Seamless and crack-free deposition

Abstract

Methods and apparatus are provided herein for depositing a material into a feature on a substrate by depositing a first portion of the material; etching a V-shaped hole at or near the feature opening; and depositing a second portion of the material to fill the feature.

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 processing may involve depositing materials into features. Depositing materials into features is challenging as features become smaller and smaller in size. Some techniques for depositing materials into small features result in seams forming in the middle of the feature, which can cause cracks or other defects that can lead to device failure.

[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 feature to a processing chamber, the feature having a feature opening; conformally depositing a first portion of a material into the feature; stopping the deposition into the feature before a seam is formed in the feature; after partially depositing the first portion of the material, exposing the substrate to an etching substance to etch an angular opening, such as a V-shaped hole, at or near the feature opening to form an etched surface; and depositing a second portion of the material onto the etched surface to fill the feature.

[0005] In various embodiments, at least one of the first portion and the second portion of the material is deposited using plasma enhanced atomic layer deposition.

[0006] In some embodiments, plasma enhanced atomic layer deposition comprises exposing a first portion of the material to a deposition precursor in a temporally separated pulsed manner to form an adsorption layer of the deposition precursor and exposing the adsorption layer of the deposition precursor to a plasma. For example, in some embodiments, the plasma is generated using a high frequency plasma. In some embodiments, the high frequency plasma is generated at a power of about 4500 W to about 6000 W. In some embodiments, the plasma is generated using a low frequency plasma. In some embodiments, the low frequency plasma is generated at a power of up to about 5000 W. In some embodiments, the plasma is generated by igniting oxygen. In some embodiments, the plasma is generated by igniting the oxygen in an environment comprising nitrous oxide and optionally argon.

[0007] In some embodiments, plasma enhanced chemical vapor deposition includes igniting a dual frequency plasma. In some embodiments, the dual frequency plasma is generated using a high frequency plasma power of about 3000 W to about 6000 W and a low frequency plasma power of about 1000 W to about 5000 W. In some embodiments, the dual frequency plasma is generated using igniting oxygen. In some embodiments, igniting oxygen is performed in an environment comprising one or more inert gases (e.g., one of nitrogen, argon, hydrogen, and combinations thereof).

[0008] In some embodiments, during plasma enhanced chemical vapor deposition, the chamber pressure is about 600 mTorr to about 5000 mTorr.

[0009] In various embodiments, the second portion of the material is deposited using plasma enhanced chemical vapor deposition.

[0010] In various embodiments, the second portion of the material is deposited using thermal chemical vapor deposition.

[0011] In some embodiments, after thermal chemical vapor deposition, a post-treatment process may be performed. In some embodiments, the post-treatment is performed in an oxygen-free environment. In some embodiments, the post-treatment includes exposing the substrate to a plasma. In some embodiments, the plasma is generated by igniting a gas such as nitrogen, argon, hydrogen, and combinations thereof. In some embodiments, the plasma is generated using a dual-frequency plasma having a high frequency and a low frequency. In some embodiments, the high-frequency plasma is generated at a power of up to about 6000W, and the low-frequency plasma is generated at a power of up to about 4000W.

[0012] In various embodiments, the processing chamber is a single wafer processing chamber.

[0013] In various embodiments, conformal deposition of the first portion and exposure of the substrate to the etching species are performed without breaking vacuum.

[0014] In various embodiments, the etching species is oxygen-free.

[0015] In various embodiments, the angular opening (or in some embodiments, V-shaped hole) is etched to a depth of about 10% to about 50% of the feature depth. In various embodiments, the V-shaped hole is etched to a depth less than about 10% of the feature depth.

[0016] 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 chamber and associated flow control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected to each other, the at least one processor is at least operably connected to the flow control hardware, and the memory stores computer executable instructions, the computer executable instructions being used to control the at least one processor to control at least the flow control hardware to: cause a first deposition precursor and a first reactant to be introduced in time-separated pulses to partially fill a feature on the substrate with a first portion of material; cause an etching gas to be introduced to etch the first portion of the material to form an angular opening or, in some embodiments, a V-shaped hole at or near a feature opening of the feature; and cause a second deposition precursor and a second reactant to be introduced and optionally generate a plasma to form a second portion of the material to fill the feature.

[0017] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Features are shown undergoing semiconductor processing, involving deposition of material into the features.

[0019] Figure 2A , 2B , 2C and 2D show process flow diagrams of operations that may be performed according to certain disclosed embodiments.

[0020] Figure 3 Features of semiconductor processing according to certain disclosed embodiments are shown, involving deposition of material into the features.

[0021] Figure 4 is a schematic diagram of a chamber that may be used in accordance with certain disclosed embodiments.

[0022] Figure 5 is a schematic diagram of a tool that may be used in accordance with certain disclosed embodiments.

[0023] Figure 6 is a schematic diagram of a tool that may be used in accordance with certain disclosed embodiments. DETAILED DESCRIPTION

[0024] 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.

[0025] Semiconductor manufacturing processes may involve depositing many materials into small features. For example, in some processes, silicon-containing materials may be deposited into features. Exemplary silicon-containing materials include, but are not limited to, silicon oxide, silicon nitride, silicon carbide, and doped variants thereof.

[0026] As devices shrink, features become narrower, resulting in smaller feature openings and feature sidewalls that are located closer together. Depositing materials into such small features can be challenging. One technique for depositing materials into features is atomic layer deposition (ALD).

[0027] ALD is a technique that uses continuous self-limiting reactions to deposit thin layers of materials. The ALD process uses surface-mediated deposition reactions to deposit films in a layer-by-layer manner in cycles. As an example, an ALD cycle may include the following operations: (i) delivering / adsorbing precursors, (ii) removing precursors from the chamber, (iii) delivering a second reactant and optionally igniting a plasma, and (iv) removing byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of the substrate affects the film composition and properties, such as non-uniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc. In the ALD deposition of silicon oxide films, the reaction involves oxygen plasma reacting with carbon and nitrogen to form gaseous species; oxidizing silicon to silicon oxide; removing trace carbon, nitrogen, and hydrogen impurities; and improving film bonding and densification.

[0028] Unlike chemical vapor deposition (CVD) techniques, the ALD process uses surface-mediated deposition reactions 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 dose 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 adsorbed layer may include the compound and derivatives of the compound. For example, the adsorbed layer of a silicon-containing precursor may include a silicon-containing precursor and a derivative of the silicon-containing precursor. After the first precursor dose, the chamber is then evacuated to remove most or all of the first 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 reactor may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant, such as an oxygen-containing gas, is introduced into the chamber so that some of these molecules react with the first precursor adsorbed on the surface. In some processes, the second reactant reacts immediately with the adsorbed silicon-containing precursor. In other embodiments, the second reactant reacts only after the activation source is temporarily applied. The chamber can then be evacuated again to remove unbonded second reactant molecules. As described above, in some embodiments the chamber may not be completely evacuated. Additional ALD cycles may be used to build film thickness.

[0029] In some embodiments, the ALD method includes plasma activation. As described herein, the ALD methods and apparatus described herein may be conformal film deposition (CFD) methods 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 “SILICONNITRIDE FILMS AND METHODS”, the entire contents of which are incorporated herein by reference.

[0030] The ALD process forms a conformal film in such a feature, which involves growing a film on the feature sidewalls and bottom. As the film grows from each sidewall, a seam is sometimes formed in the middle of the feature when the material from each sidewall touches in the middle of the feature. The seam may not have the same structural integrity as the rest of the material in the previously grown feature, but additional material may not be easily deposited into the seam to improve the structural integrity in the middle of the feature. For example, a silicon-containing deposition precursor may not be embedded in the seam. The material at the seam may not be chemically bonded, so the structural integrity of the material at the seam is weaker than the rest of the feature. Although some techniques involve annealing the substrate after filling the feature to reduce or eliminate the seam, heating can also cause cracks, especially starting from the seam, resulting in the formation of holes in the middle of the feature where the seam used to be. This may be due to the structure near the crack having lower structural integrity, resulting in periodicity or additional film cracks. In wet etch rate tests, the material at or near the seam is etched faster than the material at the sidewall. When the device is subjected to higher temperature processing (even without an annealing operation), the seam may open or crack, or both, which may be caused by shrinkage because the film before annealing may have been of lower quality. Once a crack forms in a feature, features adjacent to that feature may relax, resulting in an observable cracking frequency, depending on the original film quality and the film annealing temperature. In addition, cracking may also cause the feature structure to bend, thus affecting the structural integrity of the film formed on the substrate in subsequent operations.

[0031] As an alternative to ALD, high temperature chemical vapor deposition (CVD), such as but not limited to TEOS-based CVD, may be used because the deposited film may have a lower shrinkage and is less prone to opening or cracking. However, it is a challenge to deposit materials in features with an aspect ratio greater than about 4:1 using this technology. Another alternative is to use a high-density plasma to deposit the film. However, the use of a high-density plasma may involve additional operations, including deposition, etching performed in a separate chamber or station, further deposition, and its repeated operations to fill the feature. This may reduce the yield due to a slower process. Another alternative is to anneal at a controlled high temperature in a nitrogen-containing gas-based environment (e.g., an environment with nitrogen), thereby utilizing a gas environment to improve or reduce the seam. However, sometimes even in this embodiment, the seam may still shrink or crack.

[0032] Figure 1Examples of features in a substrate undergoing various processing operations are shown. Feature 102 has a liner layer with sidewalls 121. Feature 104 shows dielectric material 125 being conformally deposited into feature 104, whereby seam 122 is subsequently formed as the sidewalls on each side of the feature grow to merge in the center of feature 104. Feature 106 shows that the capping layer can be removed by planarization to form a level surface so that the filled dielectric material is flush with the feature opening. Feature 108 undergoes an annealing process. Feature 110 shows that after annealing, seam 122 cracks as the deposited dielectric material densifies and shrinks toward the sidewalls, forming a hole 124 in the center of the feature.

[0033] Provided herein are methods and apparatus for forming seamless and crack-free films in features. Such techniques can be used for a variety of films. In various embodiments, certain disclosed embodiments can be used for any film deposited by ALD. The methods and apparatus herein involve etching an angular opening (e.g., a V-shaped opening) at or near a feature opening to form a hole, and filling the hole with a dense, seamless film using one of a number of deposition techniques.

[0034] Some methods involve silicon oxide deposition, which does not crack during further high temperature processing after structural gap filling. As feature sizes shrink and some feature sizes become narrower, many applications have turned to ALD deposition. ALD deposition sometimes results in the formation of seams because it is deposited conformally and film growth starts from the sidewalls, such as Figure 1 This seam becomes a weak point in the membrane, and during the integration protocol, when the device is subjected to higher temperature processing, the weak seam may open and crack as described above.

[0035] Certain disclosed embodiments herein involve etching an angular opening, such as a V-shaped opening, and filling it with a dense film before the seam is closed, thereby forming a seamless film. This reduces the generation of cracks in the structure during subsequent higher temperature operation.

[0036] Certain disclosed embodiments may be performed to form seamless depositions on large area structures, such as for step fill and gap fill. Certain disclosed embodiments may also be used in other structures where seamless and / or crack-free deposition at or near a feature opening or a material surface on a substrate may be utilized. Exemplary deposition techniques that may be used to fill holes include, but are not limited to, ALD, plasma enhanced CVD (PECVD), and thermal CVD with post-processing.

[0037] Figure 2A A process flow diagram is provided that depicts operations that may be performed according to certain disclosed embodiments. Operation 201 involves providing a substrate to a processing chamber.

[0038] The substrate may be a silicon wafer, for example, a 200-mm wafer, a 300-mm wafer, or a 450-mm wafer, including a wafer having one or more layers of material, such as dielectric, conductive, or semiconductor materials deposited thereon. In various embodiments, the substrate is patterned. The patterned substrate may have "features", such as pillars, rods, trenches, through holes, or contact holes, which may be characterized by one or more narrow and / or concave openings, constrictions within the features, and high aspect ratios. The features may be formed in one or more of the above layers. An example of a feature is a pillar or rod in a semiconductor substrate or a layer on a substrate. Another example is a trench in a substrate or layer. The substrate may include a hard mask layer above the feature, wherein the hard mask is used as a mask to prevent deposition on certain areas of the substrate surface.

[0039] In some embodiments, a feature (e.g., a column) 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, at least about 100:1, or at least about 200:1 or higher. Features may also have dimensions near the opening, for example, an opening diameter or line width between about 10nm and 500nm (e.g., between about 25nm and about 300nm). Certain disclosed methods may be performed on a substrate having a feature with an opening less than about 150nm. A through hole, trench, or other concave feature may be referred to as an unfilled feature or feature. According to various embodiments, a feature profile may gradually narrow at a feature opening and / or include an overhang. A concave profile is a profile that narrows from the bottom, closed end, or interior of a feature to a feature opening. A concave profile may be generated during patterning by an overhang caused by non-conformal film step coverage in asymmetric etching dynamics and / or a previous film deposition (diffusion barrier deposition). In many examples, the opening of a feature at the top of the feature may have a width less than the width of the bottom of the feature.

[0040] In operation 203, a material is partially deposited into the features of the substrate using a deposition technique. The material may be a dielectric material. The material may be a silicon-containing material. The silicon-containing material may be silicon oxide. The deposition technique may be ALD, PECVD, or thermal CVD with post-processing.

[0041] An example of a method for partially depositing a material into a feature involves ALD. For the deposition of silicon oxide, the substrate may be exposed to a silicon-containing precursor for a duration sufficient to adsorb the silicon-containing precursor onto the surface of the substrate. The substrate may be exposed to the silicon-containing precursor by introducing the silicon-containing precursor into a processing chamber that houses the substrate. The silicon-containing precursor may be any silicon-containing precursor, such as a halosilane, or any silicon-containing precursor described elsewhere herein (e.g., in the definitions and precursor sections). The flow of the silicon-containing precursor may be stopped and the processing chamber may be optionally purged to remove excess silicon-containing precursor from the processing space in the processing chamber. Reactants, such as oxygen-containing gas or plasma, may be introduced after the purge. In some embodiments, the substrate on which the silicon-containing precursor is adsorbed is exposed to a reactant, such as an oxygen-containing gas or plasma, which converts the silicon-containing precursor into silicon oxide, thereby forming silicon oxide on the surface of the substrate. The flow of the oxygen-containing gas or plasma may be stopped, and the processing chamber may be optionally purged again. Many cycles of exposure to silicon-containing precursors and oxygen-containing gas or plasma may be used in pulses separated in time until silicon oxide of sufficient thickness is formed. For operation 203, silicon oxide may be formed until most but not all of the features are filled with silicon oxide and until at least some of the silicon oxide growing from both sidewalls of the features (being filled with silicon oxide) are in contact with each other.

[0042] In operation 205, etching may be performed to create an angular shape (e.g., a V-shape) at the feature opening without etching the hard mask. The term "angular shape" refers to the shape of the feature after etching from a cross-sectional perspective, such as later Figure 3, and further described below. An "angular" appearance refers to a sidewall that is tilted at an angle. A "V-shaped" refers to an angular shape of the side profile that looks like the letter V, with the sidewall tilting outward from the center of the feature to the widened feature opening as the sidewall approaches the surface level of the material layer. The etching in operation 205 causes the exposed surface of the material deposited in operation 203 to tilt, so that the material on the sidewall tilts downward toward the center of the feature, or tilts downward toward the gap between the two side walls. The tilt angle may affect the entire deposition process and can be adjusted by modifying the process conditions. For example, in some embodiments, the angle may be or about 45° on either sidewall. In some embodiments, the angle may be about 45° to about 60°. The angle can be determined by projecting the tilt of each sidewall to the center point of the feature center, such as from a feature cross-sectional side view. That is, an angle with a higher value means a wider opening with a less steep slope, while an angle with a lower value means a narrower opening with a steeper slope. The steeper the angle, the greater the depth of the deposited material, which will be seamless. In some embodiments, for high aspect ratio features or features with narrow openings, the angle may be less steep to avoid the risk of forming a seam during subsequent deposition. In some embodiments, the angle is greater than 45° so as not to form cracks in the deposited material. In some embodiments, the depth of the angular etch (e.g., the depth of the sidewall bevel) may be modified to be deep enough to achieve seamless deposition, but also to avoid being too deep to cause cracking. This may be referred to as a "crack stop." In some embodiments, the crack stop is about 10% to about 50% of the feature depth.

[0043] In various embodiments, the V-shaped point (e.g., the point where the projections of the sloped sidewalls would intersect at or near the center of the feature) is formed at a depth below the top flat area of ​​the substrate so that the seam will not be revealed or opened during planarization or other subsequent processing operations.

[0044] During operation 205, the substrate is exposed to a number of process conditions to achieve angled etching. One or more etching gases may be used. A plasma is ignited to produce plasma species that react with the material deposited on the substrate surface. Etching is performed using ions and free radicals and in some embodiments, sputtering is used. In some embodiments, ions and free radicals are generated using high radio frequency (RF) power. In some embodiments, sputtering occurs at most at 45° and hydrogen may be added to ignite the plasma to increase the steepness of the inclination of the V-shaped etching. Etching may result in an angle or V-shape because the material at or near the seam may be more easily etched.

[0045] In some embodiments, a bias voltage may be used. When a bias voltage is used, the power may be as high as about 1000V.

[0046] Exemplary etching gases include halogen-containing gases, such as fluorine-containing gases. An exemplary fluorine-containing gas is nitrogen trifluoride. One or more additional gases may also be used during etching, including but not limited to argon, helium, oxygen, hydrogen, and combinations thereof.

[0047] For a single wafer chamber, the etching gas may flow at a flow rate of about 100 sccm to about 500 sccm. The one or more additive gases may flow at a flow rate of about 0 slm to about 13 slm. Argon may flow at a flow rate of about 8 slm to about 13 slm. Helium may flow at a flow rate of about 0 slm to about 5 slm. Oxygen may flow at a flow rate of about 0 slm to about 5 slm.

[0048] The process conditions of plasma can vary according to the gas used and the desired depth of the angular or V-shaped etching. In some embodiments, dual frequency plasma is used. High frequency (HF) radio frequency (RF) plasma can be produced with a power of about 500W to about 3000W. Low frequency (LF) RF plasma can be produced with a power of about 2000W to about 4000W. In some embodiments, the slope of the angular or V-shaped etching can be reduced by reducing the HF power. In some embodiments, the slope of the angular or V-shaped etching can be reduced by increasing the LF power. For example, etching using about 2000W HF and 3000W LF can form an angular or V-shaped etching, which has a sidewall slope of about 60° at or near the feature opening, and etching using 500W HF and 3000W HF can form a V-shaped etching, which has a sidewall slope of about 55° at or near the feature opening. In some embodiments, higher RF power can increase the density of the film deposited in operation 203. In some embodiments, a higher density film may not necessarily be desired.In some embodiments, a seamless film may be deposited using CVD in operation 203, which does not necessarily change the density of the film.

[0049] The etching can be performed for a duration of about 1 second to about 3000 seconds, or about 1 second to about 2500 seconds, or about 1 second to about 2000 seconds, or about 1 second to about 1000 seconds, or about 1 second to about 500 seconds, or about 10 seconds to 100 seconds, or about 60 seconds. In some embodiments, increasing the etching duration can increase the slope of the angled or V-shaped etching.

[0050] During operation 205, a processing chamber containing a substrate may be set to a pressure of about 0.5 Torr to about 2 Torr.

[0051] Back to Figure 2AIn operation 207, a seamless, crack-free film is deposited and the seams may be fused. The deposited film is the same material as that deposited in operation 203. The film may be deposited using ALD, PECVD, or thermal CVD with post-processing. Deposition is performed to fill features at corners or V-shaped openings, thereby filling any seams with higher quality material, such as higher quality silicon oxide. Higher quality may refer to one or more properties, such as stress, density, k-value, wet etch rate, and others.

[0052] In various embodiments, deposition after etching a corner or V-shaped opening at or near a feature opening is seamless because the feature after etching the corner or V-shaped has a lower aspect ratio, and the deposition process gas and / or plasma species can more easily reach deeper areas of the feature, such as at the bottom of the feature. For example, ALD processes and PECVD processes can deposit seamless materials in this manner. In addition, any redeposition of sputtered material results in seamless deposition due to the lower aspect ratio; conversely, in the case of certain high aspect ratio features where a corner or V-shaped opening is not etched at or near the feature opening, a void may be formed in the middle of the feature due to redeposition of sputtered material at or near the feature opening.

[0053] In another example, CVD can be used to deposit material into the feature after etching the corner or V-shape. Among various embodiments, certain disclosed embodiments can deposit seamless material without performing post-processing or annealing after depositing the material. That is, by forming the corner or V-shaped opening before filling the feature, the deposited material is seamless without the need to anneal or process the substrate after filling the feature.

[0054] Figure 2B An example of depositing a film using ALD is provided.

[0055] In operation 213, a deposition precursor is introduced at a certain dosage. In some embodiments, the deposition precursor is a silicon-containing precursor. Silicon-containing precursors are further described in the Definitions and Precursors section below.

[0056] In various embodiments, the deposition precursor flows at a flow rate of about 0.1 slm to about 0.5 slm. During batching, the pressure may be about 1 Torr to about 25 Torr. The deposition precursor is introduced without igniting a plasma. The deposition precursor is introduced in a plasma-free environment. The deposition precursor is introduced thermally. The substrate temperature during batching is about 400° C. to about 700° C. or about 650° C. The batching may be performed for a duration of about 0.05 seconds to about 1 second.

[0057] In operation 223, the process chamber may optionally be purged. Purging the chamber may involve flowing a purge gas or purge gases, which may be carrier gases used in other operations or different gases. In some embodiments, purging may involve evacuating the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, operation 223 may include one or more evacuation sub-stages of evacuating the process chamber. Alternatively, it should be understood that operation 223 may be omitted in some embodiments. Operation 223 may have any suitable duration, such as between about 0 seconds and about 60 seconds, such as about 0.01 seconds.

[0058] In operation 233, an oxidation reactant is introduced. This may be referred to as "conversion", wherein the oxidation reactant converts the deposition precursor into the material. The oxidation reactant may be one or more oxygen-containing gases and / or oxygen-containing plasmas. The oxygen-containing plasma may be generated by igniting an oxygen-containing gas. Oxygen-containing gases include, but are not limited to, oxygen, nitrous oxide, ozone, peroxide, carbon monoxide, carbon dioxide and others. In one example, during operation 233, for a single wafer chamber, oxygen flows at a flow rate of about 1 slm to about 10 slm. For a single wafer chamber, oxygen may flow with nitrous oxide, with a flow rate of about 0 slm to about 10 slm. For a single wafer chamber, oxygen may also flow with argon, with a flow rate of about 3 slm to about 22 slm. For a single wafer chamber, oxygen may be ignited using a plasma having an HF RF power of about 4500 W to about 6000 W and an LF RF power of about 0 W to about 5000 W. In some embodiments, only HF RF plasma is used. During operation 233 , the chamber pressure may be about 2 Torr to about 6 Torr.

[0059] In operation 243, the process chamber may optionally be purged. The purge may be performed using the process conditions and gases described above with respect to operation 223.

[0060] Operations 213 and 233, or 213, 223, 233, and 243 may be cyclically repeated to deposit a film of variable thickness sufficient to deposit a seamless, crack-free film and fuse the seams, possibly due in part to the use of a high power plasma during deposition.

[0061] Figure 2C Shown in Figure 2AAnother embodiment of depositing a seamless and crack-free film in operation 207 of . In operation 253, a deposition precursor is introduced. The deposition precursor may be a silicon-containing precursor, such as any of those described above with respect to operations 203, 213, and elsewhere herein. Any suitable exposure time during operation 253 may be used. In some embodiments, the exposure time during operation 253 may be about 0.05 seconds to about 1 second. The exposure time may be the time before the plasma and oxygen-containing gas are introduced. In various embodiments, the deposition precursor flows at a flow rate of about 0.1slm to about 0.5slm. During batching, the pressure may be about 1Torr to about 6Torr. The deposition precursor is introduced without igniting the plasma. The deposition precursor is introduced into a plasma-free environment. The deposition precursor is introduced thermally. The substrate temperature during batching is about 500°C to about 700°C or about 650°C.

[0062] In operation 263, after the deposition precursor is introduced, an oxidation reactant is introduced while the deposition precursor flows. In some embodiments, this may be referred to as CVD. In some embodiments, the oxidation reactant is a plasma. In such embodiments, the process may be referred to as PECVD. The oxidation reactant may be any of those described above with respect to operation 233. In some embodiments, the oxidation reactant includes one or more oxidizing gases, and optionally one or more inert gases. In some embodiments, a mixture of oxygen and argon is introduced. In some embodiments, a mixture of oxygen, argon and hydrogen is introduced. In some embodiments, a mixture of oxygen, argon and nitrogen is introduced. In some embodiments, a mixture of oxygen, argon, hydrogen and nitrogen is introduced.

[0063] In some embodiments, oxygen flows at a flow rate of about 1 slm to about 5 slm. In some embodiments, argon flows at a flow rate of about 4.5 slm to about 22 slm. In some embodiments, hydrogen flows at a flow rate of about 0 slm to about 5 slm.

[0064] The oxidation reactants are ignited in a plasma generated using a dual frequency plasma. In some embodiments, the HF RF power is about 3 kW to about 6 kW for a single wafer chamber. In some embodiments, the LF RF power is about 1 kW to about 5 kW for a single wafer chamber.

[0065] During operation 263, for a single wafer chamber, the chamber may be set at a pressure of about 600 mTorr to about 5000 mTorr. The substrate temperature may be about 500° C. to about 700° C., or about 650° C. During dual frequency PECVD, deposition precursors and oxidation reactants are introduced so that they can react in the processing region above the substrate and form silicon oxide on the substrate. In various embodiments, this helps to form a seamless and crack-free high quality silicon oxide film over the features that now have angular surfaces (e.g., V-shaped surfaces).

[0066] Figure 2D An alternative deposition technique for performing operation 207 is shown. Figure 2D Related to enhanced thermal CVD films, or films deposited by thermal CVD and then post-treated. Treatment with plasma can be used to modify the properties of thermally deposited films, thereby forming high quality films.

[0067] exist Figure 2D In operation 253, a deposition precursor is introduced. The deposition precursor may be a silicon-containing precursor. This operation may be the same as or may use, for example, the above description of Figure 2C Any precursors and / or process conditions among those described in operation 253.

[0068] In operation 263, after the deposition precursor is introduced, an oxidation reactant is introduced while the deposition precursor is flowing. In operation 263, after the deposition precursor is introduced, an oxidation reactant is introduced while the deposition precursor is flowing. In some embodiments, this may be referred to as CVD. In some embodiments, the oxidation reactant is a plasma. In such embodiments, the process may be referred to as PECVD. The oxidation reactant may be any of those described above with respect to operation 233. This may be similar to Figure 2C The chemicals and / or process conditions in operation 263 are the same as or are used in Figure 2C The same chemical substances and / or process conditions as those of operation 263 in operation 264. In some embodiments, operation 263 is thermal, or plasma-free, or is performed in a plasma-free environment.

[0069] In some embodiments, the process conditions may vary. For example, in some embodiments, any one or more of the following features may be used: oxygen may flow at a flow rate of about 2 slm to about 10 slm; argon may flow at a flow rate of about 50 slm to about 70 slm; nitrogen may flow at a flow rate of about 15 slm to about 35 slm; and hydrogen may flow at a flow rate of about 500 sccm to about 5000 sccm.

[0070] Figure 2D The chamber pressure during operation 263 may be about 15 Torr to about 30 Torr. Figure 2DIn this example, no plasma is ignited during the introduction of the deposition precursor and / or the oxidation reactant. For example, the deposition precursor reacts thermally with the oxidation reactant, or reacts in a plasma-free environment, or reacts without igniting a plasma.

[0071] After stopping the flow of deposition precursors and / or oxidation reactants, in operation 273, the substrate is exposed to plasma treatment in an environment without precursors and oxidation reactants. Plasma treatment can be performed by introducing plasma into the chamber. In some embodiments, the processing chamber is purged between the cessation of the flow of deposition precursors and / or oxidation reactants and the introduction of plasma. In some embodiments, the plasma is generated in situ by flowing a process gas into the chamber and igniting the plasma. In some embodiments, the plasma is generated by igniting a process gas in a remote plasma generator to generate plasma species that are delivered to the processing chamber that accommodates the substrate.

[0072] In some embodiments, plasma treatment is performed by exposing the substrate to a plasma substance produced by an inert gas (e.g., argon, nitrogen, hydrogen, or helium). The plasma substance may be produced from a process gas. The process gas used during operation 273 may be oxygen-free. In some embodiments, the process gas includes one or more of nitrogen, hydrogen, and argon. In some embodiments, the process gas includes argon, nitrogen, and hydrogen. For a single wafer chamber, nitrogen may flow at a flow rate of about 15 slm to about 35 slm. For a single wafer chamber, argon may flow at a flow rate of about 50 slm to about 70 slm. For a single wafer chamber, hydrogen may flow at a flow rate of about 500 sccm to about 5000 sccm. In some embodiments, any one or more of argon, nitrogen, or hydrogen may be used as a diluent gas, a carrier gas, or a gas for stabilizing other gas flows.

[0073] Operation 273 may be performed at a chamber pressure of about 15 Torr to about 30 Torr.

[0074] The plasma generated in operation 273 may be a dual frequency plasma. In some embodiments, the plasma is a single frequency plasma.

[0075] The power of the HF RF plasma may be about 0 W to about 6000 W. The power of the LF RF plasma may be about 0 W to about 4000 W. In one example, the HF power is about 2000 W and the LF power is about 500 W. In another example, the HF power is about 6000 W and the LF power is about 4000 W.

[0076] Plasma treatment may be used to densify or modify the thermally deposited films in operations 253 and 263. In some cases, plasma treatment allows cross-linking to fuse seams and improve the integrity of the deposited film.

[0077] Operation 273 may be performed for a duration of about 0.5 seconds to about 5 seconds.

[0078] In operation 283, operations 253-273 may be optionally repeated in a cycle. For example, the plasma may be turned off before repeating operation 253, then the deposition precursor in operation 253 and the oxidation reactant in operation 263 may flow for thermal deposition, then the deposition precursor and oxidation reactant flows may be turned off, and the plasma may be turned on again to treat the film with one or more of argon, nitrogen, and hydrogen. The operations may be repeated until the film has the desired thickness. Return to Figure 2A The substrate is optionally polished to remove any capping layers deposited over the features in operation 209. The substrate may be polished by chemical mechanical planarization or by any other etching or planarization method.

[0079] In operation 211, the substrate is optionally annealed using thermal annealing or plasma annealing. Thermal annealing can be performed at a temperature of about 700° C. to about 1000° C. In some embodiments, thermal annealing can be performed using an external furnace or using rapid thermal annealing. Plasma annealing can be used. The plasma can be a single frequency or dual frequency plasma.

[0080] In some embodiments, annealing changes the properties of the deposited film by densification, increased crosslinking, hardening, altering stress, or otherwise changing other properties of the film. In some embodiments, after annealing, the material may have a wet etch rate in 100:1 HF of less than about / minute.

[0081] Figure 3 Schematic diagrams of various embodiments of features according to certain disclosed embodiments are shown. Icon 302 shows a feature having sidewalls 321. The feature may be present on a substrate, such as described above with respect to Figure 2A The substrate provided in operation 201 discussed above. Icon 304 shows that the feature from icon 302 is now partially filled with material 325 using a conformal deposition technique (e.g., ALD), but the deposition is stopped before the material completely fills the feature, thereby leaving a gap 326 in the partially filled feature. This deposition can be based on Figure 2A 203 of the embodiment. Icon 306 shows an angular opening (e.g., a V-shaped opening) being etched out so that material 325 now has an inclined exposed surface, wherein the inclination is angled toward the gap in the middle of the feature. Icon 308 shows additional material 327 being deposited, thereby filling the gap and fusing the seam, and also forming some capping layer over the feature wall. This material can be deposited as described above with respect to Figure 2B , 2C2D and 3D, thereby forming a higher quality film for the remainder of the feature fill. Icon 310 shows etching the capping layer to produce a level surface aligned with the hard mask and feature walls. Icon 312 shows an annealing operation, which can be used to further improve the quality of the film deposited in the feature, improve cross-linking, and fuse seams, thereby producing a good feature fill, although there may still be some seams in the middle of the feature, but there are almost no or no seams at or near the feature opening, which can prevent breakage, cracking, or loss of structural integrity when subjected to other post-process conditions. Device

[0082] Figure 4 A schematic diagram of an embodiment of an atomic layer deposition (ALD) processing station 400 is depicted, and the ALD processing station 400 has a processing chamber body 402. In various embodiments, in Figure 5 A single processing station 400 is implemented in the tool shown. In some embodiments, multiple ALD processing stations 400 may be included in a low pressure processing tool environment. For example, Figure 4 An embodiment of a multi-station processing tool 400 is depicted. In some embodiments, one or more hardware parameters of the ALD processing station 400 are programmably adjustable by one or more computer controllers 450, including those parameters discussed in detail below.

[0083] The ALD processing station 400 is in fluid communication with a reactant delivery system 401a to deliver process gases to the showerhead 406. The reactant delivery system 401a includes a mixing vessel 404 for mixing and / or regulating process gases, such as silicon-containing precursor gases, or oxygen-containing gases and / or nitrogen-containing gases, for delivery to the showerhead 406. One or more mixing vessel inlet valves 420 can control the introduction of process gases to the mixing vessel 404. One or more valves 405 can control the introduction of process gases to the showerhead 406.

[0084] As an example, Figure 4Embodiments include a vaporization point 403 for vaporizing liquid reactants to be supplied to a mixing container 404. In some embodiments, the vaporization point 403 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 403 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 403 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.

[0085] 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 downstream pipeline of vaporization point 403. In one case, a liquid injector can be directly mounted to a mixing vessel. In another case, a liquid injector can be directly mounted to a spray head 406.

[0086] In some embodiments, a liquid flow controller (LFC) upstream of the vaporization point 403 may be provided to control the mass flow rate of the liquid used for vaporization and delivery to the ALD processing station 400. 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.

[0087] The showerhead 406 distributes the process gas toward the substrate 412. Figure 4In the embodiment shown, substrate 412 is located below showerhead 406 and is shown disposed on pedestal 408. Showerhead 406 may have any suitable shape and may have any suitable number and arrangement of ports to distribute process gases to substrate 412.

[0088] In some embodiments, the pedestal 408 may be raised or lowered to expose the substrate 412 to the volume between the substrate 412 and the showerhead 406. It should be appreciated that in some embodiments, the pedestal height may be programmatically adjusted by a suitable computer controller 450.

[0089] In another case, adjusting the height of the pedestal 408 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 408 can be lowered to allow the substrate 412 to be removed from the pedestal 408 during another substrate transfer phase.

[0090] In some embodiments, the susceptor 408 can be temperature controlled via a heater 410. In some embodiments, the susceptor 408 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 200° C. to about 300° C. In some embodiments, the same susceptor 408 is used for annealing.

[0091] Additionally, in some embodiments, pressure control of the ALD processing station 400 may be provided by a butterfly valve 418. Figure 4 In the embodiment shown, butterfly valve 418 throttles the vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of ALD process station 400 can also be adjusted by changing the flow rate of one or more gases introduced into ALD process station 400.

[0092] In some embodiments, the position of the showerhead 406 can be adjusted relative to the pedestal 408 to change the volume between the pedestal 412 and the showerhead 406. In addition, it should be understood that the vertical position of the pedestal 408 and / or the showerhead 406 can be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 408 may include a rotation axis for rotating the orientation of the substrate 412. 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 450.

[0093] In some embodiments where plasma can be used as discussed above, the showerhead 406 and the pedestal 408 are electrically connected to a radio frequency (RF) power supply 414 and a matching network 416 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 414 and the matching network 416 can be operated at any suitable power to form a plasma with a composition of desired free radical species. An example of a suitable power for a single station chamber is about 150W to 10,000W or about 150W to 1,500W. For a 4-station chamber, the plasma power may include four generators, each generator supplying up to about 10,000W, for a total of about 40,000W. 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 414 and the matching network 416.

[0094] 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 414 may provide RF power of any suitable frequency. In some embodiments, the RF power supply 414 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 4.45 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.

[0095] 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.

[0096] In some embodiments, instructions for controller 450 may be provided via input / output control (IOC) sequence instructions. In one example, instructions for setting conditions for process stages may be included in corresponding recipe stages of a process recipe. In some cases, process recipe stages may be configured sequentially so that all instructions for a process stage are executed synchronously with the process stage. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe stage. For example, a first recipe stage may include instructions for setting the flow rate of a silicon-containing 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 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 an oxygen-containing gas or a silicon-containing gas, and time delay instructions for the third recipe stage. The fourth recipe stage may include instructions for adjusting or stopping the flow rate of inert and / or reactant gases, instructions for adjusting the flow rate of 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 etching gas to form an angular structure (e.g., a V-shaped structure), optionally heating or igniting the plasma, and instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fifth recipe stage. The subsequent sixth recipe stage may include instructions for setting the flow rate of deposition gas and / or reactant gas, instructions for heating or igniting the plasma, and instructions for adjusting the flow rate of carrier gas or purge gas, and time delay instructions for the fifth 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 450 may include the following regarding Figure 5 The system controller 550 and Figure 4 Any features described by the system controller 450.

[0097] The processing station may be included in e.g. Figure 5 In a single station chamber or single chamber tool as shown in . Figure 5 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 500 includes a processing chamber 514 having a processing station 590 that can process a wafer. Processing chamber 514 is configured to deposit silicon oxide, deposit silicon nitride, anneal a substrate using thermal annealing or plasma annealing, and the like.

[0098] The tool 500 also includes a wafer transfer unit configured to transfer 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 526 in a first wafer transfer module and a second robot unit 506 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) 508. The first robot unit 526 is configured to transfer wafers between a processing chamber 514 and the second robot unit via a module 504, which can hold multiple wafers, such as shown in the module 502 with a substrate 512. The second robot unit 506 is configured to transfer wafers between a FOUP and a module 504, or from a module 502 to a FOUP. After the wafers are prepared in the module 504, the wafer transfer unit can transfer the wafers to the first processing chamber 514 for in-situ deposition and optional annealing.

[0099] Similar to the above, the first wafer transfer module can be a vacuum transfer module (VTM). An air lock or module 504, also known as a load lock, is shown and can be individually optimized to perform various manufacturing processes. Tool 500 also includes a FOUP 508, which can be purged with nitrogen while the wafers are being processed in the processing chamber 514. This includes maintaining the processing chamber 514, as well as 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. As the wafers are transferred throughout the tool 500, the wafers are maintained under vacuum or low pressure.

[0100] In a further example, the substrate is placed in one of the FOUP 508 and the second robot unit 506, 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 504 by the second robot unit 506. Because the airlock module has the ability to match an environment between the ATM and the VTM, the substrate can be moved between the two pressure environments without damage. The substrate is moved from the airlock module 504 to the processing chamber 514 via the first wafer transfer module, or the VTM, by the first robot unit 526. To achieve this substrate movement, the first robot unit 526 uses an end effector on each of its arms.

[0101] Figure 5 Also depicted is an embodiment of a system controller 550 for controlling process conditions and hardware states of the processing tool 500. The system controller 550 may include one or more memory devices 556, one or more mass storage devices 554, and one or more processors 552. The processor 552 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 550 includes a processor for performing, for example, the above-described Figure 6 And the following about Figure 6 Machine readable instructions for these operations described.

[0102] As described above, one or more processing stations may be included in a multi-station processing tool. Figure 6 An exemplary processing apparatus according to the disclosed embodiments is depicted. Tool 600 includes a first processing chamber 602 and a second processing chamber 604. Although two processing chambers are depicted, it should be understood that in some embodiments, additional processing chambers may be used. For example, in some embodiments, three processing chambers may be used. The first processing chamber 602 includes a plurality of processing stations, four stations 680A to 680D, each of which can process a wafer. The first processing chamber 602 is configured to perform plasma processing operations on a wafer. The second processing chamber 604 is configured to perform deposition on a wafer and can be considered a deposition chamber. The second processing chamber 604 also includes a plurality of processing stations, four stations 682A to 682D, each of which can process a wafer. The first and second processing chambers 602 and 604 can be considered as multi-station processing chambers.

[0103] The tool 600 also includes a wafer transfer unit configured to transfer one or more wafers within the tool 600. Other features of the tool 600 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 608 in a first wafer transfer module 610 and a second robot unit 612 in a second wafer transfer module 614, 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) 616. The first robot unit 608 is configured to transfer wafers between the first processing chamber 602 and the second processing chamber 604, and between the second robot unit 612. The second robot unit 612 is configured to transfer wafers between the FOUP and the first robot unit 608. After the wafers have been processed in the first processing chamber 602, the wafer transfer unit can transfer the wafers from the first processing chamber 602 to the second processing chamber 604 where one or more layers of encapsulation material can be deposited on the one or more wafers.

[0104] Similar to the above, the first wafer transfer module 610 can be a vacuum transfer module (VTM). An air lock 620, also referred to as a load lock or transfer module, is shown and can be optimized individually to perform various manufacturing processes. The tool 600 also includes a FOUP 616 configured to reduce the pressure of the tool 600 to a vacuum or a low pressure, such as between about 1mTorr and about 10Torr, and maintain the tool 600 at this pressure. This includes maintaining the first and second processing chambers 602 and 604, and the first wafer transfer module 610 at a vacuum or low pressure. The second wafer transfer module 614 can be at a different pressure, such as atmospheric pressure. Since the wafer is transferred everywhere in the tool 600, the wafer is maintained at a vacuum or low pressure. For example, since the wafer is transferred from the first processing chamber 602 into the first wafer transfer module 610 and arrives at the second processing chamber 604, the wafer is maintained at a vacuum or low pressure without being exposed to atmospheric pressure.

[0105] In a further example, the substrate is placed in one of the FOUP 618 and the second robot unit 612, or the front end robot transfers the substrate from the FOUP 618 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 620 by the second robot unit 612. 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 620 via the first wafer transfer module 610, or the VTM 610 into the first processing chamber 602 by the first robot unit 608. To achieve this substrate movement, the first robot unit 608 uses an end effector on each of its arms.

[0106] Figure 6 Also depicted is an embodiment of a system controller 629 for controlling process conditions and hardware states of the tool 600. The system controller 629 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.

[0107] In some embodiments, the system controller 629 controls all activities of the tool 600. The system controller 629 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 629. 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 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 600. 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.

[0108] 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 629 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.

[0109] 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 600.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] The pressure control program may include code for maintaining pressure in a reaction chamber according to embodiments herein.

[0114] In some embodiments, there may be a user interface associated with the system controller 629. 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.

[0115] In some embodiments, the parameters adjusted by the system controller 429 may relate to process conditions. Non-limiting examples include process gas composition and flow 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.

[0116] Signals for monitoring the process may be provided from various process tool sensors by analog and / or digital input connections of the system controller 629. Signals for controlling the process may be output via analog and / or digital output connections of the process tool 600. 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.

[0117] The system controller 629 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.

[0118] The system controller 629 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 629.

[0119] In some implementations, the controller 629 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 629 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.

[0120] In a broad sense, the system controller 629 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 629 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 (kinds of) layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0121] In some implementations, the system controller 629 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 629 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, examine the history of past manufacturing operations, examine trends or performance criteria for multiple manufacturing operations, change parameters of a current process, set a process step to follow the current process, or start a new process. In some embodiments, a remote computer (e.g., a server) may provide a process recipe to the system via a network, which may include a local network or the Internet. The remote computer may include a user interface that 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 629 receives instructions in the form of data that specify parameters for each process 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 629 is configured to connect or control the tool type. Thus, as described above, the system controller 629 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.

[0122] 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.

[0123] As described above, depending on the one or more processing steps to be performed by the tool, the system controller 629 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.

[0124] 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.

[0125] 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

[0126] Experiments were conducted on wafers having multiple negative features therein. The features were partially filled using atomic layer deposition (ALD), leaving a gap in the center of the feature. The first substrate was exposed to a dual frequency plasma with an HF power of 2000 W and an LF power of 3000 W for 400 seconds, which resulted in the formation of an angular opening, such as a V-shaped opening, at or near the feature opening. The second substrate was exposed to a dual frequency plasma with an HF power of 2000 W and an LF power of 3000 W for 800 seconds, which resulted in the formation of an angular opening, such as a V-shaped opening, at or near the feature opening with a wider critical dimension opening and a deeper V-shape with a steeper slope (compared to the first substrate). The third substrate was exposed to a dual frequency plasma with an HF power of 500 W and an LF power of 3000 W for 400 seconds, which resulted in the formation of a V-shaped opening (about 60°) at or near the feature opening with a narrower critical dimension and a less steep sidewall slope at or near the feature opening (compared to the first substrate and the second substrate). The fourth substrate was exposed to a dual frequency plasma with 500 W of HF power and 3000 W of LF power for 800 seconds, which resulted in the formation of a V-shaped opening (about 55°) at or near the feature opening having a critical dimension wider than that of the third substrate and a sidewall slope at or near the feature opening that was not steeper than that of the first and second substrates. Definition and Precursors definition

[0127] 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 include 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.

[0128] "Alkanoyloxy" refers to an alkanoyl group, as defined herein, attached to a parent molecular group through an oxy group, as defined herein. An example of such a group is 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.

[0129] "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 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.

[0130] "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.

[0131] "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.

[0132] "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.

[0133] "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.

[0134] "Alkyl-aryl", "alkenyl-aryl" and "alkynyl-aryl" mean an alkyl, alkenyl or alkynyl, respectively, as defined herein, coupled (or connected) or can be coupled (or connected) to a parent molecular group through an aryl, as defined herein. Alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl can be substituted with one or more substituents, as described herein for alkyl and / or aryl. 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-C4-18 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 atoms (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.

[0135] "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 by one or more substituents, as described herein for alkyl.Non-restrictive alkenyl includes allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, etc.

[0136] "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.

[0137] "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.

[0138] "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 can be substituted or unsubstituted. For example, the alkoxycarbonyl group can 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.

[0139] "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) saturated monovalent hydrocarbon, wherein the saturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from one carbon atom of the parent compound (e.g., alkane). The alkyl group can be branched, straight or cyclic (e.g., cycloalkyl). 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 R 2 , 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) 3-8Cycloalkyl; (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) 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); (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 C1-6 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.

[0140] "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 , C2-16 , C 2-18 , C 2-20 or C 2-24 Alkylene, alkenylene or alkynylene. Alkylene, alkenylene or alkynylene can be branched or unbranched. Alkylene, alkenylene or alkynylene can also be substituted or unsubstituted. For example, alkylene, alkenylene or alkynylene can be substituted with one or more substituents, as described herein for alkyl.

[0141] "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.

[0142] "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.

[0143] "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 C 1-6 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).

[0144] "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.

[0145] "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 examples thereof include 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 connection to the parent molecular group or an appropriate connection 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.

[0146] 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.

[0147] "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 2 Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0148] "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 2Each 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.

[0149] "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.

[0150] "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 2Each 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.

[0151] 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, by functional groups as described herein. For example, aromatic groups may be substituted by one or more substituents, as described herein for alkyl and / or aryl.

[0152] "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.

[0153] "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.

[0154] "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.

[0155] "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.

[0156] "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 1-6 Alkyl); (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 2Together 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 1-6 Alkyl (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 C1-6 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 1-6 Alkyl; (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 1-6Alkyl (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-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (40)-(CH2) r NR 1 R 2 , 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 1-6Alkyl (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.

[0157] "Aryl-alkyl", "aryl-alkenyl" and "aryl-alkynyl" refer to an aryl group, as defined herein, coupled (or connected) to a parent molecular group through an alkyl, alkenyl or alkynyl group, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl can be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl can be substituted with one or more substituents, as described herein for aryl and / or alkyl. 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 7-16aryl-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.

[0158] "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.

[0159] "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.

[0160] "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.

[0161] "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.

[0162] "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 C5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

[0163] "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.

[0164] "Azide" refers to a -N3 group.

[0165] "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.

[0166] "Azo" refers to the group -N=N-.

[0167] "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 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.

[0168] "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.

[0169] "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.

[0170] "Carbonyl" refers to a -C(O)- group, which may also be represented as >C=O.

[0171] "Carboxyl" refers to a -CO2H group or its anion.

[0172] "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.

[0173] "Cyanato" refers to an -OCN group.

[0174] "Cyano" refers to a -CN group.

[0175] "Cycloaliphatic" means a cyclic aliphatic radical as defined herein.

[0176] "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.

[0177] "Cycloalkylalkoxy" means a -OLR group where L is alkyl or alkylene as defined herein and R is cycloalkyl as defined herein.

[0178] Unless otherwise indicated, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 8 carbons, and examples thereof are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], etc. Cycloalkyl may also be substituted or unsubstituted. For example, cycloalkyl may be substituted with one or more groups including those described herein for alkyl. In addition, cycloalkyl may include one or more double bonds and / or triple bonds.

[0179] "Cycloheteroaliphatic" refers to a heteroaliphatic group as defined herein that is cyclic.

[0180] "Disilyl" refers to a group containing a Si-Si bond. In some embodiments, the disilyl group is -SiR S1 R S2 -SiR S3 RS4 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.

[0181] "Disulfide" means -SSR, wherein R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0182] 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.

[0183] "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.

[0184] "Halo" refers to F, Cl, Br or I.

[0185] "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).

[0186] "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.

[0187] "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).

[0188] "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.

[0189] "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.

[0190] "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.

[0191] "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.

[0192] "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.

[0193] "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.

[0194] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to polyvalent (eg, divalent) forms of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0195] "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.

[0196] 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.

[0197] "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.

[0198] "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.

[0199] "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.

[0200] "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.

[0201] "Heteroarylene" refers to a polyvalent (eg, divalent) form of a heteroaryl group as described herein.

[0202] "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.

[0203] 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.

[0204] "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.

[0205] "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.

[0206] "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.

[0207] "Hydroxyl" refers to -OH.

[0208] "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 examples thereof are 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.

[0209] "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.

[0210] "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.

[0211] "Isocyanato" refers to a -NCO group.

[0212] "Isocyano" refers to a -NC group.

[0213] "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.

[0214] "Nitro" refers to a -NO2 group.

[0215] "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.

[0216] "Oxo" refers to a =0 group.

[0217] "Oxy" refers to -O-.

[0218] "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.

[0219] "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.

[0220] "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., January 1977; 66 (1): 1-19; and in "Handbook of Pharmaceutical Salts: Properties, Selection, and Use", Wiley-VCH Press, April 2011 (Second Revised Edition), PH Stahl and CG Weinmuth. Salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or prepared separately by reacting a free base group with a suitable organic acid (thereby producing anionic salts) or by reacting an acid group with a suitable metal or organic salt (thereby producing cationic salts). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, ethylenediaminetetraacetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrobromide, hydrochloride, hydroiodide, isethionate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, malate, The invention also includes but is not limited to iodine, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethyl iodide, toluenesulfonate, undecanoate, valerate, and the like.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, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted 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).

[0221] "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 2and 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.

[0222] "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.

[0223] "Sulfinyl" refers to a -S(O)- group.

[0224] "Sulfo" refers to a -S(O)2OH group.

[0225] "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.

[0226] "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.

[0227] "Thiol" refers to a -SH group.

[0228] Those of ordinary skill in the art will recognize that the definitions provided above are not intended to encompass unallowed substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such unallowed substitution patterns are readily recognized by those of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

[0229] As used herein, the term "about" means + / - 10% of any stated value. As used herein, the term modifies any recited value, range of values, or endpoint(s) of a range.

[0230] As used herein, the terms "top", "bottom", "upper", "lower", "above", and "below" are used to provide relative relationships between structures. The use of these terms does not indicate or require that a particular structure must be located in a particular position in a device.

[0231] Other features and advantages of the invention will be apparent from the following description and claims. Precursor

[0232] Any useful silicon-containing precursor (Si-containing precursor) may be used to deposit the film. Silicon-containing precursors suitable for use according to the disclosed embodiments include polysilane (H3Si-(SiH2) n -SiH3, wherein n≥0). Examples of silanes are monosilane (SiH4), disilane (Si2H6), and organosilanes such as methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, dimethylsilane, diethylsilane, di-tert-butylsilane, allylsilane, sec-butylsilane, tert-hexylsilane (thexylsilane), isopentylsilane, tert-butyldisilane, di-tert-butyldisilane, and the like.

[0233] Halosilanes include at least one halogen group and may or may not include hydrogen and / or carbon groups. Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Although halosilanes (especially fluorosilanes) may form reactive halide species that can etch silicon materials when plasma is ignited, in some embodiments, halosilanes may not be introduced into the chamber when plasma is ignited, so the formation of reactive halide species from halosilanes may be reduced. Specific chlorosilanes are tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallyl silane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert-butylchlorosilane, di-tert-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, tert-butyldimethylchlorosilane, tert-hexyldimethylchlorosilane, etc.

[0234] Aminosilanes include 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), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted mono-, di-, tri-, and tetra-aminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2(BTBAS), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, and the like. A further example of an aminosilane is trisilylamine (N(SiH3)3). In some embodiments, the precursor comprises a structure of formula (I): Si(R')4 (I), Wherein at least one R' comprises a carbon atom. In other embodiments, at least one R' comprises a heteroatom (e.g., nitrogen, oxygen and / or silicon). In other embodiments, at least one R' comprises a carbon atom and a heteroatom (e.g., nitrogen, oxygen and / or silicon). In specific embodiments, R' does not comprise a halogen atom.

[0235] In other embodiments, the precursor comprises a structure of formula (II): (R')3Si-[L-Si(R')2]-R' (II), Wherein at least one R' comprises a carbon atom and L is a linker. In some embodiments, at least one R' comprises a heteroatom (e.g., nitrogen, oxygen and / or silicon). In other embodiments, at least one R' comprises a carbon atom and a heteroatom (e.g., nitrogen, oxygen and / or silicon). In specific embodiments, R' does not comprise a halogen atom.

[0236] For Formula (II), non-limiting linking groups for L include covalent bonds, oxy (—O—), carbonyl (—C(O)—), optionally substituted carboimidoyl (e.g., —C(NR)—), optionally substituted imino (e.g., —NR—), optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, and the like.

[0237] For any formula herein (e.g., for formula (I) or (II)), R' can be H, an aliphatic group, a heteroaliphatic group, an aromatic group, a heteroaromatic group, an amino group, a hydrazine group, an azido group, a hydroxyl group, a silyl group (e.g., an aminosilyl group, an alkoxysilyl group, etc.), a siloxy group (e.g., an aminosiloxy group, an alkoxysiloxy group, etc.), a cyanato group (-OCN), an isocyanato group (-NCO), a cyano group (-CN), or an isocyano group (-NC), any of which can be optionally substituted.

[0238] In a specific embodiment, at least one, two, three, four or more R' in any formula herein (e.g., for formula (I) or (II)) comprises an optionally substituted aliphatic group. Non-limiting aliphatic groups include alkyl, alkenyl or alkynyl, including their linear, branched, cyclic, saturated or unsaturated forms. Such groups can be unsubstituted or substituted, for example, substituted with one or more substituents described herein for alkyl. Other examples of aliphatic groups include methyl (Me), ethyl (Et), propyl (Pr), isopropyl (iPr), cyclopropyl (cPr), butyl (Bu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu), pentyl (Pe), tert-pentyl (tPe), allyl (All), vinyl (Vi), ethynyl, etc.

[0239] In some embodiments, at least one, two, three, four or more R' in any formula herein (e.g., for formula (I) or (II)) comprises an optionally substituted heteroaliphatic group. The heteroaliphatic group can comprise any group comprising one or more carbon atoms and one or more heteroatoms (e.g., oxygen, nitrogen, etc.).

[0240] Non-limiting examples of heteroaliphatic groups include aliphatic-carbonyl (e.g., alkanoyl or -C(O)R Ak ), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R Ak ), aliphatic-oxy ​​(e.g., alkoxy or -OR Ak ), aliphatic-oxycarbonyl (eg, alkoxycarbonyl or -C(O)OR Ak ), amino groups (e.g., -NR N1 R N2 ), aromatic-carbonyl (e.g., aroyl or -C(O)RAr ), aromatic-carbonyloxy (e.g., aroyloxy or -OC(O)R Ar ), aromatic-oxy ​​(e.g., aryloxy or -OR Ar ), aromatic-oxycarbonyl (e.g., aryloxycarbonyl or -C(O)OR Ar ), imino (e.g., -C(NR N1 )H、-C(NR N1 )R Ak or -C(NR N1 )R Ar ), carbamoyl (e.g., -C(O)NR N1 R N2 ), carbamoyloxy (e.g., -OC(O)NR N1 R N2 ), carboxyl (-CO2H), formyl (-C(O)H), heteroaromatic, heterocyclic (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, etc.), hydrazine (e.g., -NR N1 -NR N2 R N3 ), silyl (e.g., -SiR S1 R S2 R S3 ) and silyloxy groups (e.g., -O-SiR S1 R S2 R S3 ). Each of these groups may be optionally substituted with any substituent described herein (e.g., as described herein for alkyl). The heteroaliphatic group may include its linear, branched, cyclic (e.g., heterocyclyl), saturated, or unsaturated forms.

[0241] Heteroaliphatic groups may contain R Ak and / or R Ar In some embodiments, R Ak is optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl. In other embodiments, R Ar is an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.

[0242] Nitrogen-containing groups (e.g., amino, imino, etc.) include R N1 , R N2and / or R N3 In some embodiments, R N1 , R N2 and R N3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, or optionally substituted siloxy. N1 and R N2 or R N2 and R N3 Together with the nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group. This nitrogen-containing group may be contained within other moieties, such as a silyl group or a siloxy group.

[0243] The silicon-containing group (eg, silyl group, etc.) may include R S1 , R S2 and / or R S3 In some embodiments, R S1 , R S2 and R S3 Each is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, or an optionally substituted amino. Such silicon-containing groups may be contained within other moieties, such as an amino group.

[0244] In some embodiments, the silyl group is an alkylsilyl group having one or more aliphatic groups attached to the silicon atom. In one instance, the alkylsilyl group is -Si(R) a (R Ak ) b , wherein R is independently H, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R Ak is an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Other non-limiting alkylsilyl groups include -SiH2R Ak 、-SiH[R Ak ]2 or -Si[R Ak ]3, where R Ak Any of the ones provided herein.

[0245] In some embodiments, the silyl group is an alkoxysilyl group having one or more aliphatic groups attached to the silicon atom via an oxy group (-O-). In one case, the alkoxysilyl group is -Si(R) a (OR Ak ), wherein R is independently H, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R Ak is an optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; a ≥ 0; b ≥ 1; and a + b = 3. Other non-limiting alkoxysilyl groups include -SiH2 [OR Ak ]、-SiH[OR Ak ]2 or -Si[OR Ak ]3, where R Ak Any of those described herein.

[0246] In other embodiments, the silyl group is an arylsilyl group having one or more aromatic groups attached to the silicon atom. In one case, the arylsilyl group is -Si(R) a (R Ar ) b , wherein R is independently H, aliphatic, heteroaliphatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R Ar is an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; a ≥ 0; b ≥ 1; and a + b = 3. Other non-limiting arylsilyl groups include -SiH2R Ar 、-SiH[R Ar ]2 or -Si[R Ar ]3, where R Ar Any of those described herein.

[0247] In other embodiments, the silyl group is an aryloxysilyl group having one or more aromatic groups attached to the silicon atom via an oxy group (-O-). In one case, the arylsilyl group is -Si(R) a (OR Ar ) b , wherein R is independently H, aliphatic, heteroaliphatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R Ar is an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted aryl group, or an optionally substituted heteroaryl group; a ≥ 0; b ≥ 1; and a + b = 3. Other non-limiting aryloxysilyl groups include -SiH2 [OR Ar ]、-SiH[OR Ar ]2 or -Si[OR Ar ]3, where R Ar Any of those described herein.

[0248] Silyl groups may also include aminosilyl groups having one or more optionally substituted amino groups attached to a silicon atom. In one embodiment, the aminosilyl group is -Si(R) a (NR N1 R N2 ) b , wherein R is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R N1 and R N2 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy, wherein R N1 and R N2 can be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclic group; a ≥ 0; b ≥ 1; and a + b = 3. Other non-limiting embodiments of the aminosilyl group include -SiH2 [NR N1 R N2 ]、-SiH[R Ak ]NR N1 R N2 ]、-Si[R Ak2[NR N1 R N2 、 -SiH[NR N1 R N2 2、 -Si[R Ak [NR N1 R N2 2、 or -Si[NR N1 R N2 3), such as -SiH2[NH2], -SiHR Ak [NH2], -Si[R Ak 2[NH2], -SiH2[NH(R Ak )], -SiHR Ak [NH(R Ak )], -Si[R Ak 2[NH(R Ak )], -SiH2[N(R Ak )2], -SiHR Ak [N(R Ak )2], -Si[R Ak 2[N(R Ak )2], -SiH[NH2]2, -SiR Ak [NH2]2, -SiH[NH(R Ak )]2, -SiR Ak [NH(R Ak )]2, -SiH[NH(R Ak )][NH2], -SiR Ak [NH(R Ak )][NH2], -SiH[N(R Ak )2]2, -SiR Ak [N(R Ak )2]2, -SiH[N(R Ak )2][NH2], -SiR Ak [N(R Ak )2][NH2], -Si[NH2]3, -Si[N(R Ak )2][NH2]2, -Si[N(R Ak )2]2[NH2], -Si[N(R Ak )2]3, -Si[NH(R Ak )][NH2]2, -Si[NH(R Ak )2]2[NH2], -Si[NH(R Ak )]3, -Si[NH(R Ak )][N(R Ak )2]2, -Si[NH(R Ak )]2[N(RAk )2], etc., where R Ak is an optionally substituted aliphatic, heteroaliphatic, alkyl, alkenyl, alkynyl or alkoxyl group; and R N1 and R N2 Each is any one described herein.

[0249] In some embodiments, the silyl group is -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. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0250] In other embodiments, any silyl group herein may be attached to the parent compound via an oxy bond. In some embodiments, the silyloxy group is -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. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl. Other non-limiting siloxy groups include -O-Si(R) a (R Ak ) b 、-O-Si(R) a (OR Ak ) b 、-O-Si(R) a (R Ar ) b 、-O-Si(R) a (OR Ar )b 、-O-Si(R) a (NR N1 R N2 ) b , wherein R is independently H, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxyl, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano or isocyano, any of which may be optionally substituted; R Ak R is optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, or optionally substituted heterocyclyl; R Ar is an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted aryl group or an optionally substituted heteroaryl group; R N1 and R N2 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy, wherein R N1 and R N2 Together with the nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group; a≥0; b≥1; and a+b=3. Other non-limiting silyloxy groups include alkylsilyloxy groups (e.g., -O-SiH2R Ak 、-O-SiH[R Ak ]2 or -O-Si[R Ak ]3); alkoxysilyloxy (e.g., -O-SiH2[OR Ak ]、-O-SiH[OR Ak ]2 or -O-Si[OR Ak ]3); arylsilyloxy (e.g., -O-SiH2R Ar 、-O-SiH[R Ar ]2 or -O-Si[R Ar ]3); or aryloxysilyloxy (e.g., -O-SiH2[OR Ar ]、-O-SiH[OR Ar ]2 or -O-Si[OR Ar ]3). In some embodiments, the silyl group is an aminosilyloxy group (e.g., -O-SiH2[NR N1 R N2 ]、-O-SiH[R Ak ]NRN1 R N2 ]、-O-Si[R Ak ]2[NR N1 R N2 ]、-O-SiH[NR N1 R N2 ]2. -O-Si[R Ak ]NR N1 R N2 ]2, or -O-Si[NR N1 R N2 ]3).

[0251] Silyl and siloxy groups can have mixed combinations of aliphatic and aromatic groups. In one embodiment, the silyl group is -Si(R) a (R Ak ) b (R Ar ) c or -Si(R) a (OR Ak ) b (OR Ar ) c , wherein R is independently H, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R Ak is an optionally substituted aliphatic (eg, optionally substituted alkyl) or an optionally substituted heteroaliphatic (eg, optionally substituted alkoxy or optionally substituted amino); R Ar is an optionally substituted aromatic group or an optionally substituted heteroaromatic group; a, b and c are each ≥0; and a+b+c=3.

[0252] In another embodiment, the silyl group is -Si(R) a (NR Ak 2) b 、-Si(R) a (NR Ak R Ar ) b , or -Si(R) a (NR Ar 2) b, wherein R is independently H, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxy, silyl (e.g., aminosilyl, alkoxysilyl, etc.), siloxy (e.g., aminosiloxy, alkoxysiloxy, etc.), cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; R N1 and R N2 are each independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy, wherein R N1 and R N2 together with the nitrogen atom to which they are attached, may form an optionally substituted heterocyclic group; a and b are each ≥0; and a+b=3.

[0253] In yet another embodiment, the silyloxy group is -O-Si(R) a (R Ak ) b (R Ar ) c 、-O-Si(R) a (OR Ak ) b (OR Ar ) c 、-O-Si(R) a (NR Ak 2) b 、-O-Si(R) a (NR Ak R Ar ) b , or -O-Si(R) a (NR Ar 2) b , where R, R Ak and R Ar is any one described herein; and a, b and c are any one described herein.

[0254] In some embodiments, at least one, two, three, four, or more R' in any of the formulae herein (e.g., for formula (I) or (II)) comprises an optionally substituted aliphatic-oxy, heteroaliphatic-oxy, aromatic-oxy, or heteroaromatic-oxy. For example, R' can be -OR, wherein R is an optionally substituted aliphatic (e.g., alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, or cycloalkynyl), an optionally substituted heteroaliphatic (e.g., heteroalkyl, heteroalkenyl, heteroalkynyl, or heterocyclyl), an optionally substituted aromatic (e.g., aryl), an optionally substituted heteroaromatic (e.g., heteroaryl), an optionally substituted aliphatic-carbonyl (e.g., alkanoyl, or -C(O)RAk , where R Ak is an optionally substituted aliphatic or any of those described herein), an optionally substituted silyl (e.g., -SiR S1 R S2 R S3 or -Si(R') a (OR) b (NR2) c , including any of those described herein) or an optionally substituted amino group (e.g., -NR N1 R N2 , including any one described herein).

[0255] In certain embodiments, at least one, two, three, four or more R' in any formula herein (e.g., for formula (I) or (II)) comprises an optionally substituted aromatic group or an optionally substituted heteroaromatic group. Non-limiting aromatic and heteroaromatic groups include phenyl, benzyl, naphthyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, and the like.

[0256] In certain embodiments, at least one, two, three, four or more R' in any of the formulae herein (eg, for formula (I) or (II)) comprises an optionally substituted amino group (eg, -NH2, -NR N1 H or -NR N1 R N2 ). In a specific embodiment, R N1 and R N2 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxy, 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 N1 and R N2 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0257] R N1 and R N2 Non-limiting examples of may include H, aliphatic, alkyl (e.g., -R Ak ), alkenyl, alkynyl, aliphatic carbonyl (e.g., alkanoyl or -C(O)R Ak ), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R Ak ), aliphatic-oxy ​​(e.g., alkoxy or -OR Ak), aliphatic-oxycarbonyl (eg, alkoxycarbonyl or -C(O)OR Ak ), amino (e.g., -NR2, wherein each R is, for example, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), aromatic (e.g., aryl or -R Ar ), aromatic-carbonyl (e.g., aroyl or -C(O)R Ar ), aromatic-carbonyloxy (e.g., aroyloxy or OC(O)R Ar ), aromatic-oxy ​​(e.g. aryloxy or -OR Ar ), aromatic-oxycarbonyl (e.g., aryloxycarbonyl or -C(O)OR Ar ), imino (e.g., -C(NR)H, -C(NR)R Ak or -C(NR)R Ar , wherein each R is, for example, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carbamoyl (e.g., —C(O)NR2, wherein each R is, for example, H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic), carbamoyloxy (e.g., —OC(O)NR2, wherein each R is, for example, H, optionally substituted substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic or optionally substituted heteroaromatic), carboxyl (-C02H), formyl (-C(O)H), heteroaromatic, heterocyclic (e.g., optionally substituted furanyl, tetrahydrofuranyl, pyrrolidinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, piperidinyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, oxazolyl, morpholinyl, etc.), hydroxyl (-OH), silyl (e.g., -SiR S1 R S2 R S3 or -Si(R') a (OR) b (NR2) c ) and silyloxy groups (e.g. -O-SiR S1 R S2 R S3 or -O-Si(R') a (OR) b (NR2) c ). For any of these groups, when indicated, R Ak , R Ar , R', R, R S1 , R S2 , R S3, a, b and c can be any of those described herein.

[0258] Other non-limiting amino groups include -NH2, -NHMe, -NMe2, -NHEt, -NMeEt, -NEt, -NHnPr, -NMenPr, -NnPr2, -NHiPr, -NMeiPr, -NiPr2, -NHsBu, -NMesBu, -NsBu2, -NHtBu, -NMetBu, -NtBu2, -N[SiH3]2, -N[Si(Me)3]2, -N[Si(Et)3]2, -NH[SiH3], -NH[Si(Me)3], -NH[Si(Et)3], -NMe[SiH3], - NMe[Si(Me)3], -NMe[Si(Et)3], -N[SiH2Me]2, -N[SiHMe2]2, -N[SiH2Et]2, -N[SiHEt2]2, -N[SiHMeEt]2, -NH[SiH2Me], -NH[SiHMe 2], -NH[SiH2Et], -NH[SiHEt2]2, -NH[SiHMeEt], -NMe[SiH2Me], -NMe[SiHMe2], -NMe[SiH2Et], -NMe[SiHEt2]2, -NMe[SiHMeEt], etc.

[0259] In certain embodiments, at least one, two, three, four or more R' in any of the formulae herein (e.g., for formula (I) or (II)) comprises an optionally substituted hydrazine group (e.g., -NH-NH2 or -NR N1 -NR N2 R N3 ). In a specific embodiment, R N1 , R N2 and R N3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, hydroxy, 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 N1 and R N2 or R N2 and R N3Can form optionally substituted heterocyclic radical together with the nitrogen atom that each is connected.Other non-limiting hydrazino groups include -NH-NH2, -NMe-NH2, -NH-NHMe, -NH-NMe2, -NMe-NMe2, -NEt-NH2, -NH-NHEt, -NH-NEt2, -NMe-NEt2, etc.

[0260] In some embodiments, at least one, two, three, four, or more R' in any of the formulae herein (eg, for formula (I) or (II)) comprises an optionally substituted silyl group. In one embodiment, the silyl group is -SiR S1 R S2 R S3 , where R S1 , R S2 and R S3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted amino, optionally substituted hydrazine, azido, hydroxy, optionally substituted silyl, optionally substituted siloxy, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted heteroalkyl, optionally substituted heteroalkenyl, optionally substituted heteroalkynyl, optionally substituted heterocyclyl, optionally substituted aryl, optionally substituted aryloxy, cyanato, isocyanato, cyano, isocyano, etc. Non-limiting silyl groups include any of those described herein, such as -Si(R) a (R Ak ) b 、-Si(R) a (OR Ak ) b 、-Si(R) a (R Ar ) b 、-Si(R) a (OR Ar ) b 、-Si(R) a (NR N1 R N2 ) b 、-Si(R') a (OR) b (NR2) cEtc. Other non-limiting silyl groups include -SiH3, -SiH2Me, -SiHMe2, -SiMe3, -Si(OH)3, -SiH2(OMe), -SiH(OMe)2, -Si(OMe)3, -SiH2(NH2), -SiHMe(NH2), -SiMe2(NH2), -SiH(NH2)2, -SiMe(NH2)2, -Si(NH2)3, -SiH2(NMe2), -SiH2(NMe2), -SiHMe(NMe2), -Si(Me)2(NMe2)2, -SiMe(NMe2)2, -Si(NMe2)3, -SiH2(NHMe), -SiHMe(NHMe), -SiH(NHMe)2, -SiMe(NHMe)2, -Si(NHMe)3, etc.

[0261] In other embodiments, at least one, two, three, four or more R' in any formula herein (e.g., for formula (I) or (II)) comprises an optionally substituted silyloxy group. Non-limiting silyloxy groups include any of those described herein, such as -O-Si(R) a (R Ak ) b 、-O-Si(R) a (OR Ak ) b 、-O-Si(R) a (R Ar ) b 、-O-Si(R) a (OR Ar ) b 、-O-Si(R) a (NR N1 R N2 ) b 、-O-Si(R') a (OR) b (NR2) cOther non-limiting silyloxy groups include -O-SiH3, -O-SiH2Me, -O-SiHMe2, -O-SiMe3, -O-Si(OH)3, -O-SiH2(OMe), -O-SiH(OMe)2, -O-Si(OMe)3, -O-SiH2(NH2), -O-SiHMe(NH2), -O-SiMe2(NH2), -O-SiH(NH2)2, -O-SiMe(NH2)2, -O -Si(NH2)3, -O-SiH2(NMe2), -O-SiH2(NMe2), -O-SiHMe(NMe2), -O-Si(Me)2(NMe2)2, -O-SiMe(NMe2)2 , -O-Si(NMe2)3, -O-SiH2(NHMe), -O-SiHMe(NHMe), -O-SiH(NHMe)2, -O-SiMe(NHMe)2, -O-Si(NHMe)3, etc.

[0262] In other embodiments, at least one, two, three, four or more R' in any formula herein (e.g., for formula (I) or (II)) comprises an azido group (-N3), a hydroxyl group (-OH), a cyanato group (-OCN), an isocyanate group (-NCO), a cyano group (-CN) and / or an isocyano group (-NC).

[0263] The organosilicon-containing precursor may be selected from the group consisting of silane, disilane, trisilane, tetrasilane, amine-substituted versions of any of the foregoing silanes, and trisilylamine.

[0264] Examples of organic silicon-containing precursors include, but are not limited to, silanes, polysilanes, halosilanes, and aminosilanes. Silanes contain hydrogen and / or carbon groups, but do not contain halogens. Polysilanes may have the formula (H3Si-(SiH2) n -SiH3), where n > 1. Examples of silanes include silane (SiH4), disilane (Si2H6), trisilane, tetrasilane, and organosilanes such as methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, dimethylsilane, diethylsilane, di-tert-butylsilane, allylsilane, sec-butylsilane, dimethylsilane, isopentylsilane, tert-butyldisilane, di-tert-butyldisilane, tetraethyl orthosilicate (also known as tetraethoxysilane or TEOS), and the like.

[0265] 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, for example, tert-butylaminosilane, methylaminosilane, tert-butylsilylamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2(BTBAS), tert-butylsilylcarbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), etc. Another example of an aminosilane is trimethylsilylamine (N(SiH3)3).

[0266] The example of the silicon-containing precursor for depositing silicon carbide includes siloxane, alkylsilane or hydrocarbon-substituted silane or nitrogen-containing carbon reactant.The example of siloxane includes 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), heptamethylcyclotetrasiloxane (HMCTS), silsesquioxane, disiloxane such as pentamethyldisiloxane (PMDSO) or tetramethyldisiloxane (TMDSO) and trisiloxane such as hexamethyltrisiloxane or heptamethyltrisiloxane.Alkylsilane includes central silicon atom, and it has one or more alkyls bonded thereto and one or more hydrogen atoms bonded thereto.In some embodiments, any one or more alkyls contain 1-5 carbon atoms.Hydrocarbyl can be saturated or undersaturated (for example, olefin (for example, vinyl), alkynes and aromatic groups). Examples include, but are not limited to, trimethylsilane (3MS), triethylsilane, pentamethyldisilylmethane ((CH3)2Si-CH2-Si(CH3)3), and dimethylsilane (2MS). Additionally, disilane, trisilane, or other higher order silanes may be used in place of monosilane. In some embodiments, one of the silicon atoms may have a carbon-containing or hydrocarbon group attached thereto, and one of the silicon atoms may have a hydrogen atom attached thereto. Examples of carbon-containing reactants that include nitrogen include methyl-substituted disilazanes and trisilazanes, such as tetramethyldisilazane and hexamethyltrisilazane.

[0267] Other examples of organic silicon-containing precursors can include siloxanes, such as cyclotetrasiloxane, such as heptamethylcyclotetrasiloxane (HMCTS) and tetramethylcyclotetrasiloxane. Other cyclic siloxanes may also include, but are not limited to, cyclotrisiloxane and cyclopentasiloxane. Other examples of suitable precursors include linear siloxanes, such as, but are not limited to, disiloxanes, such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO), hexamethyltrisiloxane and heptamethyltrisiloxane. For undoped silicon carbide, examples of suitable precursors include silanes substituted by one or more alkyl, olefin and / or alkyne groups containing, for example, 1-5 carbon atoms. Examples include, but are not limited to, trimethylsilane (3MS), dimethylsilane (2MS), triethylsilane (TES) and pentamethyldisilazane. Additionally, disilane, trisilane or other higher silanes may be used to replace monosilane. An example of such a disilane from alkylsilanes is hexamethyldisilane (HMDS). Another example of a disilane from the class of alkylsilanes may include pentamethyldisilane (PMDS). Other types of alkylsilanes may include alkylcarbosilanes, which may have a branched polymer structure with carbon bonded to silicon atoms and alkyl groups bonded to silicon atoms. Examples include dimethyltrimethylsilylmethane (DTMSM) and bis-dimethylsilylethane (BDMSE). Examples of other suitable precursors include, for example, alkyldisilazanes and possible compounds, which include amino groups (-NH2) and alkyl groups bonded to one or more silicon atoms, respectively. Alkyldisilazanes include silazane and alkyl groups bonded to two silicon atoms. An example includes 1,1,3,3-tetramethyldisilazane (TMDSN).

[0268] In the Si-containing precursors described herein, different species of R' may be attached to the silicon atom.Additional Si-containing precursors are described herein. Aminosilane

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] The precursor may include 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.

[0277] 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.

[0278] The precursor may contain one or more hydrogen atoms attached to the 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.

[0279] 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.

[0280] 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.

[0281] 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.

[0282] 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 is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In another embodiment, 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.

[0283] 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-).

[0284] 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.

[0285] The precursor may contain heterocyclic groups 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.

[0286] 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.

[0287] 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.

[0288] 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、(R')3Si(NHR Ak In 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.

[0289] 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]); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]); tert-butylamino 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[NCy2]); N-isopropylcyclohexyl ... H3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], wherein Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], wherein Py is pyrrolyl); pyrrolidinyltrimethylsilane (SiMe3[NHPyr], wherein Pyr is pyrrolidinyl); piperidinyltrimethylsilane (SiMe3[NHPip], wherein Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], wherein Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], wherein 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. Isocyanate silane

[0290] The silicon-containing precursor may contain one or more isocyanate groups, thereby providing non-limiting isocyanatosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(NCO) x ,in: x is 1, 2, 3, or 4; and 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.

[0291] In another embodiment, the precursor has the formula (R') z Si(NCO) x (NR"2) y ,in: x is 1, 2, 3, or 4; y and z are each independently 0, 1, 2 or 3; x+y+z=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.

[0292] In yet another embodiment, the precursor has the formula (NCO) x (R') 3-x Si-L-Si(R') 3-x (NCO) x ,in: Each x is independently 0, 1, 2, or 3; L is a linker such as a covalent bond, 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 group, or a silyl group; and 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.

[0293] 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.

[0294] 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.

[0295] The precursor may include any of the following, for example, (R')Si(NCO)(NR"2)2, (R')2Si(NCO)(NR"2), (R')2Si(NCO)(N[SiR3]2), or tetraisocyanatosilane (Si[NCO]4). In 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 is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted aryl, or optionally substituted heteroaryl. Azidosilane

[0296] The silicon-containing precursor may include one or more azido groups, thereby providing non-limiting azidosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(N3) x ,in: x is 1, 2, 3, or 4; and 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.

[0297] In another embodiment, the precursor has the formula (R') z Si(N3) x (NR"2) y ,in: x is 1, 2, 3, or 4; y and z are each independently 0, 1, 2 or 3; x+y+z=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.

[0298] In yet another embodiment, the precursor has formula (N3) x (R') 3-x Si-L-Si(R') 3-x (N3) x ,in: Each x is independently 0, 1, 2, or 3; L is a linker such as a covalent bond, 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 group, or a silyl group; and 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.

[0299] 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.

[0300] 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.

[0301] The precursor may include any of the following, such as (R')3Si(N3), (R')2Si(N3)2, (R')Si(N3)3, or Si(N3)(NR"2)3. In some embodiments, R' and R" may each independently be any of those described herein (e.g., H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, or an optionally substituted alkynyl). Non-limiting examples of precursors also include tris(dimethylamino)silyl azide ([Me2N]3SiN3); di-tert-butyldiazide silane (tBu2Si(N3)2); ethylsilicon triazide (EtSi(N3)3); and the like. Hydrazinosilane

[0302] The silicon-containing precursor may contain one or more optionally substituted hydrazino groups, thereby providing non-limiting hydrazinosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(NR"-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.

[0303] In another embodiment, the precursor has the formula (NR"2-NR") x (R') 3-x Si-L-Si(R') 3-x (NR"-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.

[0304] In yet another embodiment, the precursor has the formula (R') 4-x Si(NR"-L-NR"2) x , wherein: x is 1, 2, 3 or 4; and each L, R' and R" can be any one described herein.

[0305] 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. In other embodiments, L is -NR-NR-, wherein R is any one described herein (e.g., 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).

[0306] 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.

[0307] The precursor may contain any useful combination of R' and hydrazine groups. In one embodiment, the precursor has the formula (R')3Si(NR"-L-NR"2) or (R')3Si(NR"-NR"2), wherein L, R' and R" may be any of those described herein.

[0308] The precursor may contain multiple hydrazines. In one embodiment, the precursor has the formula (R')2Si(NR"-L-NR"2)2, (R')2Si(NR"-NR"2)2, or (R')2Si(NH-NHR")2, wherein L, R' and R" may be any of those described herein.

[0309] The precursor may include at least two silicon atoms. In one embodiment, the precursor has the formula (NR"2-NR")(R')2Si-Si(R')2(NR"-NR"2), wherein each R' and R" may be any of those described herein.

[0310] Non-limiting precursors may include bis(tert-butylhydrazino)diethylsilane (SiEt2[NH-NHtBu]2); tris(dimethylhydrazino)silane (SiH[NH-NMe2]3); and the like. Siloxane and its derivatives

[0311] The silicon-containing precursor may contain one or more aliphatic-oxy, aromatic-oxy ​​and / or oxy groups, thereby providing a siloxane or derivative thereof having one or more Si-O, O-Si-O or Si-O-Si bonds. In one embodiment, the precursor has the formula (R') 4-x Si(OR"') 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, silyl, or siloxy, any of which may be optionally substituted.

[0312] In another embodiment, the precursor has the formula (R"'O) x (R') 3-x Si-L-Si(R') 3-x (OR"') 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, silyl, or siloxy, any of which may be optionally substituted.

[0313] 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. In other embodiments, L is -O-L'-O-, wherein L' is an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an optionally substituted silyl group (e.g., -SiR2-), an optionally substituted alkylene group (e.g., -(CH2) n -, wherein n is 1 to 6), optionally substituted arylene, and the like. In other embodiments, L is oxy.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] The precursor may contain one or more hydrogen atoms attached to the silicon atom. In one embodiment, the precursor has the formula H3Si(OR"'), H2Si(OR"')2 or HSi(OR"')3, wherein each R"' may independently be any one described herein.

[0318] The precursor may contain any combination of R' and OR"' groups within the precursor. In one embodiment, the precursor has the formula (R')3Si(OR"'), (R')2Si(OR"')2, or (R')Si(OR"')3, wherein R' and R"' may each independently be any of those described herein. The precursor may contain an alkyl group, such as in the case of a precursor having the formula (R')3Si(OR"'), (R')2Si(OR"')2, or (R')Si(OR"')3. Ak )3Si(OR Ak )、(R Ak )2Si(OR Ak )2 or (R Ak )Si(OR Ak )3 precursor, wherein R Ak is optionally substituted alkyl.

[0319] 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"'O) x (R') 3-x Si-Si(R') 3-x (OR"') x , wherein R' and R"' can be any of those described herein. In one embodiment, the precursor has the formula (R"'O)(R')2Si-Si(R')2(OR"'), wherein R' and R"' can be any of those described herein.

[0320] The precursor may contain a combination of R' groups and linkers having heteroatoms. In one instance, the precursor has the formula (R')3Si-O-Si(R')3, where R' can be any of those described herein. In another instance, the precursor has the formula (R')3Si-O-L'-O-Si(R')3, where L' and R' can be any of those described herein. In yet another instance, the precursor has the formula (R')3Si-(OSiR'2) z -R', wherein R' can be any of those described herein; and wherein z is 1, 2, 3, 4 or greater. In another embodiment, the precursor has the formula (R') 4-x Si-[(OSiR'2) z -R'] x , wherein R' can be any described herein; x is 1, 2, 3, or 4; and z is 1, 2, 3, 4 or greater.

[0321] The precursor may contain any useful combination of R' and OR"' groups combined with two silicon atoms. In one case, the precursor has the formula (R"'O) x (R') 3-x Si-O-Si(R') 3-x (OR"') x , wherein R' and R"' can be any of those described herein. In another embodiment, the precursor has the formula (R"'O) x (R') 3-x Si-O-L'-O-Si(R') 3-x (OR"') x , wherein L', R' and R"' can be any of those described herein.

[0322] Non-limiting precursors may include methoxydimethylsilane (SiHMe2[OMe]); ethoxydimethylsilane (SiHMe2[OEt]); isopropoxydimethylsilane (SiHMe2[OiPr]); tert-butoxydimethylsilane (SiHMe2[OtBu]); tert-amyloxydimethylsilane (SiHMe2[OtPe]); phenoxydimethylsilane (SiHMe2[OPh]); acetoxydimethylsilane (SiHMe2[OAc]); methoxytrimethylsilane (SiMe3[OMe]); ethoxytrimethylsilane (SiMe3[OEt]); isopropoxytrimethylsilane (SiMe3[OiPr]); tert-butoxytrimethylsilane (SiMe3[OtBu]); tert-amyloxytrimethylsilane (SiMe3[OtPe]); phenoxytrimethylsilane (SiMe3[OPh]); acetoxytrimethylsilane (SiMe3[OAc]); methoxytriethylsilane (SiEt3[OMe]); ethoxytriethylsilane (SiEt3[OEt]); isopropoxytriethylsilane (SiEt3[OiPr]); tert-butoxytriethylsilane (SiEt3[OtBu]); tert-amyloxytriethylsilane (SiEt3[OtPe]); phenoxytriethylsilane (SiEt3[OPh]); acetoxytriethylsilane (SiEt3[OAc]); dimethoxysilane (SiH2[O Me]2); diethoxysilane (SiH2[OEt]2); diisopropoxysilane (SiH2[OPr]2); di-tert-butoxysilane (SiH2[OtBu]2 or DTBOS); di-tert-pentyloxysilane (SiH2[OtPe]2 or DTPOS); diacetoxysilane (SiH2[OAc]2); dimethoxydimethylsilane (SiMe2[OMe]2); diethoxydimethylsilane (SiMe2[OEt]2); diisopropoxydimethylsilane (SiMe2[OPr]2); di-tert-butoxydimethylsilane (SiMe2[OtBu]2); diacetoxydimethylsilane (SiMe2[OAc]2); dimethoxydiethylsilane alkane (SiEt2[OMe]2); diethoxydiethylsilane (SiEt2[OEt]2); diisopropoxydiethylsilane (SiEt2[OiPr]2); di-tert-butoxydiethylsilane (SiEt2[OtBu]2); diacetoxydiethylsilane (SiEt2[OAc]2); dimethoxydiphenylsilane (SiPh2[OMe]2); dimethoxydiisopropylsilane (Si[iPr]2[OMe]2); diethoxydiisopropylsilane (Si[iPr]2[OEt]2); diisopropoxydiisopropylsilane (Si[iPr]2[OiPr]2); di-tert-butoxydiisopropylsilane (Si[iPr]2[OtBu]2);Diacetoxydiisopropylsilane (Si[iPr]2[OAc]2); dimethoxymethylvinylsilane (SiMeVi[OMe]2); diethoxymethylvinylsilane (SiMeVi[OEt]2); diisopropoxymethylvinylsilane (SiMeVi[OiPr]2); di-tert-butyl-p-cresol (SiMeVi[OtBu]2); diacetoxymethylvinylsilane (SiMeVi[OAc]2); triethoxysilane (SiH[OEt]3 or TES); trimethoxyethylsilane (SiEt[OMe]3); triethoxymethylsilane (SiMe[OEt]3); triethoxyphenylsilane (SiPh[OEt]3); tetramethoxy Silane (Si[OMe]4); tetraethoxysilane (Si[OEt]4 or TEOS); tetra-n-propoxysilane (Si[OnPr]4); tetraisopropoxysilane (Si[OiPr]4); tetra-n-butoxysilane (Si[OnBu]4); tetra-tert-butoxysilane (Si[OtBu]4); tetramethyldisiloxane (O[SiHMe2]2 or TMDO); hexamethyldisiloxane (O[SiMe3]2); hexaethyldisiloxane (O[SiEt3]2); hexapropyldisiloxane (O[SiPr3]2); hexaphenyldisiloxane (O[SiPh3]2); hexamethyltrisiloxane (Me2SiH-O-SiMe2-O-SiHMe2); etc. ; Mixed silane containing oxygen and nitrogen

[0323] The silicon-containing precursor may contain one or more optionally substituted amino groups having aliphatic-oxy ​​or aromatic-oxy ​​groups, thereby providing non-limiting mixed silanes. In one embodiment, the precursor has the formula (R') z Si(OR"') x (NR"2) y ,in: x and y are each independently 1, 2, 3 or 4; z is 0, 1, or 2; x+y+z=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; 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; and Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or siloxy, any of which may be optionally substituted.

[0324] In another embodiment, the precursor has the formula (R2N): y (R"'O) x (R') z Si-L-Si(R') z (OR"') x (NR"2) y ,in: x and y are each greater than 0 (e.g., 1 or 2); z is 0 or 1; x+y+z=3; L is a linker, such as a covalent bond, 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 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; 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; and Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or siloxy, any of which may be optionally substituted.

[0325] Non-limiting examples of R', R", and R'" are described herein, such as aminosilane, siloxane, or derivatives thereof.

[0326] The precursor may contain any combination of R', NR"2, and OR"' groups. In one embodiment, the precursor has the formula (R')Si(OR"')2(NR"2) or (R')2Si(OR"')2(NR"2), wherein R', R" and R"' may each independently be any of those described herein. In other embodiments, the precursor has the formula (R')2Si(OR"')(N[SiR3]2), wherein R' and R"' may each independently be any of those described herein; and R is independently H, an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, or an optionally substituted heteroaromatic.

[0327] The precursor may contain only amino and oxy groups attached to silicon atoms. In one embodiment, the precursor has the formula Si(OR"')3(NR"2), Si(OR"')2(NR"2)2 or Si(OR"')(NR"2)3, wherein R" and R"' can each independently be any of those described herein. Non-limiting precursors can include, for example, diethoxy(isopropylamino)silane (SiH[NHiPr][OEt]2); diethoxy(tert-butylamino)silane (SiH[NHtBu][OEt]2); diethoxy(tert-amylamino)silane (SiH[NHtPe][OEt]2); di-tert-butoxy(methylamino)silane (SiH[NHMe][OtBu]2); di-tert-butoxy(ethylamino)silane (SiH[NHEt][OtBu]2); di-tert-butoxy (isopropylamino) silane (SiH[NHiPr][OtBu]2); di-tert-butoxy(n-butylamino) silane (SiH[NHnBu][OtBu]2); di-tert-butoxy(sec-butylamino) silane (SiH[NHsBu][OtBu]2); di-tert-butoxy(isobutylamino) silane (SiH[NHiBu][OtBu]2); di-tert-butoxy(tert-butylamino) silane (SiH[NHtBu][OtBu]2); di-tert-pentyloxy(methyl ... iH[NHMe][OtPe]2); di-tert-pentyloxy(ethylamino)silane (SiH[NHEt][OtPe]2); di-tert-pentyloxy(isopropylamino)silane (SiH[NHiPr][OtPe]2); di-tert-pentyloxy(n-butylamino)silane (SiH[NHnBu][OtPe]2); di-tert-pentyloxy(sec-butylamino)silane (SiH[NHsBu][OtPe]2); di-tert-pentyloxy(isobutylamino)silane (SiH[NHiBu][OtPr]2); e]2); di-tert-pentyloxy(tert-butylamino)silane (SiH[NHtBu][OtPe]2); dimethoxy(phenylmethylamino)silane (SiH[NPhMe][OMe]2); diethoxy(phenylmethylamino)silane (SiH[NPhMe][OEt]2); dimethoxy(phenylmethylamino)methylsilane (SiMe[NPhMe][OMe]2); diethoxy(phenylmethylamino)methylsilane (SiEt[NPhMe][OEt]2); and the like. Silylamine

[0328] The silicon-containing precursor may contain one or more optionally substituted silyl groups attached to a nitrogen atom, thereby providing a non-limiting silylamine. In one embodiment, the precursor has the formula (R'3-yN(SiR'3)y, wherein: y is 1, 2, or 3; 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, amino, silyl, or siloxy, 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.

[0329] In another embodiment, the precursor has the formula (R'3Si) y (R") 2-y NLN(R") 2-y (SiR'3) y ,in: Each y is independently 0, 1, or 2; 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, Optionally, wherein NLN together form a multivalent heterocyclic group.

[0330] In one case, at least one y is not 0. In another embodiment, y can be 0 (e.g., if L comprises carbon atoms or heteroatoms). In yet another embodiment, y 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 (e.g., —NR— or —N(SiR 3 )—), or a silyl (e.g., —SiR 2 —), and combinations thereof (e.g., —SiR 2 —NR—, —NR—SiR 2 —, —SiR 2 —NR—SiR 2 —, etc.). In specific embodiments, each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic.

[0331] 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 or -SiR2-L-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 groups), aromatic-oxy ​​groups (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In specific embodiments, 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, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted aryl group, and an optionally substituted heteroaromatic group; 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, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group. L can be any available linking group (e.g., a covalent bond, an optionally substituted alkylene group, an optionally substituted heteroalkylene group, an oxy group, an imino group, a silyl group, and the like).

[0332] 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.

[0333] The precursor may contain at least one R" group attached to the nitrogen atom. In one embodiment, the precursor has the formula (R")N(SiR'3)2 or (R")2N(SiR'3), wherein R' and R" may be any of those described herein. In another embodiment, the precursor has the formula (R")2N(SiH3) or (R")N(SiH3)2, wherein R" may be any of those described herein. In a specific embodiment, R' is an optionally substituted alkyl, amino or alkoxy group; and R" is an optionally substituted alkyl or amino group, optionally wherein the two R" together with the nitrogen atoms to which they are attached form a heterocyclic group.

[0334] The precursor may include at least one hydrogen atom attached to the nitrogen atom. In one embodiment, the precursor has the formula (H)N(SiR'3)2, wherein R' may be any of those described herein. In another embodiment, the precursor has the formula (H)N(SiR Ak 3)2, where R Ak It may be an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group.

[0335] The precursor may comprise three silicon atoms attached to a nitrogen atom. In one embodiment, the precursor has the formula N(SiR'3)3, wherein R' may be any of those described herein. In another embodiment, the precursor has the formula N(SiH3)(SiR'3)2, wherein R' may be any of those described herein. In yet another embodiment, the precursor has the formula N(SiH3)(SiR'3)2 Ak 3)2, where R Ak It may be an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group.

[0336] The precursor may have two or more nitrogen atoms, wherein the precursor comprises a N-N bond. In one instance, the precursor has the formula (R'3Si)2N-N(SiR'3)2, wherein R' may be any of those described herein.

[0337] The linking group may be present between nitrogen atoms. In one case, the precursor has the formula (R'3Si)(R")NLN(R")(SiR'3) or (R'3Si)2N-LN(SiR'3)2, wherein R' and R" may be any of those described herein. In some embodiments, L is a covalent bond, an optionally substituted alkylene, an optionally substituted heteroalkylene, -O-, -SiR2-, or -Si-. In specific embodiments, at least one R" is not H. In another case, the precursor has the formula (H3Si)(R")NLN(R")(SiH3), wherein R" may be any of those described herein.

[0338] The linking group may comprise a silicon atom. In one instance, the precursor has the formula (R'3Si)2N-SiR'2-N(SiR'3)2, wherein R' may be any of those described herein. In another instance, the precursor has the formula ((R'3Si)(R")N-SiR'2-N(R")(SiR'3) or (R'3Si)2N-SiR'2-N(R")2, wherein R' and R" may be any of those described herein.

[0339] The linking group may comprise a SiH2 group. In one instance, the precursor has the formula (R'3Si)2N-SiH2-N(SiR'3)2, wherein R' may be any of those described herein. In another instance, the precursor has the formula (R'3Si)HN-SiH2-NH(SiR'3) or (R'3Si)2N-SiH2-N(R")2, wherein R' and R" may be any of those described herein.

[0340] Multiple nitrogen and silicon containing moieties may be present in the precursor. In one embodiment, the precursor has the formula (R'3Si)(R")N-SiR'2-N(R")-SiR'2-N(R")(SiR'3), wherein R' and R" may be any of those described herein.

[0341] Non-limiting precursors may include, for example, 1,1,3,3-tetramethyldisilazane (NH[SiHMe2]2 or TMDS); 1,1,2,3,3-pentylmethyldisilazane (NMe[SiHMe2]2); 1,1,1,3,3,3-hexamethyldisilazane (NH[SiMe3]2 or HMDS); heptamethyldisilazane (NMe[SiMe3]2); 1,1,1,3,3,3-hexamethyl-2-ethyldisilazane (NEt[SiMe3]2); 1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane (NiPr [SiMe3]2); 1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane (NiPr[SiEt3]2); 1,1,3,3-tetramethyl-2-isopropyldisilazane (NiPr[SiHMe2]2); 1,1,3,3-tetraethyl-2-isopropyldisilazane (NiPr[SiHEt2]2); 1,3-diethyltetramethyldisilazane (NH[SiMe2Et]2); 1,1,3,3-tetraethyldisilazane (NH[SiHEt2]2); 1,1,3,3-tetraethyl-2-methyldisilazane (NMe [SiHEt2]2); 1,1,1,3,3,3-hexaethyldisilazane (NH[SiEt3]2); 1,1,1,3,3,3-hexaethyl-2-methyldisilazane (NMe[SiEt3]2); 1,1,1,2,3,3,3-heptaethyldisilazane (NEt[SiEt3]2); 1,2,3-trimethyltrisilazane (N[SiH2Me]3); nonylmethyltrisilazane (N[SiMe3]3); diisopropylsilylamine (NiPr2[SiH3]); diethylsilylamine (NEt2[SiH3]); di Isopropylsilylamine (NiPr2[SiH3]); di-sec-butylsilylamine (NsBu2[SiH3]); di-tert-butylsilylamine (NtBu2[SiH3]); disilylmethylamine (NMe[SiH3]2); disilylethylamine (NEt[SiH3]2); disilylisopropylamine (NiPr[SiH3]2); disilyltert-butylamine (NtBu[SiH3]2); bis(trimethylsilyl)amine (NH[SiMe3]2); bis(triethylsilyl)amine (NH[SiEt3]2); and the like. Silazane and its derivatives

[0342] The silicon-containing precursor may contain one or more amino, silyl and / or imino groups, thereby providing a silazane or derivative thereof having one or more Si-N, N-Si-N, Si-N-Si, N-Si-Si or N-Si-N-Si bonds. In one embodiment, the precursor has the formula (R") 3-yN(SiR'2-L-SiR'3) y ,in: y is 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, and combinations thereof; 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, amino, silyl, or siloxy, 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.

[0343] In another embodiment, the precursor has the formula (R") 3-y N(SiR'2-L-SiR'2-NR"2) y , wherein y is 1, 2 or 3; and L, R' and R" can each be any one described herein.

[0344] In yet another embodiment, the precursor has formula (R") 3-y N(SiR'2-L-NR"2) y , wherein y is 1, 2 or 3; and L, R' and R" can each be any one described herein.

[0345] In one embodiment, the precursor has the formula (R') 4-x Si(NR"-L-SiR'3) x ,in: x is 1, 2, 3, or 4; 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, and combinations thereof; 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, amino, silyl, or siloxy, 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.

[0346] In another embodiment, the precursor has the formula ((R'2N)-(SiR'2-L) z -SiR'3, wherein z is 1, 2 or 3; and L, R' and R" can each be any one described herein.

[0347] In some embodiments, L comprises optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (—O—), imino (e.g., —NR— or —N(SiR3)—), or silyl (e.g., —SiR2—), and combinations thereof (e.g., —SiR2-NR—, —NR-SiR2—, —SiR2-NR-SiR2—, etc.). In specific embodiments, each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic.

[0348] 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 or -SiR2-L-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 groups), aromatic-oxy ​​groups (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In specific embodiments, 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, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted aryl group, and an optionally substituted heteroaromatic group; 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, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aryl group. L can be any available linking group (e.g., a covalent bond, an optionally substituted alkylene group, an optionally substituted heteroalkylene group, an oxy group, an imino group, a silyl group, and the like).

[0349] 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.

[0350] The precursor may contain one or more disilyl groups and amino groups. In one embodiment, the precursor has the formula R"2N-SiR'2-SiR'3, wherein L, R' and R" may be any of those described herein. In other embodiments, the precursor has the formula R"2N-SiH2-SiH3, wherein R" is any of those described herein. In another embodiment, the precursor has the formula (R") 3-y N-(SiR'2-SiR'3) y , wherein y, R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R") 3-y N-(SiH2-SiH3) y , wherein y and R" can be any of those described herein.

[0351] The precursor may contain a divalent disilane group. In one embodiment, the precursor has the formula R"2N-SiR'2-SiR'2-L-NR"2, wherein L, R' and R" may be any of those described herein. In another embodiment, the precursor has the formula R"2N-SiR'2-SiR'2-NR"2, wherein R' and R" may be any of those described herein.

[0352] The linker L may be present between two silyl groups. In one embodiment, the precursor has the formula R"2N-SiR'2-L-SiR'3 or R"N-(SiR'2-L-SiR'3)2, wherein L, R' and R" may be any of those described herein. In another embodiment, the precursor has the formula R"2N-SiR'2-L-SiR'2-NR"2, wherein L, R' and R" may be any of those described herein. In yet another embodiment, the precursor has the formula (R") 3-y N-(SiR'2-L-SiH3) y , wherein y, L, R' and R" can be any of those described herein.

[0353] The precursor may contain -SiH3 as a silyl group. In one embodiment, the precursor has the formula R"2N-SiH2-SiH3, wherein R" may be any of those described herein. In another embodiment, the precursor has the formula (R")N-(SiH2-L-SiH3)2 or (R")2N-(SiH2-L-SiH3), wherein L and R" may be any of those described herein.

[0354] The precursor may include a silyl-substituted amino group, such as -NR"-SiR'3, where R' and R" may be any of those described herein. In one embodiment, the precursor has the formula (R') 4-x Si(NR"-SiR'3) x or (R') 4-x Si(NH-SiR'3) x , wherein x is 1, 2, 3 or 4; and wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula H2Si(NR"-SiR'3)3, wherein R' and R" can be any of those described herein.

[0355] The precursor may include a bis-trimethylsilylamino group, such as -N(SiR'3)2, where R' may be any of those described herein. In one embodiment, the precursor has the formula R"2N-SiR'2-N(SiR'3)2, where R' and R" may be any of those described herein. In another embodiment, the precursor has the formula R"2N-SiH2-N(SiH3)2, where R' may be any of those described herein. In yet another embodiment, the precursor has the formula (R'3Si)2N-[SiR'2-N(SiR'3)] z (SiR'3), wherein z is 0, 1, 2 or 3; and wherein R' and R" can be any of those described herein.

[0356] The precursor may include a linker group L disposed between the silicon atom and the nitrogen atom. In one embodiment, the precursor has the formula R"2N-SiR'2-L-NR"2, wherein L, R' and R" may be any of those described herein.

[0357] The precursor may include a linker group L located between two nitrogen atoms. In one embodiment, the precursor has the formula R'3Si-SiR'2-NR"-L-NR"-SiR'2-SiR'3, wherein L, R' and R" may be any of those described herein.

[0358] The linking group may include a silyl imino group, such as -N(SiR'3)-, where R' may be any group described herein. In one embodiment, the precursor has the formula R"2N-[SiR'2-N(SiR'3)] z -SiR'3 or R"2N-[N(SiR'3)] z -SiR'3, wherein z is 1, 2, 3 or greater; and wherein R' and R" can be any of those described herein.

[0359] The linking group may include a silyl group and an imino group. In one embodiment, the precursor has the formula R"2N-[SiR'2-NR"] z -SiR'3, wherein z is 1, 2, 3 or greater; and wherein R' and R" can be any of those described herein.

[0360] Non-limiting precursors include, for example, diisopropylaminodisilane ([iPr2N]-SiH2-SiH3); di-sec-butylaminodisilane ([sBu2N]-SiH2-SiH3); methylcyclohexylaminodisilane ([MeCyN]-SiH2-SiH3); methylphenylaminodisilane ([MePhN]-SiH2-SiH3); piperidinedisilane; 3,5-dimethylpiperidinedisilane; diisopropylaminotrisilylamine ([iPr2N]-SiH2-N[SiH3]2); diethylaminotrisilylamine ([Et2N]-SiH2-N[SiH3]2); isopropylaminotrisilylamine ([iPrHN]-SiH2-N[SiH3]2); and the like. A mixed amine containing silicon and oxygen

[0361] The silicon-containing precursor may contain one or more amino groups substituted with a silyl group, thereby providing a non-limiting mixed amine. In one embodiment, the precursor has the formula (R") 3-y N[Si(OR"') x R' 3-x ] y ,in: x and y are each independently 1, 2 or 3; 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; 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; and Each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or siloxy, any of which may be optionally substituted.

[0362] Non-limiting examples of R', R", and R'" are described herein, such as aminosilane, siloxane, silylamine, or derivatives thereof.

[0363] The precursor may contain any combination of R" groups and silicon-containing groups. In one embodiment, the precursor has the formula (R")3-y N[Si(OR Ak ) x R Ak 3-x ] y or (R Ak ) 3-y N[Si(OR Ak ) x R Ak 3-x ] y , wherein R", x and y are any of those described herein; and wherein R Ak is H, optionally substituted aliphatic or optionally substituted heteroaliphatic. In a specific embodiment, RR Ak is H, optionally substituted alkyl, optionally substituted alkylene or optionally substituted alkynyl. In other embodiments, the precursor has the formula (R") 3-y N[Si(OR Ak ) x H 3-x ] y or (R") 3-y N[Si(OR Ak )H(R Ak )] y , where R", R Ak , x and y are any described herein.

[0364] The precursor may contain two silicon-containing groups. In one embodiment, the precursor has the formula (R")N[Si(OR Ak ) x R Ak 3-x ]2 or (R Ak )N[Si(OR Ak ) x R Ak 3-x ]2, where R", R Ak , x and y are any of those described herein. In specific embodiments, x is 1 or 2.

[0365] The precursor may contain a hydrogen atom attached to a nitrogen atom. In one embodiment, the precursor has the formula (H) 3-y N[Si(OR Ak ) x R Ak 3-x ] y or (H) 3-y N[Si(OR Ak ) x H 3-x ] y or (H) 3-yN[Si(OR Ak )H(R Ak )] y , where R Ak , x and y are any of those described herein. In specific embodiments, x is 1 or 2.

[0366] Non-limiting precursors include, for example, bis(dimethoxysilyl)amine (NH[Si(OMe)2H]2); bis(diethoxysilyl)amine (NH[Si(OEt)2H]2); N-isopropylbis(diethoxysilyl)amine (NiPr[Si(OEt)2H]2); bis(methoxymethylsilyl)amine (NH[Si(OMe)MeH]2); tris(dimethoxysilyl)amine (N[Si(OMe)2H]3); tris(methoxymethylsilyl)amine (N[Si(OMe)MeH]3); tris(diethoxysilyl)amine (N[Si(OEt)2H]3); tris(trimethoxysilyl)amine (N[Si(OMe)3]3); and the like. Cyclosilazane

[0367] The silicon-containing precursor may contain a cyclic group having one or more nitrogen atoms. In one embodiment, the precursor has the formula [NR"-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; n is 1, 2 or 3; 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, amino, silyl, or siloxy, 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.

[0368] In one embodiment, the precursor has the formula [NR"-(SiR'2) n -L-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; Each n is independently 1, 2 or 3; Each L is independently 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, and combinations thereof; 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, amino, silyl, or siloxy, 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.

[0369] In another embodiment, the precursor has the formula [NR"-L-NR"-(SiR'2) n ] z , wherein: z is 1, 2, 3, 4, 5 or greater; each n is independently 1, 2 or 3; and wherein R' and R" can be any of those described herein.

[0370] In yet another embodiment, the precursor has the formula [L-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; each n is independently 1, 2 or 3; L is imino (e.g., -NR-), optionally substituted aliphatic, optionally substituted heteroaliphatic, or a combination thereof; and wherein R' can be any of those described herein. In specific embodiments, if L does not contain heteroatoms, R' contains one or more heteroatoms (e.g., nitrogen atoms).

[0371] 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.

[0372] In another 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.

[0373] In yet another embodiment, the precursor has the formula wherein R" and R"' can be any described herein, and wherein n is 1, 2, 3 or 4. In specific embodiments, each R"' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl or siloxy, any of which can be optionally substituted.

[0374] In one embodiment, the precursor has the formula wherein R′ may contain a heteroatom (eg, a nitrogen atom, such as in an optionally substituted amino, azido, isocyanato, or optionally substituted hydrazine group), and wherein n is 1, 2, 3, or 4.

[0375] In some embodiments, L comprises optionally substituted aliphatic, optionally substituted alkylene, optionally substituted alkenylene, optionally substituted alkynylene, optionally substituted heteroaliphatic, optionally substituted heteroalkylene, optionally substituted heteroalkenylene, optionally substituted heteroalkynylene, optionally substituted aromatic, optionally substituted arylene, optionally substituted heteroaromatic, optionally substituted heteroarylene, oxy (—O—), imino (e.g., —NR— or —N(SiR3)—), or silyl (e.g., —SiR2—), and combinations thereof (e.g., —SiR2-NR—, —NR-SiR2—, —SiR2-NR-SiR2—, etc.). In specific embodiments, each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted aryl, and optionally substituted heteroaromatic.

[0376] In other embodiments, L is optionally substituted alkylene and at least one R' comprises optionally substituted heteroaliphatic, optionally substituted amino, optionally substituted aliphatic-oxy, or optionally substituted alkoxy.

[0377] In some embodiments, each R' is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aromatic, or optionally substituted aryl. In other embodiments, each R' is independently optionally substituted heteroaliphatic, optionally substituted amino, or optionally substituted alkoxy.

[0378] In other embodiments, each R" is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted silyl, optionally substituted amino, optionally substituted aromatic, optionally substituted aryl, optionally substituted heteroaromatic, or optionally substituted heteroaryl.

[0379] Non-limiting precursors include 1,3,3-trimethylcyclodisilazane ([NH-SiMe2][NH-SiMeH]); hexamethylcyclotrisilazane ([NH-SiMe2]3); octamethylcyclotetrasilazane ([NH-SiMe2]4); and the like. Cyclic siloxane

[0380] The silicon-containing precursor may contain a cyclic group having one or more oxygen atoms. In one embodiment, the precursor has the formula [L-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; n is 1, 2 or 3; L is an oxygen-containing linker (eg, oxy or heteroalkylene); and 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.

[0381] In one embodiment, the precursor has the formula [O-L'-O-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; n is 1, 2 or 3; Each L' is independently a linker, such as an optionally substituted aliphatic, an optionally substituted heteroaliphatic, an optionally substituted aromatic, an optionally substituted heteroaromatic, an optionally substituted silyl (e.g., -SiR2-), an optionally substituted alkylene (e.g., -(CH2) n -, wherein n is 1 to 6) and an optionally substituted arylene group; and wherein R' is any one described herein.

[0382] In another embodiment, the precursor has the formula [O-(SiR'2) n -L-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; Each n is independently 1, 2 or 3; Each L is independently 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, and combinations thereof; and wherein R' is any one described herein.

[0383] In yet another embodiment, the precursor has the formula [L-(SiR'2) n ] z ,in: z is 1, 2, 3, 4, 5 or more; each n is independently 1, 2 or 3; L is oxy (-O-), optionally substituted aliphatic, optionally substituted heteroaliphatic, or a combination thereof; and wherein R' can be any of those described herein. In specific embodiments, if L does not contain a heteroatom, R' contains one or more heteroatoms (e.g., an oxygen atom).

[0384] In one embodiment, the precursor has the formula wherein R' can be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0385] In another 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.

[0386] In yet another embodiment, the precursor has the formula wherein R'" can be any described herein, and wherein n is 1, 2, 3, or 4. In specific embodiments, each R'" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, silyl, or siloxy, any of which can be optionally substituted.

[0387] In one embodiment, the precursor has the formula wherein R′ may include a heteroatom (e.g., an oxygen atom, as in an optionally substituted aliphatic-oxy, aliphatic-oxycarbonyl, aliphatic-carbonyl, aliphatic-carbonyloxy, optionally substituted alkoxy, optionally substituted alkoxycarbonyl, optionally substituted alkanoyl, optionally substituted alkanoyloxy, etc.), and wherein n is 1, 2, 3 or 4.

[0388] In some embodiments, each R' is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aminoalkyl, optionally substituted aromatic group or optionally substituted aryl. In other embodiments, each R' is independently optionally substituted heteroaliphatic, optionally substituted amino or optionally substituted alkoxy.

[0389] Non-limiting precursors include, for example, tetramethylcyclotetrasiloxane ([OSiHMe]4 or TMCTS); hexamethylcyclotetrasiloxane ([OSiMe2OSiHMe]2 or HMCTS); octamethylcyclotetrasiloxane ([OSiMe2]4, C8H 24 O4Si4 or OMCTS); decamethylcyclopentasiloxane ([OSiMe2]5 or C 10 H 30 O5Si5); 2-dimethylamino-2,4,4,6,6-pentamethylcyclotrisiloxane ([OSiMe2]2[OSiMe(NMe2)]); 2-dimethylamino-2,4,4,6,6,8,8-heptamethylcyclotetrasiloxane ([OSiMe2]3[OSiMe(NMe2)]); and the like. Aminosiloxane and its derivatives

[0390] The silicon-containing precursor may include a siloxane or a derivative thereof having one or more amino group substitutions, thereby providing a siloxane or a derivative thereof having one or more Si-O, O-Si-O or Si-O-Si bonds and having one or more -NR2 substitutions. In one embodiment, the precursor has the formula (R") 3-y N[SiR'2-(OSiR'2) z -R'] y ,in: y is 1, 2, or 3; z is 1, 2, 3 or greater; 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.

[0391] In another embodiment, the precursor has the formula (R") 3-y N[(SiR'2-O) z -SiR'3] y , wherein R', R", y and z can be any of those described herein.

[0392] The precursor may comprise an optionally substituted amino group having an optionally substituted silyl group. In one embodiment, the precursor has the formula R"2N-SiR'2-(OSiR'2) z -R'or R"2N-SiR'2-O-SiR'3, wherein R', R" and z can be any of those described herein. In another embodiment, the precursor has the formula R"2N(SiR'2-O) z -SiR'3, wherein R', R" and z can be any of those described herein.

[0393] The precursor may contain two optionally substituted amino groups. In one embodiment, the precursor has the formula R"2N-SiR'2-(OSiR'2) z -NR"2, wherein R', R" and z can be any as described herein.

[0394] In some embodiments, R' is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In specific embodiments, z is 1, 2, or 3.

[0395] Non-limiting precursors may include, for example, 1-dimethylamino-pentamethyldisiloxane (Me2N-SiMe2-OSiMe3); 1-diethylamino-pentamethyldisiloxane (Et2N-SiMe2-OSiMe3); 1-ethylmethylamino-pentamethyldisiloxane (EtMeN-SiMe2-OSiMe3); 1,3-bis(dimethylamino)tetramethyldisiloxane (Me2N-SiMe2-OSiMe2-NMe2); 1-dimethylamino-heptamethyltrisiloxane (Me2N-SiMe2-[OSiMe2]2-Me); 1,5-bis(dimethylamino)hexamethyltrisiloxane (Me2N-SiMe2-[OSiMe2]2-NMe2); and the like. Silanols, including alkylsilanols or alkoxysilanols

[0396] The silicon-containing precursor may contain one or more hydroxyl groups, thereby providing non-limiting silanols. In one embodiment, the precursor has the formula (R') 4-x Si(OH) x ,in: x is 1, 2, 3, or 4; and 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.

[0397] In other embodiments, the precursor has the formula (R') z Si(OH) x (OR"') y ,in: x is 1, 2, 3, or 4; y and z are each independently 0, 1, 2 or 3; x+y+z=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, silyl, or siloxy, any of which may be optionally substituted.

[0398] The precursor may have one hydroxyl group. In one embodiment, the precursor has the formula (R')3Si(OH), wherein each R' may be any of those described herein. In another embodiment, the precursor has the formula Si(OH)(OR"')3, wherein each R"' may be any of those described herein. In a specific embodiment, R"' is an optionally substituted alkyl group (e.g., Me, Et, nPr, iPr, sBu, or tBu), wherein the optionally substituted alkyl group is linear, branched, substituted, or unsubstituted.

[0399] Non-limiting precursors include, for example, tri(tert-butyloxy)silanol (SiOH[OtBu]3); tri(tert-pentyloxy)silanol (SiOH[OtPe]3); and the like. Carbonyloxysilane

[0400] The silicon-containing precursor may contain one or more optionally substituted aliphatic-carbonyloxy groups, thereby providing non-limiting carbonyloxysilanes. In one embodiment, the precursor has the formula (R') 4-x Si(OC(O)-R″″) x ,in: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazine, 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, amino, or aminooxy, any of which may be optionally substituted.

[0401] In another embodiment, the precursor has the formula (R""-C(O)O) x (R') 3-x Si-L-Si(R') 3-x (OC(O)-R″″) 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-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazine, 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, amino, or aminooxy, any of which may be optionally substituted.

[0402] 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-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.

[0403] In some embodiments, R"" is H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted amino, or optionally substituted aminooxy.

[0404] Non-limiting precursors include those having the formula (R')2Si(OC(O)-R"")2, where R' and R"" can be any of those described herein. in conclusion

[0405] Although the foregoing embodiments have been described in considerable 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 present embodiments 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 feature having a feature opening to a processing chamber; conformally depositing a first portion of a material into the feature; ceasing deposition into the feature before a seam is formed in the feature; After partially depositing the first portion of the material, exposing the substrate to an etching substance to etch an angular opening at or near the feature opening to form an etched surface; as well as A second portion of the material is deposited onto the etched surface to fill the features. 2 . The method of claim 1 , wherein at least one of the first portion and the second portion of the material is deposited using plasma enhanced atomic layer deposition.

3. The method of claim 1, wherein the second portion of the material is deposited using plasma enhanced chemical vapor deposition.

4. The method of claim 1, wherein the second portion of the material is deposited using thermal chemical vapor deposition and a post-treatment process. The method of claim 1 , wherein the processing chamber is a single wafer processing chamber.

6. The method of claim 1, wherein conformal deposition of the first portion and exposing the substrate to the etching substance are performed without breaking vacuum. The method of claim 1 , wherein the etching species is free of oxygen.

8. The method of claim 1, wherein the corner opening is etched to a depth that is less than about 10% of the depth of the feature.

9. The method of claim 4, wherein the post-treatment is performed in an oxygen-free environment and / or the post-treatment comprises exposing the substrate to plasma.

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 into the process chamber and associated flow control hardware; as well as A controller having at least one processor and a memory, wherein The at least one processor and the memory 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 a first deposition precursor and a first reactant to be introduced in temporally separated pulses to partially fill a feature on the substrate with a first portion of material; causing an etching gas to be introduced to etch the first portion of the material to form an angular opening at or near a feature opening of the feature; as well as A second deposition precursor and a second reactant are caused to be introduced and a plasma is optionally generated to form a second portion of the material to fill the feature.

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