process performed by the tool 500. The system control software may be configured in any suitable manner. For example, various processing tool component subroutines or control targets may be written to control the operation of processing tool components used to implement the processes of various processing tools. The system control software may be encoded in any suitable computer-readable programming language.

[0112] In some embodiments, the system control software may include input / output control (IOC) sequence instructions for controlling the various parameters described above. Other computer software and / or programs stored on mass storage devices and / or memory devices associated with the system controller 529 may be employed in some embodiments. Examples of programs or program segments for this purpose include substrate positioning programs, process gas control programs, pressure control programs, heater control programs, and plasma control programs.

[0113] The substrate positioning program may contain program code for processing tool components used to load a substrate onto a pedestal and control the spacing between the substrate and other parts of the tool 500.

[0114] The process gas control program may include code for controlling gas composition (e.g., silicon-containing precursor gas, nitrogen-containing gas, carrier gas, inert gas, and / or purge gas as described herein) and flow rate, and optionally code for flowing gas into one or more process stations to stabilize pressure in the process station prior to deposition. The pressure control program may include code for controlling pressure in a process station by adjusting, for example, a throttle valve in an exhaust system of the process station, gas flow into the process station, and the like.

[0115] The heater control program may include code for controlling the current to a heating unit for heating the substrate.Alternatively, the heater control program may control the delivery of a heat transfer gas (eg, helium or nitrogen) to the substrate.

[0116] The plasma control program may include code for setting RF power levels applied to process electrodes in one or more process stations according to embodiments herein.

[0117] The pressure control program may include code for maintaining pressure in a reaction chamber according to embodiments herein.

[0118] In some embodiments, there may be a user interface associated with the system controller 529. The user interface may include a display screen, a graphical software display of apparatus and / or processing conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, and the like.

[0119] In some embodiments, the parameters adjusted by the system controller 529 may relate to process conditions. Non-limiting examples include process gas composition and flow rate, temperature, pressure, plasma conditions (e.g., RF bias power level), etc. These parameters may be provided to the user in the form of a recipe, which may be entered using the user interface.

[0120] Signals for monitoring the process may be provided from various process tool sensors by analog and / or digital input connections of the system controller 529. Signals for controlling the process may be output through analog and / or digital output connections of the process tool 500. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (e.g., manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain process conditions.

[0121] The system controller 529 may provide program instructions for implementing the above-described deposition process. The program instructions may control various process parameters, such as DC power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate the in-situ deposition of the film stack according to various embodiments described herein.

[0122] The system controller 529 will typically include one or more memory devices and one or more processors configured to execute instructions so that the apparatus will perform methods according to the disclosed embodiments. A machine-readable medium containing instructions for controlling process operations according to the disclosed embodiments may be coupled to the system controller 529.

[0123] In some implementations, the controller 529 is part of a system that can be part of the above-described embodiments. Such a system can include a semiconductor processing device that includes one or more processing tools, one or more processing chambers, one or more platforms for processing, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems can be integrated with electronic devices for controlling their operations before, during, and after processing semiconductor wafers or substrates. The electronic device can be referred to as a "controller" that can control various components or subcomponents of one or more systems. Depending on the type of processing conditions and / or system, the system controller 529 can be programmed to control any of the processes disclosed herein, including controlling process gas delivery, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings in some systems, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and operation settings, wafer transfer in and out of tools and other transfer tools and / or load locks connected to or connected to a specific system through an interface.

[0124] In a broad sense, the system controller 529 can be defined as an electronic device with various integrated circuits, logic, memory and / or software that receives instructions, issues instructions, controls operations, enables cleaning operations, enables endpoint measurements, etc. The integrated circuit can include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions can be instructions transmitted to the system controller 529 in the form of various separate settings (or program files) that define operating parameters for performing specific processing on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer for completing one or more processing steps during the preparation of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0125] In some implementations, the system controller 529 may be part of or coupled to a computer that is integrated with, coupled to, or connected to the system or a combination thereof via a network. For example, the system controller 529 may be in the "cloud" or all or part of a wafer fab host system, thereby allowing remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of a manufacturing operation, check the history of past manufacturing operations, check trends or performance criteria for multiple manufacturing operations, change parameters of a current process, set processing steps to follow the current process, or start a new process. In some embodiments, a remote computer (e.g., a server) may provide a processing recipe to the system via a network, which may include a local network or the Internet. The remote computer may include a user interface that allows input or programming of parameters and / or settings, which are then transmitted from the remote computer to the system. In some embodiments, the system controller 529 receives instructions in the form of data that specify parameters for each processing step to be performed during one or more operations. It should be understood that the parameters may be for the type of process to be performed and the type of tool to which the system controller 529 is configured to connect or control the tool type. Thus, as described above, the system controller 529 can be distributed, for example, by including one or more discrete controllers that are networked together and work toward a common goal (e.g., processing and control as described herein). An embodiment of a distributed controller for these purposes can be one or more integrated circuits on the chamber that communicate with one or more remote integrated circuits (e.g., at the platform level or as part of a remote computer) that are combined to control the processing within the chamber.

[0126] Example systems may include, but are not limited to, plasma etch chambers or modules, deposition chambers or modules, spin cleaning chambers or modules, metal plating chambers or modules, cleaning chambers or modules, chamfer edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, ALD chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing system that may be associated with or used in the preparation and / or manufacture of semiconductor wafers.

[0127] As described above, depending on the one or more processing steps to be performed by the tool, the system controller 529 can communicate with one or more of the following: other tool circuits or modules, other tool components, combination tools, other tool interfaces, adjacent tools, adjacent tools, tools located throughout the factory, a host computer, another controller, or tools used in material handling to move containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing facility.

[0128] Suitable apparatus for performing the methods disclosed herein are further discussed and described in U.S. patent application Ser. No. 13 / 084,399, filed on Apr. 11, 2011, and entitled “PLASMA ACTIVATED CONFORMAL FILMDEPOSITION” (now U.S. Patent No. 8,728,956); and U.S. patent application Ser. No. 13 / 084,305, filed on Apr. 11, 2011, and entitled “SILICON NITRIDE FILMS AND METHODS,” each of which is incorporated herein in its entirety.

[0129] The apparatus / processes described herein can be used in conjunction with photolithographic patterning tools or processes, e.g., for preparing or manufacturing semiconductor devices, displays, LEDs, photovoltaic panels, etc. Typically, though not necessarily, these tools / processes will be used or operated together in a common manufacturing facility. Photolithographic patterning of films typically includes some or all of the following operations, each of which enables multiple available tools: (1) coating a workpiece, i.e., substrate, with photoresist using a spin coating or spray coating tool; (2) curing the photoresist using a hot plate or oven or UV curing tool; (3) exposing the photoresist to visible light or UV light or X-rays using a tool such as a wafer stepper; (4) developing the resist so as to selectively remove the resist and thereby pattern it using a tool such as a wet cleaning station; (5) transferring the resist pattern to an underlying film or workpiece by using a dry or plasma assisted etching tool; and (6) removing the resist using a tool such as a radio frequency or microwave plasma resist stripper. experiment Experiment 1

[0130] The substrate with silicon oxynitride deposited thereon was exposed to 0 cycles of protective layer deposition by decomposition, 1 cycle of protective layer deposition by decomposition, and 5 cycles of protective layer deposition by decomposition; all three substrates were wet etched in dilute hydrofluoric acid with a dilution ratio of 100:1 for 30 minutes, and the amount of silicon oxynitride loss was measured. The results are shown in Figure 6 , it is shown that the silicon oxynitride loss is comparable on all substrates, so the silicon oxynitride is not damaged by decomposition to deposit the protective layer. Experiment 2

[0131] The substrate with silicon oxynitride deposited thereon was exposed to 0 cycles of protective layer deposition by decomposition, 1 cycle of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma, 5 cycles of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma, and 10 cycles of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma. All four substrates were wet etched in dilute hydrofluoric acid with a dilution ratio of 100:1 for 30 minutes, and the amount of silicon oxynitride loss was measured. The results are shown in Figure 7 It shows that the silicon oxynitride loss without any protective layer is A thin protective layer reduces the SiO2 loss to 10.9, and a thicker protective layer reduces the SiO2 loss to Total damage is less than These results indicate that SiO2 damage can be reduced by increasing the thickness of the protective layer. Experiment 3

[0132] The substrate having silicon oxynitride deposited thereon was exposed to 0 cycles of protective layer deposition by decomposition, 1 cycle of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma, 1 cycle of protective layer deposition by decomposition followed by cyclic silicon nitride deposition using thermal ammonia conversion and nitrogen / ammonia plasma, 5 cycles of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma, 5 cycles of protective layer deposition by decomposition followed by cyclic silicon nitride deposition using thermal ammonia conversion and nitrogen / ammonia plasma, 10 cycles of protective layer deposition by decomposition followed by silicon nitride deposition using nitrogen plasma, and 10 cycles of protective layer deposition by decomposition followed by cyclic silicon nitride deposition using thermal ammonia conversion and nitrogen / ammonia plasma. All 7 substrates were wet etched in dilute hydrofluoric acid with a 100:1 dilution ratio for 30 minutes and the silicon oxynitride loss was measured. The results are shown in Figure 8, it is shown that in comparison between the two deposition techniques, silicon oxynitride damage can be reduced by increasing the thickness of the protective layer, regardless of the type of plasma used for silicon nitride deposition. Definition and Precursors definition

[0133] The terms "acyl" or "alkanoyl" used interchangeably herein refer to a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms or hydrogen in straight chain, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent molecular group through a carbonyl group as defined herein. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, wherein R is hydrogen, an aliphatic group or an aromatic group, as defined herein.

[0134] "Alkanoyloxy" refers to an alkanoyl group, as defined herein, attached to a parent molecular group through an oxy group, as defined herein. Such a group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, alkanoyloxy is -OC(O)-R, wherein R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0135] "Aliphatic" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), and hydrocarbon groups including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and also including straight chain and branched arrangements, as well as all stereo and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0136] "Aliphatic-carbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0137] "Aliphatic-carbonyloxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, aliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0138] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, aliphatic-oxy ​​is -OR, wherein R is an optionally substituted aliphatic group as defined herein.

[0139] "Aliphatic-oxycarbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, aliphatic-oxycarbonyl is -C(O)OR, wherein R is an optionally substituted aliphatic group as defined herein.

[0140] "Alkyl-aryl", "alkenyl-aryl" and "alkynyl-aryl" mean an alkyl, alkenyl or alkynyl, respectively, as defined herein, coupled (or linked) or capable of being coupled (or linked) to a parent molecular group through an aryl, as defined herein. Alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted with one or more substituents, as described herein for alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon (C 2+) atoms. 7-16 alkyl-aryl), and those having an alkyl group containing 1 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkenyl-aryl), and those having an alkenyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbon (C 7-16 alkynyl-aryl), and those having an alkynyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, alkyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkynyl as defined herein.

[0141] "Alkenyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent olefin. The alkenyl group can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 Alkyl. Alkenyl can be monovalent or multivalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecular group or a suitable connection between the parent molecular group and another substituent. Alkenyl can also be substituted or unsubstituted. For example, alkenyl can be substituted with one or more substituents, as described herein for alkyl. Non-limiting alkenyl includes allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, etc.

[0142] "Alkoxy" refers to -OR, where R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 Alkoxy.

[0143] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups contain 2 to 12 carbon (C 2-12 alkoxyalkyl), and those having an alkyl group containing 1 to 6 carbons and an alkoxy group containing 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl is -LOR, wherein L and R are each independently alkyl as defined herein.

[0144] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In specific embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group may be substituted or unsubstituted. For example, the alkoxycarbonyl group may be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 Alkoxycarbonyl.

[0145] "Alkyl" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, straight or cyclic (e.g., a cycloalkyl group). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can also be substituted or unsubstituted. The alkyl group may be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to the parent molecular group or between the parent molecular group and another substituent. For example, the alkyl group may be substituted with one, two, three, or in the case of an alkyl group of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (2) C 1-6 Alkylsulfinyl (e.g., C 1-6 , wherein R is a C1-6 alkyl group); (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (4) amino (e.g., -NR 1 R2 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein, or R 1 and R 2 (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C(O)-R; (12) C(O)-R; (13) C(O)-R; (14) C(O)-R; (15) C(O)-R; (16) C(O)-R; (17) C(O)-R; (18) C(O)-R; (19) C(O)-R; (20) C(O)-R; (21) C(O)-R; (22) C(O)-R; (23) C(O)-R; (24) C(O)-R; (25) C(O)-R; (26) C(O)-R; (27) C(O) 3-8 Cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -OR, wherein R is heterocyclyl, as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is heterocyclyl, as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 , where R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (23)-C(O)NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 alkyl.

[0146] "Alkylene", "alkenylene" or "alkynylene" refers to a polyvalent (e.g., divalent) form of an alkyl, alkenyl or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, alkylene is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 The alkylene, alkenylene or alkynylene groups may be branched or unbranched. The alkylene, alkenylene or alkynylene groups may also be substituted or unsubstituted. For example, the alkylene, alkenylene or alkynylene groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0147] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -S(O)- group. In some embodiments, unsubstituted alkylsulfinyl is C 1-6 or C 1-12 In other embodiments, alkylsulfinyl is -S(O)-R, wherein R is alkyl as defined herein.

[0148] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, unsubstituted alkylsulfinylalkyl is C 2-12 or C 2-24 Alkylsulfinylalkyl (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In other embodiments, alkylsulfinylalkyl is -LS(O)-R, wherein L and R are each independently alkyl as defined herein.

[0149] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO2- group. In some embodiments, unsubstituted alkylsulfonyl is C1-6 or C 1-12 In other embodiments, alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., as described herein, comprising optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0150] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24 Alkylsulfonylalkyl (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In other embodiments, alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0151] "Alkynyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent alkyne. The alkynyl group can be branched, straight chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include optionally substituted C 2-24 Alkyl. Alkyl groups can be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or an appropriate bond between the parent molecular group and another substituent. Alkyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl.

[0152] 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.

[0153] "Amide" refers to -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, an aromatic group as defined herein, or any combination thereof, or wherein R 1 and R 2Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0154] "Amino" refers to -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted siloxy. In specific embodiments, R 1 and R 2 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0155] "Aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminoalkyl is -L-NR 1 R 2 , wherein L is alkyl as defined herein, and R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. In other embodiments, aminoalkyl is -LC(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each is independently H or alkyl as defined herein.

[0156] "Aminooxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminooxy is -O-NR 1 R 2 , where R 1 and R 2 R is each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl or optionally substituted siloxy.

[0157] Unless otherwise indicated, "aromatic group" refers to a cyclic conjugated group or moiety having 5 to 15 ring atoms of a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous delocalized π electron system. Typically, the number of out-of-plane π electrons corresponds to the Huckel rule (4n+2). The point of connection to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aromatic groups may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

[0158] "Aromatic-carbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0159] "Aromatic-carbonyloxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0160] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, aromatic-oxy ​​is -OR, wherein R is an optionally substituted aromatic group as defined herein.

[0161] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted aromatic group as defined herein.

[0162] "Aryl" refers to a group comprising at least 5 carbon atoms and up to 15 carbon atoms (C 5-15 ), such as 5 to 10 carbon atoms (C 5-10 ), an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic groups, heteroaliphatic groups, aromatic groups, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl groups, which are defined as groups containing aromatic groups having at least one heteroatom bound to the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl is also included in the term aryl, which defines groups containing aromatic groups without heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 Alkyl); (2) C 1-6 Alkyl; (3)C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, wherein L and R are each independently C 1-6 Alkyl); (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 Alkyl); (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, wherein L and R are each independently C 1-6Alkyl); (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 Alkyl); (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein); (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 Alkyl; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each independently is H or C 1-6 alkyl); (12) heteroaryl; (13) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (14) aroyl (e.g., C(O)-R, wherein R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehydes (e.g., -C(O)H); (19) aldehydes-C 1-6Alkyl (e.g., -LC(O)H, where L is C 1-6 Alkyl); (20)C 3-8 Cycloalkyl; (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 Cycloalkyl); (22) halo; (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each independently is H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -OR, wherein R is a heterocyclyl, as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, wherein R is a heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (29) nitro; (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C 1-6Alkyl; (33) Oxo (eg, =O); (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, wherein L and R are each independently C 1-6 Alkyl); (36)-(CH2) r CO2R 1 , where r is an integer from 0 to 4, and R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (37)-(CH2) r CONR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 and R 2 are each independently selected from: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (38)-(CH2) r S02R 1 , where r is an integer from 0 to 4, and where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C 4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 (41) thiols (e.g., -SH); (42) perfluoroalkyls (e.g., -(CF2) n CF3, wherein n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, wherein n is an integer from 0 to 10); (44) aryloxy (e.g., -OR, wherein R is aryl); (45) cycloalkoxy (e.g., -OR, wherein R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, wherein L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl). In specific embodiments, the unsubstituted aryl is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Aryl.

[0163] "Aryl-alkyl", "aryl-alkenyl" and "aryl-alkynyl" refer to an aryl group, as defined herein, coupled (or linked) to a parent molecular group through an alkyl, alkenyl or alkynyl group, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted with one or more substituents, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbon atoms (C 7-16 aryl-alkyl), and those having an aryl group of 4 to 18 carbons and an alkyl group of 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbon (C 7-16 aryl-alkenyl), and those having an aryl group containing 4 to 18 carbons and an alkenyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbon (C 7-16 aryl-alkynyl), and those having an aryl group containing 4 to 18 carbons and an alkynyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, wherein L is alkyl or alkylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkenyl group is -LR, wherein L is alkenyl or alkenylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkynyl group is -LR, wherein L is alkynyl or alkynylene as defined herein, and R is aryl as defined herein.

[0164] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthracene, or phenanthrenyl. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Arylene. Arylene can be branched or unbranched. Arylene can also be substituted or unsubstituted. For example, arylene can be substituted with one or more substituents, as described herein for aryl.

[0165] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, arylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is aryl, as defined herein.

[0166] "Aryloxy" refers to -OR, where R is an optionally substituted aryl as described herein. In some embodiments, unsubstituted aryloxy is C 4-18 or C 6-18 In other embodiments, R is aryl optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0167] "Aryloxycarbonyl" refers to an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aryloxycarbonyl is C 5-19 Aryloxycarbonyl. In other embodiments, aryloxycarbonyl is -C(O)OR, wherein R is aryl as defined herein.

[0168] "Aroyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aroyl is C 7-11 Aroyl or C 5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

[0169] "Aroyloxy" refers to an aroyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, unsubstituted aroyloxy is C 5-19 In other embodiments, aroyloxy is -OC(O)-R, wherein R is aryl as defined herein.

[0170] "Azide" refers to a -N3 group.

[0171] "Azidoalkyl" refers to an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, azidoalkyl is -L-N3, wherein L is an alkyl group as defined herein.

[0172] "Azo" refers to the group -N=N-.

[0173] "Carbamoyl" refers to an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 Group, where R 1 and R 2are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0174] "Carbamoyloxy" refers to a carbamoyl group, as defined herein, appended to the parent molecular group through n oxy groups, as defined herein. In some embodiments, the carbamoyl group is -OC(O)NR 1 R 2 Group, where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0175] "Carboimidoyl" refers to a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof.

[0176] "Carbonyl" refers to a -C(O)- group, which may also be represented as >C=O.

[0177] "Carboxyl" refers to a -CO2H group or its anion.

[0178] "Catalyst" refers to a compound capable of catalyzing a synthesis reaction, typically present in a small amount relative to the reactants, as readily understood by one of ordinary skill in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0179] "Cyanato" refers to an -OCN group.

[0180] "Cyano" refers to a -CN group.

[0181] "Cycloaliphatic" means a cyclic aliphatic radical as defined herein.

[0182] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, cycloalkoxy is -OR, wherein R is a cycloalkyl group, as defined herein.

[0183] "Cycloalkylalkoxy" means a -OLR group where L is alkyl or alkylene as defined herein and R is cycloalkyl as defined herein.

[0184] Unless otherwise indicated, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 8 carbons, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyls may also be substituted or unsubstituted. For example, cycloalkyls may be substituted with one or more groups, including those described herein for alkyls. In addition, cycloalkyls may include one or more double bonds and / or triple bonds.

[0185] "Cycloheteroaliphatic" refers to a heteroaliphatic group as defined herein that is cyclic.

[0186] "Disilyl" refers to a group containing a Si-Si bond. In some embodiments, the disilyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 Or-SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 and R S5 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0187] "Disulfide" means -SSR, wherein R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0188] An "electron donating group" refers to a functional group that is capable of donating at least a portion of its electron density to the ring to which it is directly attached, such as by resonance.

[0189] "Electron withdrawing group" refers to a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

[0190] "Halo" refers to F, Cl, Br or I.

[0191] "Haloaliphatic" means an aliphatic group as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0192] "Haloalkyl" refers to an alkyl group as defined herein, wherein one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently replaced by halogen atoms, e.g., fluorine, bromine, chlorine, or iodine. In independent embodiments, haloalkyl can be a -CX3 group, wherein each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, haloalkyl is -LX, wherein L is an alkyl group as defined herein, and X is fluorine, bromine, chlorine, or iodine. In other embodiments, haloalkyl is -LC(X)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0193] "Haloheteroaliphatic" refers to a heteroaliphatic group as defined herein wherein one or more hydrogen atoms, eg, 1 to 10 hydrogen atoms, are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0194] "Heteroaliphatic" refers to an aliphatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaliphatic groups may be substituted with one or more substituents, such as described herein for alkyl groups.

[0195] "Heteroaliphatic-carbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0196] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0197] "Heteroaliphatic-oxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0198] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, heteroaliphatic-oxycarbonyl is -C(O)OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0199] "Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" refer to an alkyl, alkenyl or alkynyl group (which may be branched, straight chain or cyclic) as defined herein, respectively, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms, which heteroatoms may be selected from but are not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and oxidized forms thereof.

[0200] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to polyvalent (eg, divalent) forms of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0201] "Heteroaromatic" refers to an aromatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups may be substituted with one or more substituents, such as described herein for alkyl and / or aryl groups.

[0202] By "heteroaromatic-carbonyl" is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0203] "Heteroaromatic-carbonyloxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0204] "Heteroaromatic-oxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​is -OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0205] "Heteroaromatic-oxycarbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0206] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms (e.g., one to four heteroatoms) in the ring, wherein the heteroatoms are selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups may have a monocyclic or multiple condensed rings, wherein the condensed rings may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of an aromatic heteroaryl group. Heteroaryl groups may be substituted by one or more groups that are not hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n+2 π electrons in a monocyclic or polycyclic ring system.

[0207] "Heteroarylene" refers to a polyvalent (eg, divalent) form of a heteroaryl group as described herein.

[0208] "Heteroatom" refers to an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, heteroatoms do not include halogen atoms, such as when valence restrictions do not permit.

[0209] Unless otherwise indicated, "heterocyclyl" refers to a 5, 6 or 7-membered ring containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur or halide). The 5-membered ring has 0 to 2 double bonds, and the 6-membered and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic and tetracyclic groups, wherein any of the above heterocyclic rings is fused with one, two or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothienyl, etc. The heterocyclic group includes thiirane, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridinyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidinone, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isoxazolidinyl, thiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furanyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxathiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0210] "Heterocyclyloxy" refers to a heterocyclyl, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -OR, wherein R is heterocyclyl, as defined herein.

[0211] "Heterocycloacyl" means a heterocyclyl, as defined herein, attached to the parent molecular moiety through a carbonyl group. In some embodiments, heterocycloacyl is -C(O)-R, wherein R is a heterocyclyl, as defined herein.

[0212] "Hydrazino" refers to -NR 1 -NR 2 R 3 , where R 1 , R 2 and R 3are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 A combination of or 2 and R 3 The combination of together with the nitrogen atom to which they are attached may form a heterocyclic group as defined herein. 1 , R 2 or R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl. In specific embodiments, R 2 and R 3 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0213] "Hydroxyl" refers to -OH.

[0214] "Hydroxyalkyl" refers to an alkyl group as defined herein substituted with 1 to 3 hydroxy groups, provided that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, hydroxyalkyl is -L-OH, wherein L is an alkyl group as defined herein. In other embodiments, hydroxyalkyl is -LC(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0215] "Imino" refers to a moiety comprising a carbon imino group. In some embodiments, the imino group is C(NR 1 )R 2 , where R 1 and R 2 Each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof. In other embodiments, the imino group is -C(NR 1 )H、-C(NR 1 )R Ak or -C(NR N1 )R Ar , where R1 R is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, or optionally substituted siloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic; and R Ar is an optionally substituted aryl group or an optionally substituted aromatic group.

[0216] "Imino" refers to a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0217] "Isocyanato" refers to a -NCO group.

[0218] "Isocyano" refers to a -NC group.

[0219] "Ketone" refers to -C(O)R or a compound containing this group, wherein R is selected from aliphatic, heteroaliphatic, aromatic or any combination thereof as defined herein. Examples of ketones may include R 1 C(O)R, where R and R 1 Each is independently selected from aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0220] "Nitro" refers to a -NO2 group.

[0221] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with 1 to 3 nitro groups. In some embodiments, nitroalkyl is -L-NO, wherein L is an alkyl group, as defined herein. In other embodiments, nitroalkyl is -LC(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0222] "Oxo" refers to a =0 group.

[0223] "Oxy" refers to -O-.

[0224] "Perfluoroalkyl" refers to an alkyl group as defined herein in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, wherein n is an integer from 0 to 10.

[0225] "Perfluoroalkoxy" refers to an alkoxy group as defined herein wherein each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, wherein R is a perfluoroalkyl group as defined herein.

[0226] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that contains a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in: Berge SM et al., "Pharmaceutical salts," J. Pharm. Sci. 1977 January; 66 (1): 1-19; and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. PHStahland C G Wermuth. Salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or separately by reacting the free base groups with suitable organic acids (thereby producing anionic salts) or by reacting the acid groups with suitable metals or organic salts (thereby producing cationic salts). Representative anionic salts include acetates, adipates, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphor sulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrobromide, hydrochloride, hydroiodide, isethionate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, methanesulfonate (m esylate), methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophylline Representative cationic salts include metal salts, such as alkali metal or alkaline earth metal salts, for example, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, etc.; other metal salts, such as aluminum, bismuth, iron and zinc; and non-toxic ammonium, quaternary ammonium and amino cations, including but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, etc.Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine and procaine. Other salts include ammonium, sulfonium, sulfoxonium, phosphorus, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepi nium), optionally substituted indolium, optionally substituted isoindolinium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0227] "Silyl" refers to -SiR 1 R 2 R 3 Or-SiR 1 R 2 - group. In some embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyl is -Si(R) a (OR)b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0228] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, silyloxy is -O-SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyloxy is —O—Si(R) a (OR) b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0229] "Sulfinyl" refers to a -S(O)- group.

[0230] "Sulfo" refers to a -S(O)2OH group.

[0231] "Sulfonyl" or "sulfonate" refers to a -S(O)2- group or -SO2R, where R is selected from hydrogen, an aliphatic, a heteroaliphatic, a haloaliphatic, a haloheteroaliphatic, an aromatic group as defined herein, or any combination thereof.

[0232] "Thioalkyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 In some embodiments, the thioalkyl group is -SR, wherein R is alkyl as defined herein.

[0233] "Thiol" refers to a -SH group.

[0234] One of ordinary skill in the art will recognize that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such impermissible substitution patterns are readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

[0235] As used herein, the term "about" refers to a difference of ±10% from any stated value. As used herein, the term modifies any stated value, range of values, or endpoints of one or more ranges.

[0236] As used herein, the terms "top", "bottom", "lower", "above", and "below" are used to provide relative relationships between multiple structures. The use of these terms does not indicate or require that a particular structure must be located at a particular position in the device.

[0237] Other features and advantages of the invention will become apparent from the following description and from the claims. Silicon-containing precursor

[0238] In various embodiments, the silicon-containing precursor is a silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In specific embodiments, the silicon-containing precursor comprises a halosilane precursor. In specific embodiments, the silicon-containing precursor comprises an aminosilane precursor.

[0239] Aminosilanes contain at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), and substituted mono-, di-, tri-, and tetra-aminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilylamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2(BTBAS), tert-butylsilylcarbamate, Si(NH2)4, and tert-butylsilylaminosilane. H(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), etc. Another example of aminosilane is trisilylamine (N(SiH3)3). In one example, the silicon-containing precursor is DIPAS. In another example, the silicon-containing precursor is BTBAS.

[0240] The silicon-containing precursor may contain one or more optionally substituted amino groups, thereby providing non-limiting aminosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(NR"2) x ,in: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and Each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0241] In another embodiment, the precursor has the formula (R"2N) x (R') 3-x Si-L-Si(R') 3-x (NR"2) x ,in: Each x is independently 0, 1, 2 or 3; L is a linking group such as a covalent bond, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an oxy group (—O—), an imino group or a silyl group; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and Each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0242] In specific embodiments, L is an optionally substituted imino group, such as -NR-, wherein R is H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group. In other embodiments, L is an optionally substituted silyl group, such as -SiR2-, wherein each R is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group.

[0243] In one case, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0; and / or L comprises an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (—O—), an imino, or a silyl group.

[0244] In specific embodiments, at least one R' or R" is not H. The precursor can have any useful combination of R' groups and amino groups (NR"2) attached to one or more silicon atoms.

[0245] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy ​​(e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic-oxy-silyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic groups (e.g., aryl), aromatic-oxy ​​groups (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), etc. In specific embodiments, each R is independently H, optionally substituted aliphatic groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted aryl groups, and optionally substituted heteroaromatic groups; a≥0; b≥1; and a+b=3. In some embodiments, two R groups may form an optionally substituted heterocyclic group together with the nitrogen atom to which they are attached. In other embodiments, each R is independently H, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, or optionally substituted aryl groups.

[0246] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted siloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiR3, -Si(R') a (OR) b 、-Si(R) a (OR) b 、-Si(R') a (NR2) b 、-Si(R) a (NR2) b 、-Si(R') a (OR)b (NR2) c 、-Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b 、-O-Si(R) a (OR) b 、-O-Si(R') a (NR2) b 、-O-Si(R) a (NR2) b 、-O-Si(R') a (OR) b (NR2) c or -O-Si(R) a (OR) b (NR2) c , wherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic or optionally substituted heteroaromatic; a, b and c are each ≥ 0; and a+b+c=3 or a+b=3 (if c is absent). In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl.

[0247] The precursor may comprise at least one R' group attached to a silicon atom. In one embodiment, the precursor has the formula (R')(H) 3-x Si(NR"2) x , wherein R' and R" can be any of those described herein, and wherein x is 1, 2 or 3. In another embodiment, the precursor has the formula (R')(H)2Si(NR"2), wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')(H)Si(NR"2)2, wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R')2(H)Si(NR"2), wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R')2Si(NR"2)2, wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')3Si(NR"2), wherein R' and R" can be any of those described herein.

[0248] The precursor may have no R' groups attached to the silicon atom. In one embodiment, the precursor has the formula (H) 4- x Si(NR"2) x , wherein each R" can independently be any of those described herein, and wherein x is 1, 2, 3 or 4. In another embodiment, the precursor has the formula Si(NR"2) x , wherein each R" can independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0249] The precursor may contain one or more hydrogen atoms attached to a silicon atom. In one embodiment, the precursor has the formula (H)3Si(NR"2) or (H)2Si(NR"2)2 or (H)Si(NR"2)3, wherein each R" may independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, wherein any of these groups may be optionally substituted.

[0250] The precursor may contain a heterocyclic group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, wherein Het is an optionally substituted heterocyclic group containing at least one nitrogen atom. In a specific embodiment, the precursor has the formula wherein the heterocyclyl group may be optionally substituted (e.g., substituted with any substituent described herein as substituted with an alkyl group), and wherein n is 1, 2, 3, 4, or 5. In one embodiment, the formula is of the formula R'3Si-Het, wherein Het is an optionally substituted heterocyclyl group comprising at least one nitrogen atom, and each R' may independently be any of those described herein. In a specific embodiment, the precursor is of the formula wherein the heterocyclyl group can be optionally substituted (eg, with any substituent described herein as substituted with alkyl); each R′ can independently be any of those described herein; and wherein n is 1, 2, 3, 4, or 5.

[0251] In some cases, the precursor may have two or more silicon atoms, wherein the precursor may contain Si-Si bonds. In a specific embodiment, the precursor has the formula (R"2N): x (R') 3-x Si-Si(R') 3-x (NR"2) x, wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R"2N)(R')2Si-Si(R')2(NR"2), wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R"2N)2(R')Si-Si(R')(NR"2)2, wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R"2N)3Si-Si(NR"2)3, wherein each R" can independently be any of those described herein.

[0252] The precursor may include different groups attached to the silicon atom. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-SiH3, wherein R' and R" can be any of those described herein.

[0253] The linking group may be present between two silicon atoms. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-NR-Si(R') 3-x (NR"2) x , wherein R' and R" can be any of those described herein, and wherein R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another instance, the precursor has the formula (R"2N) x (H) 3-x Si-NR-Si(H) 3-x (NR"2) x , wherein R, R' and R" can be any of those described herein.

[0254] The precursor may comprise a combination of an R' group and a linker having a heteroatom. In one instance, the precursor has the formula (R')3Si-NR-Si(R')3, wherein R and R' may be any of those described herein. In another instance, the precursor has the formula (R')3Si-L-Si(R')3, wherein L and R' may be any of those described herein. In a specific embodiment, L is an oxy group (-O-), an optionally substituted imino group (e.g., -NR-), or an optionally substituted silyl group (e.g., -SiR2-).

[0255] The precursor may include any useful combination of R' and NR"2 groups in combination with two silicon atoms. In one instance, the precursor has the formula (R"2N)(R')2Si-L-Si(R')2(NR"2) x , wherein L, R' and R" can be any of those described herein.

[0256] The precursor may contain a heterocyclic group containing silicon and nitrogen atoms. In one embodiment, the precursor has the formula wherein R' and R" can be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0257] In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein each R" can independently be any of those described herein; and wherein n is 1, 2, 3 or 4. In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein R" can independently be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0258] In any of the precursors herein, two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclic group.

[0259] The precursor may comprise any of the following, for example, (R Ak )Si(NH2)(NR Ak 2)2、(R Ak )Si(NR Ak 2)3、(R Ak )2Si(NHR Ak 2)2、(R Ak )(H)Si(NHR Ak )2、(R Ak )3Si(NR Ak 2) (R Ak )3Si(NHR Ak )、H2Si(NHR Ak 2)2、(R Ak )(H)Si(NR Ak 2)2、HSi(NH2)(NR Ak 2) 2、HSi(NR Ak 2)3、Si(NR Ak 2)4, (R')(H)Si(NR"2)2, (R')2Si(NR Ak 2)2、 (R')2Si(N[SiH3]2)2, (R')2Si(N[SiR"3]2)2 or (R')3Si(NHR AkIn some embodiments, R' and R" can each independently be any of those described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. Ak It is methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu) and the like.

[0260] Non-limiting examples of precursors include any of the following: methylaminotrimethylsilane (SiMe3[NHMe]); dimethylaminodimethylsilane (SiMe2H[NMe2]); dimethylaminotrimethylsilane (SiMe3[NMe2]); dimethylaminodiethylsilane (SiHEt2[NMe2]); dimethylaminotriethylsilane (SiEt3[NMe2]); ethylmethylaminodimethylsilane (SiHMe2[NMeEt]); ethylmethylaminotrimethylsilane (SiMe3[NMeEt]); ethylmethylaminodiethylsilane (SiHEt2[NMeEt]); ethylmethylaminotriethylsilane (SiEt3[NMeEt]); diethylaminomethylsilane (SiH2Me[NEt2]); diethylaminoethylsilane (SiH 2Et[NEt2]); ethylaminotrimethylsilane (SiMe3[NHEt]); diethylaminodimethylsilane (SiHMe2[NEt2]); diethylaminodiethylsilane (SiHEt2[NEt2]); diethylaminotrimethylsilane (SiMe3[NEt2]); diethylaminotriethylsilane (SiEt3[NEt2]); isopropylaminodimethylsilane (SiHMe2[NHiPr]); isopropylaminotrimethylsilane (SiMe3[NHiPr]); isopropylaminodiethylsilane (SiHEt2[NHiPr]); isopropylaminotriethylsilane (SiEt3[NHiPr]); diisopropylaminotrimethylsilane (SiMe3[NiPr2]); diisopropylaminosilane (SiH3[NiPr2], C6H 17NSi or DIPAS); diisopropylaminomethylsilane (SiH2Me[NiPr2]); diisopropylaminodimethylsilane (SiHMe2[NiPr2]); diisopropylaminodiethylsilane (SiHEt2[NiPr2]); diisopropylaminotriethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]) ; tert-butylaminodimethylsilane (SiHMe2[NHtBu]); tert-butylaminotrimethylsilane (SiMe3[NHtBu]); tert-butylaminodiethylsilane (SiHEt2[NHtBu]); tert-butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl); N-propylisopropylaminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N-ethylcyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], where Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], where Py is pyrrolyl); pyrrolidinyltrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolidinyl); piperidinyltrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], where Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm] , wherein Im is an imidazolyl group); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino)methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2);Bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); Bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2); Bis(diethylamino)silane; (SiH2[NEt2]2, C8H 22 N2Si or BDEAS); bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(isopropylamino)dimethylsilane (SiMe2[NHiPr]2); bis(isopropylamino)diethylsilane (SiEt2[NHiPr]2); bis(isopropylamino)methylvinylsilane (SiMeVi[NHiPr]2 ); bis(diisopropylamino)silane (SiH2[NiPr2]2); bis(diisopropylamino)dimethylsilane (SiMe2[NiPr2]2); bis(diisopropylamino)diethylsilane (SiEt2[NiPr2]2); bis(diisopropylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec-butylamino)methylsilane (SiHMe [NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS); bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2); bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); bis(1-imidazolyl)dimethylsilane (SiMe2[Im]2, where I m is imidazolyl); tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS); tris(dimethylamino)phenylsilane (SiPh[NMe2]3); tris(dimethylamino)methylsilane (SiMe[NMe2]3); tris(dimethylamino)ethylsilane (SiEt[NMe2]3); tris(ethylmethylamino)silane (SiH[NEtMe]3); tris(diethylamino)silane (SiH[NEt2]3); tris(isopropylamino)silane (SiH[NHiPr]3, C9H 25N3Si or TIPAS); tris(dimethylamino)silylamide (Si[NMe2]3[NH2]); tetrakis(dimethylamino)silane (Si[NMe2]4); tetrakis(ethylmethylamino)silane (Si[NEtMe]4); tetrakis(diethylamino)silane (Si[NEt2]4); 1,2-diethyl-tetrakis(diethylamino)disilane ([Et2N]2EtSi-SiEt[NEt2]2); 1,2-dimethyl-tetrakis(dimethylamino)disilane ([ Hexa(methylamino)disilane ([MeHN]3Si-Si[NHMe]3); Hexa(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3); Hexa(dimethylamino)disilazane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), etc.

[0261] In some embodiments, the silane precursor is a halosilane precursor. A halosilane precursor is defined as a precursor having at least one halogen-containing atom and at least one silicon atom. Halogens include chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane precursor comprises a structure of formula (I): Si(X)4, At least one of X comprises a halogen atom.

[0262] For example, a monohalosilane is tetrachlorosilane or silicon tetrachloride (SiCl4). Another example of a chemical formula of a halosilane is Si n X y H z , wherein X is a halogen and H is hydrogen; n is an integer greater than or equal to 1 and equal to the number of Si atoms in the molecule; in some embodiments, y is from about 1 to about 4, and z is 4-y. Additional examples include, but are not limited to, SiHCl3, SiH2Cl2, and SiH3Cl.

[0263] Examples of halosilanes are iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane (DCS), monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert-butylchlorosilane, di-tert-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, tert-butyldimethylchlorosilane, tert-hexyldimethylchlorosilane, hexachlorodisilane (HCDS), and the like.

[0264] In some embodiments, the halosilane is carbon-free. In some embodiments, the halosilane is an organic silicon-containing precursor.

[0265] In some embodiments, the halosilane precursor (eg, in formula (I)) has at least one optionally substituted C 1-2 Non-limiting examples of haloaliphatic groups include -CX y H 3-y , wherein y is 1, 2, or 3, and wherein each X is independently halogen (F, Cl, Br, or I); -CX z H 2-z CX y H 3-y , wherein z is 0, 1, or 2, wherein y is 0, 1, 2, or 3, and wherein each X is independently a halogen (F, Cl, Br, or I), wherein at least one of z or y is not 0; or -CH2CX y H 3-y , wherein y is 1, 2, or 3, and wherein each X is independently halogen (F, Cl, Br, or I). Still other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chlorofluoromethyl (-CHF Cl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CH2CH2F), 2-chloroethyl (-CH2CH2Cl), 2-bromoethyl (-CH2CH2Br), 2-iodoethyl (-CH2CH2I), 2,2-difluoroethyl (-CH2CHF2), 2,2-dichloroethyl (-CH2CHCl2), 2,2-dibromoethyl (-CH2CHBr2), 2,2-diiodoethyl (-CH2CHI2), 2,2-fluoroiodoethyl (-CH2CHFI), and the like. In certain embodiments, C 1-2 Haloalkyl groups include β-halo-substituted ethyl groups. Still other haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Halogenated alkenyl, and C 2-4 Haloalkynyl. Summarize

[0266] Although the foregoing embodiments have been described in some detail for the purpose of clarity of understanding, it is apparent that certain changes and modifications may be implemented within the scope of the appended claims. It should be noted that there are many alternative ways to implement the processes, systems and devices of the present embodiments. Therefore, the embodiments presented are considered to be illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method for processing a substrate, the method comprising: providing a substrate having a dielectric material deposited thereon; depositing a protective layer on the dielectric material in a plasma-free environment; as well as After depositing the protective layer, the substrate is exposed to a first plasma to deposit a first silicon nitride while converting at least a portion of the protective layer to a second silicon nitride. 2 . The method of claim 1 , wherein the protective layer is deposited by thermally decomposing a deposition precursor on the surface of the substrate.

3. The method of claim 1, wherein the protective layer is deposited by: exposing the substrate to a deposition precursor; and heating the substrate to a temperature sufficient to decompose the deposition precursor onto the surface of the substrate.

4. The method of claim 1, wherein the protective layer is deposited by time-alternating pulses of: exposing the substrate to a deposition precursor; and exposing the substrate to an inert gas. 5 . The method of claim 1 , wherein exposing the substrate to the first plasma comprises generating the first plasma using one or more nitrogen-containing gases. 6 . The method of claim 1 , wherein the protective layer is deposited by: decomposing a deposition precursor on the surface of the substrate to form a decomposed film; and exposing the decomposed film to a second plasma to form the protective layer.

7. The method according to claim 3 or 6, wherein the deposition precursor is diisopropylaminosilane or bis(tert-butylamino)silane.

8. A method for processing a substrate, the method comprising: providing a substrate having a silicon oxynitride material deposited thereon to a processing chamber; directing a first silicon-containing precursor into the processing chamber, the processing chamber being under process conditions sufficient to decompose the first silicon-containing precursor in a plasma-free environment and form the decomposed first silicon-containing precursor on the surface of the substrate to form a protective layer including the decomposed first silicon-containing precursor; After forming the protective layer, introducing a second silicon-containing precursor into the process chamber to form an adsorption layer of the second silicon-containing precursor on the surface of the protective layer; as well as A nitrogen-containing plasma is directed into the processing chamber to convert the second silicon-containing precursor into silicon nitride and to convert at least a portion of the protective layer into silicon nitride. 9 . The method of claim 8 , wherein at least one of the first silicon-containing precursor and the second silicon-containing precursor is diisopropylaminosilane or bis(tert-butylamino)silane.

10. An apparatus for processing a substrate, the apparatus comprising: one or more process chambers, each process chamber including a chuck; one or more gas inlets leading to the process chamber and associated flow control hardware; as well as A controller having a memory and at least one processor, wherein The memory and the at least one processor are communicatively connected to each other, The at least one processor is operatively connected to at least the flow control hardware, and The memory stores computer executable instructions for controlling the at least one processor to at least control the flow control hardware to: causing, without igniting a plasma, to direct a first silicon-containing precursor to the one or more processing chambers for a duration sufficient to adsorb at least some of the first silicon-containing precursor to a surface of a substrate; causing the chuck to be heated to decompose the first silicon-containing precursor and form a protective layer on the surface of the substrate; causing, without igniting a plasma, to direct a second silicon-containing precursor to the one or more processing chambers for a duration sufficient to adsorb at least some of the second silicon-containing precursor to a surface of the protective layer; as well as A nitrogen-containing gas is used to generate a plasma to convert the second silicon-containing precursor into silicon nitride and convert at least a portion of the protective layer into silicon nitride.

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