Conformal Silicon Oxide Deposition Using Aminosilane and Chlorosilane Precursors

Abstract

SUMMARY OF THE DISCLOSURE Provided herein are methods and apparatus for forming silicon oxide using chlorosilane and aminosilane precursors.

Description

[Technical field]

[0001] CROSS REFERENCE TO RELATED APPLICATIONS: A PCT application has been filed contemporaneously herewith as a part of this application. Each application identified in the contemporaneously filed PCT application to which this application claims benefit or priority is hereby incorporated by reference in its entirety for all purposes. [Background technology]

[0002] The fabrication of semiconductor devices may involve the deposition of silicon oxide films. Such films are used in a variety of applications. For example, silicon oxide films may be used in self-aligned double patterning and / or quad patterning or other fabrication processes.

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

[0004] One aspect includes a method of treating a substrate, the method including: introducing a substrate having features; exposing the substrate to a silicon-containing precursor for a period of time sufficient to cause at least a portion of the silicon-containing precursor to adsorb on a surface of the substrate; exposing the surface of the substrate to an oxygen-containing gas without igniting a plasma to form a silicon oxide film; and annealing the silicon oxide film to form an annealed silicon oxide film, wherein the silicon-containing precursor is selected from the group consisting of a halosilane precursor and an aminosilane precursor.

[0005] In various embodiments, the silicon-containing precursor is dichlorosilane.

[0006] In various embodiments, the silicon-containing precursor is diisopropylaminosilane (DIPAS).

[0007] In various embodiments, the annealing is performed at a temperature of at least about 500°C.

[0008] In various embodiments, exposing the substrate to a silicon-containing precursor, exposing the surface to an oxygen-containing gas, and annealing are performed at a temperature of at least about 500°C.

[0009] In various embodiments, the annealing process includes exposing the silicon oxide film to hydrogen gas and oxygen gas for a period of time from about 0.1 seconds to about 900 seconds.

[0010] In various embodiments, the annealing process includes exposing the silicon oxide film to a plasma generated by igniting hydrogen gas and oxygen gas.

[0011] In various embodiments, hydrogen is introduced at a flow rate of about 0 sccm to about 5000 sccm.

[0012] In various embodiments, oxygen is introduced at a flow rate of about 0 sccm to about 20,000 sccm, In various embodiments, the plasma reduces the halogen content of the silicon oxide film.

[0013] In various embodiments, the method also includes adjusting process conditions during the plasma treatment to modify the stress of the silicon oxide film.

[0014] In various embodiments, the method also includes adjusting process conditions during the plasma treatment to reduce the wet etch rate of the silicon oxide film.

[0015] In various embodiments, the annealing process includes exposing the silicon oxide film to a plasma generated by igniting nitrogen gas.

[0016] In various embodiments, the annealed silicon oxide film has a chlorine content of less than about 0.5%.

[0017] In various embodiments, the annealed silicon oxide film has a hydrogen content of less than about 0.5%.

[0018] In various embodiments, the silicon oxide film is conformal.

[0019] In various embodiments, the method also includes cyclically exposing the substrate to a silicon-containing precursor and exposing the surface of the substrate to an oxygen-containing gas.

[0020] In various embodiments, the method also includes purging after exposing the substrate to the silicon-containing precursor and before exposing the surface of the substrate to the oxygen-containing gas.

[0021] In various embodiments, the method also includes purging the surface of the substrate after exposing it to the oxygen-containing gas.

[0022] In various embodiments, the repeating is performed for about 1 to about 100 cycles.

[0023] Another aspect includes an apparatus for processing a substrate, the apparatus including one or more process chambers, each process chamber including a chuck, one or more gas inlets to the process chambers and associated flow control hardware, and a controller having at least one processor and a memory, the at least one processor and the memory communicatively coupled to each other, the at least one processor operatively coupled to the flow control hardware, and the memory storing computer executable instructions for controlling the at least one processor to control at least the flow control hardware to introduce an aminosilane or halosilane precursor to the one or more process chambers for a period of time sufficient to adsorb at least a portion of the aminosilane or halosilane precursor to a surface of the substrate, introduce an oxygen-containing gas without igniting a plasma to form a silicon oxide film, and anneal the silicon oxide film to form an annealed silicon oxide film.

[0024] In various embodiments, the chuck is set to a temperature of at least about 500 degrees Celsius.

[0025] In various embodiments, the computer-executable instructions further include instructions for generating a plasma during the annealing process.

[0026] In various embodiments, the computer-executable instructions further include instructions for introducing hydrogen gas, oxygen gas, a mixture of hydrogen and oxygen gas, or nitrogen gas during the annealing process.

[0027] These and other aspects are further described below with reference to the drawings. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 is a process flow diagram illustrating operations for methods according to certain disclosed embodiments.

[0029] [Diagram 2]FIG. 2 is a schematic diagram of an example process chamber for carrying out certain disclosed embodiments.

[0030] [Diagram 3] FIG. 3 is a schematic diagram of an example of a process tool for implementing certain disclosed embodiments.

[0031] [Figure 4] FIG. 4 is a schematic diagram of an example of a process tool for implementing certain disclosed embodiments.

[0032] [Diagram 5] FIG. 5 is a Fourier Transform Infrared Spectrophotometer (FTIR) spectrum of a silicon oxide material deposited using certain disclosed embodiments.

[0033] [Figure 6] FIG. 6 is a graph showing the concentrations of carbon, fluorine, hydrogen, and chlorine, as well as the intensities of silicon and oxygen, for silicon oxide films deposited using certain disclosed embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] In the following description, numerous specific details are set forth in order to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail so as not to unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in connection with specific embodiments, it will be understood that they are not intended to limit the disclosed embodiments.

[0035] Semiconductor manufacturing processes often include the deposition of silicon oxide films, however, some methods of depositing silicon oxide films can encounter challenges.

[0036] Provided herein are methods and apparatus for depositing silicon oxide on a semiconductor substrate using a silicon-containing precursor in a thermal atomic layer deposition (ALD) process. The silicon-containing precursor may be an aminosilane or a halosilane. The method can be performed in the same tools used to deposit silicon nitride, making the process more efficient and resulting in higher throughput. Certain disclosed embodiments form silicon oxide films with superior properties such as uniform conformal deposition, conformal deposition on high aspect ratio structures, such as structures with aspect ratios of about 180:1 or greater, low impurity content, neutral stress, and controlled deposition.

[0037] The techniques described herein include thermal atomic layer deposition (ALD). That is, in various embodiments, the reaction between an aminosilane or halosilane and an oxygen-containing reactant to form silicon oxide is carried out without igniting a plasma. ALD is a technique that uses continuous, self-limiting reactions to deposit thin layers of materials. Typically, an ALD cycle includes the operations of delivering and adsorbing at least one reactant to a substrate surface, and then reacting the adsorbed reactant with one or more reactants to form a sublayer of a film. As another example, a silicon oxide deposition cycle may include the following operations: (i) delivery / adsorption of a silane precursor, (ii) purging the silane precursor from the chamber, (iii) delivery of an oxygen-containing gas, and (iv) purging the oxygen-containing gas from the chamber.

[0038] Unlike chemical vapor deposition (CVD) techniques, ALD processes use surface-mediated deposition reactions to deposit films layer by layer. In one example of an ALD process, a substrate surface containing a collection of surface active sites is exposed to a gas-phase distribution of a first precursor, such as a silicon-containing precursor, in a single dose provided to a chamber housing the substrate. Molecules of this first precursor are adsorbed on the substrate surface and include chemisorbed and / or physisorbed species of the first precursor. It should be understood that when a compound is adsorbed on a substrate surface as described herein, the adsorbed layer may include derivatives of the compound as well as the compound. For example, an adsorbed layer of a halosilane precursor may include derivatives of the halosilane precursor as well as the halosilane precursor. After the dose of the first precursor, the chamber is then evacuated to remove most or all of the halosilane precursor remaining in the gas phase, leaving primarily the adsorbed species or only the adsorbed species. In some embodiments, the chamber may not be completely evacuated. For example, the chamber may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to mitigate reaction. A second reactant, such as an oxygen-containing reactant, is introduced into the chamber, causing some of these molecules to react with the surface-adsorbed halosilane precursor. In some processes, the second reactant reacts immediately with the adsorbed halosilane precursor. The chamber may then be evacuated again to remove unbound second reactant molecules. As noted above, in some embodiments, the chamber may not be fully evacuated. Additional ALD cycles may be used to increase film thickness.

[0039] In certain embodiments, the input of the ALD first precursor partially saturates the substrate surface. In some embodiments, the input phase of the ALD cycle is completed before the precursor contacts the substrate and uniformly saturates the surface. Typically, the precursor flow is stopped or redirected at this point, and only the purge gas flows. By operating in this subsaturated state, the ALD process shortens cycle time and increases throughput. However, because precursor adsorption is not saturation limited, the concentration of adsorbed precursor may vary slightly at the substrate surface. An example of an ALD process operating in a subsaturated state is provided in U.S. Patent Application No. 14 / 061,587 (now U.S. Patent No. 9,355,839), filed October 23, 2013, entitled "SUB-SATURATED ATOMIC LAYER DEPOSITION AND CONFORMAL FILM DEPOSITION," which is incorporated herein by reference in its entirety.

[0040] In some embodiments, the ALD method may include plasma activation. However, in the thermal ALD processes described herein, a plasma is not ignited. As described herein, the ALD methods and apparatus described herein may be conformal film deposition (CFD) methods, as generally described in U.S. Patent Application No. 13 / 084,399, filed April 11, 2011 (now U.S. Patent No. 8,728,956), entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," and U.S. Patent Application No. 13 / 084,305, filed April 11, 2011, entitled "SILICON NITRIDE FILMS AND METHODS," both of which are incorporated herein by reference in their entireties.

[0041] 1 is a process flow diagram depicting operations that may be performed according to certain disclosed embodiments. In operation 102, a substrate is provided to a process chamber. In various embodiments, the process chamber is a single wafer chamber. In some embodiments, the process chamber is a station within a multi-station chamber. The process conditions described herein are suitable for a single wafer chamber.

[0042] The process chamber may be set to a chamber pressure of about 10 mTorr to about 25 Torr, or about 10 Torr to about 25 Torr. Such chamber pressures may be used throughout operations 102-116 described herein. In some embodiments, the chamber pressure may vary between different operations.

[0043] The substrate may be heated to a substrate temperature of about 25° C. to about 800° C., or about 500° C. to about 700° C., or at least about 650° C. during operations 104-112. Substrate temperature as used herein refers to a temperature set on a pedestal that holds the substrate, and it will be understood that in some embodiments, a substrate on a pedestal provided to a process chamber may be heated to a desired substrate temperature prior to processing of the substrate. The substrate temperature may be the same throughout operations 102-114 described herein.

[0044] The substrate may be any suitable substrate. The substrate may be a silicon wafer, e.g., a 200 mm wafer, a 300 mm wafer, a wafer having one or more layers of material, such as a dielectric, conductive, or semiconductive material, deposited thereon, etc. Non-limiting examples of underlayers include dielectric layers and conductive layers, e.g., silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers. In some embodiments, the substrate comprises silicon oxide and silicon. In some embodiments, the substrate comprises a partially fabricated 3D-NAND structure.

[0045] In some embodiments, the feature(s) may have an aspect ratio of at least about 1:1, at least about 2:1, at least about 4:1, at least about 6:1, at least about 10:1, or more. The feature(s) may also have a dimension near the opening, e.g., an opening diameter or line width between about 10 nm and 500 nm, e.g., between about 25 nm and about 300 nm. The disclosed methods may be performed on a substrate having feature(s) with an opening of less than about 150 nm. Vias, trenches, or other recessed features may be referred to as unfilled features or features. According to various embodiments, the feature profile may narrow gradually and / or include an overhang at the feature opening. A re-entrant profile is a profile that narrows from the bottom, closed end, or interior of the feature toward the feature opening. A re-entrant profile may be generated by an overhang due to asymmetric etching kinetics during patterning and / or non-conformal film step coverage in a preceding film deposition, such as deposition of a diffusion barrier. In various examples, a feature may have an opening with a smaller width at the top of the feature than at the bottom of the feature.

[0046] One or more features may have a high aspect ratio, which is defined as having an aspect ratio greater than about 100:1, or greater than about 150:1, or greater than about 180:1.

[0047] In some embodiments, the substrate may be partially fabricated to form a memory device, hi some embodiments, the exposed regions of the substrate comprise silicon-containing surfaces, including but not limited to silicon and silicon oxynitride.

[0048] A silicon-containing precursor is introduced into the process chamber in operation 104. In certain embodiments, the silicon-containing precursor comprises an aminosilane precursor.

[0049] 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 tetraaminosilanes (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), as well as substituted mono-, di-, tri-, and tetraaminosilanes, such as t-butylaminosilane, methylaminosilane, tert-butylsilane amine, bis(tertiary butylamino)silane ( Examples include SiH2(NHC(CH3)3)2 (BTBAS), tert-butylsilyl carbamate, SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamido)silane (DIPAS), bis(diethylamino)silane (BDEAS), etc. A further example of an aminosilane is trisilylamine (N(SiH3)3).

[0050] The silicon-containing precursor can include one or more optionally substituted amino groups to provide non-limiting aminosilanes. In one embodiment, the precursor has the formula (R'): 4-x Si(NR”2) x wherein 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, hydroxyl, silyl, silyloxy, 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 two R" together with the nitrogen atom to which they are attached may form an optionally substituted heterocyclyl.

[0051] In another embodiment, the precursor has the formula (R″2N) x (R') 3-x Si-L-Si(R') 3-x (NR”2) x wherein each x is independently 0, 1, 2, or 3; L is a linker such as a covalent bond, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, oxy (—O—), imino, or silyl; 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, hydroxyl, silyl, silyloxy, 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 two R" together with the nitrogen atom to which they are attached may form an optionally substituted heterocyclyl.

[0052] In certain embodiments, L is an optionally substituted imino, such as -NR-, where R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In other embodiments, L is an optionally substituted silyl, such as -SiR-, where each R is independently H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic.

[0053] In one example, at least one x is not 0. In another embodiment, x can be 0 (e.g., when 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.

[0054] In certain embodiments, at least one R' or R" is not H. The precursors can have any useful combination of R' groups and amino groups (NR"2) bonded to one or more silicon atoms.

[0055] In some embodiments, R' is H, optionally substituted amino (e.g., -NR), aliphatic-oxy ​​(e.g., alkoxy, i.e., -OR), aliphatic-carbonyl, (e.g., alkanoyl, i.e., -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy, i.e., -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl, i.e., -C(O)OR), silyl (e.g., -SiR), aliphatic-oxy-silyl (e.g., alkoxysilyl, i.e., Si(R)). a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic-oxy-silyloxy (e.g., alkoxysilyloxy, i.e., -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b ), aromatic (e.g., aryl), aromatic-oxy ​​(e.g., aryloxy, i.e., -OR), hydroxyl (-OH), formyl (-C(O)H), and the like. In certain 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, where a > 0, b > 1, and a + b = 3. In some embodiments, two R groups, together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl. In other embodiments, each R is independently H, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aryl.

[0056] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted silyloxy. In some embodiments, R" is an optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR', -SiR, -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) cwherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazino, azido, hydroxyl, silyl, silyloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted, and each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is > 0, and a + b + c = 3, or a + b = 3 (if c is absent). In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl.

[0057] The precursor may include at least one R' group bonded 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 x is 1, 2, or 3. In another embodiment, the precursor has the formula (R')(H)Si(NR"2), where R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')(H)Si(NR"2), where R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R')(H)Si(NR"2), where R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R')Si(NR"2), where R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')Si(NR"2), where R' and R" can be any of those described herein.

[0058] The precursor may also lack an R' group bonded to the silicon atom. In one embodiment, the precursor has the formula (H): 4-x Si(NR”2) xwhere each R" can be independently any described herein and 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 anything described herein. In certain embodiments, each R″ is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0059] The precursor may include one or more hydrogen atoms bonded 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, where each R" may independently be any of those described herein. In certain embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted.

[0060] The precursor may include a heterocyclyl group having a nitrogen atom. In one embodiment, the above formula has the formula H3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom. In certain embodiments, the precursor has the formula 1, where the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as a substituent on an alkyl), and n is 1, 2, 3, 4, or 5. In one embodiment, the above formula has the formula R'3Si-Het, where Het is an optionally substituted heterocyclyl containing at least one nitrogen atom, and each R' can be independently any of those described herein. In certain embodiments, the precursor has the formula 2, where the heterocyclyl group can be optionally substituted (e.g., with any of the substituents described herein as a substituent on an alkyl), and each R' can be independently any of those described herein, and n is 1, 2, 3, 4, or 5. [ka] [ka]

[0061] In some examples, the precursor may have two or more silicon atoms, where the precursor may include a Si-Si bond. In certain embodiments, the precursor has the formula (R"2N): x (R') 3-x Si-Si(R') 3-x (NR”2) x where 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), where 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), where 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), where each R" can independently be any of those described herein.

[0062] The precursor may contain different groups bonded to the silicon atom. In one example, the precursor has the formula (R″2N): x (R') 3-x Si-SiH3, where R' and R" can be any of those described herein.

[0063] A linker may be present between the two silicon atoms. In one example, the precursor has the formula (R″2N): x (R') 3-x Si-NR-Si(R') 3-x (NR”2) x where R′ and R″ can be any of those described herein, and R is H, optionally substituted aliphatic, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, or optionally substituted aromatic. In another example, the precursor has the formula (R″N): x (H) 3-x Si-NR-Si(H) 3-x (NR”2) x where R, R', and R" can be any of those described herein.

[0064] The precursor may include a combination of R' groups and linkers with heteroatoms. In one example, the precursor has the formula (R')3Si-NR-Si(R')3, where R and R' can be any of those described herein. In another example, the precursor has the formula (R')3Si-L-Si(R')3, where L and R' can be any of those described herein. In certain embodiments, L is oxy (-O-), optionally substituted imino (e.g., -NR-), or optionally substituted silyl (e.g., -SiR2-).

[0065] The precursor may include any useful combination of R′ and NR″ groups in combination with two silicon atoms. In one example, the precursor has the formula (R″N)(R′)Si-L-Si(R′)(NR″) x where L, R', and R" can be any of those described herein.

[0066] The precursor may include a heterocyclic group including a silicon atom and a nitrogen atom. In one embodiment, the precursor has formula 3, where R′ and R″ may be any of those described herein, and n is 1, 2, 3, or 4. [ka]

[0067] In another embodiment, the precursor has formula 4, where R′ and R″ can be any of those described herein, and n is 1, 2, 3, or 4. In yet another embodiment, the precursor has formula 5, where each R″ can be independently any of those described herein, and n is 1, 2, 3, or 4. In another embodiment, the precursor has formula 6, where R′ and R″ can be any of those described herein, and n is 1, 2, 3, or 4. In yet another embodiment, the precursor has formula 7, where R″ can be independently any of those described herein, and n is 1, 2, 3, or 4. [ka] [ka] [ka] [ka]

[0068] In any precursor herein, two R″, together with the nitrogen atom to which they are each attached, can form an optionally substituted heterocyclyl.

[0069] The precursor may include any of the following, for example, (R Ak )Si(NH2)(NR Ak 2)2, (R Ak )Si(NR Ak 2)3, (R Ak )2Si(NHR Ak 2)2, (R Ak )(H)Si(NHR Ak )2, (R Ak )3Si(NR Ak 2), (R Ak )3Si(NHR Ak ), H2Si(NHR Ak 2)2, (R Ak )(H)Si(NR Ak 2)2, HSi(NH2)(NR Ak 2)2, HSi(NR Ak 2)3, Si(NR Ak 2)4, (R')(H)Si(NR”2)2, (R')2Si(NR Ak 2)2, (R')2Si(N[SiH3]2)2, (R')2Si(N[SiR”3]2)2, or (R')3Si(NHR AkIn some embodiments, each of R' and R" can 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 is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. In certain embodiments, R Ak are methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), sec-butyl (sBu), iso-butyl (iBu), tert-butyl (tBu), etc.

[0070] 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 (SiH2Et [NEt2]), Ethylaminotrimethylsilane (SiMe3[NHEt]), Diethylaminodimethylsilane (SiHMe2[NEt2]), Diethylaminodiethylsilane (SiHEt2[NEt2]), Diethylaminotrimethylsilane (SiMe3[NEt2]), Diethylaminotriethylsilane (SiEt3[NEt2]), Iso-propylaminodimethylsilane (SiHMe2[NHiPr]), Iso-propylaminotrimethylsilane (SiMe3[NHiPr]), Iso-propylaminodiethylsilane (SiHEt2[NHiPr]), Iso-propylaminotriethylsilane (SiEt3[NHiPr]), Di-isopropylaminotrimethylsilane (SiMe3[NiPr2]), Di-iso-propylaminosilane (SiH3[NiPr2], C6H 17NSi, or DIPAS), di-isopropylaminomethylsilane (SiH2Me[NiPr2]), di-isopropylaminodimethylsilane (SiHMe2[NiPr2]), di-isopropylaminodiethylsilane (SiHEt2[NiPr2]), di-isopropylaminotriethylsilane (SiEt3[NiPr2]), n-propylaminotrimethylsilane (SiMe3[NHnPr]), di-sec-butylaminosilane (SiH3[NsBu2] or DSBAS), di-sec-butylaminomethylsilane (SiH2Me[NsBu2] ), iso-butylaminotrimethylsilane (SiMe3[NHiBu]), n-butylaminotrimethylsilane (SiMe3[NHnBu]), tert-butylaminodimethylsilane (SiHMe2[NHtBu]), tert-butylaminotrimethylsilane (SiMe3[NHtBu]), tert-butylaminodiethylsilane (SiHEt2[NHtBu]), tert-butylaminotriethylsilane (SiEt3[NHtBu]), dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl), N-propylisopropylaminosilane (SiHMe2[NHtBu]), n ...HMe2[NHtBu]), n-butylaminotrimethylsilane (SiMe3[NHtBu]), n-butylaminodiethylsilane (SiHMe2[NHtBu]), n-butylaminodiethylsilane (SiHMe2[NHtBu]), n-butylaminodiethylsilane (SiHMe2[NHtBu]), n-butylaminodiethylsilane (SiHMe2[NHtBu]), n-butylaminodiethylsilane (SiEt3[NHtBu]), Propylaminosilane (SiH3[NiPrnPr]), N-methylcyclohexylaminosilane (SiH3[NMeCy]), N-ethylcyclohexylaminosilane (SiH3[NEtCy]), allylphenylaminosilane (SiH3[NAllPh]), N-isopropylcyclohexylaminosilane (SiH3[NiPrCy]), allylcyclopentylaminosilane (SiH3[NAllCp]), phenylcyclohexylaminosilane (SiH3[NPhCy]), cyclohexylaminotrimethylsilane (SiMe3[NHCy], where where Cy is cyclohexyl), pyrrolyltrimethylsilane (SiMe3[NHPy], where Py is pyrrolyl), pyrrolidinotrimethylsilane (SiMe3[NHPyr], where Pyr is pyrrolinyl), piperidinotrimethylsilane (SiMe3[NHPip], where Pip is piperidinyl), piperazinotrimethylsilane (SiMe3[NHPz], where Pz is piperazinyl), imidazolyltrimethylsilane (SiMe3[NHIm], where Im is imidazolyl), 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, CH, 22N2Si, or BDEAS), bis(diethylamino)dimethylsilane (SiMe2[NEt2]2), bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2), bis(diethylamino)diethylsilane (SiEt2[NEt2]2), bis(iso-propylamino)dimethylsilane (SiMe2[NHiPr]2), bis(iso-propylamino)diethylsilane (SiEt2[NHiPr]2), bis(iso-propylamino)methylvinylsilane (SiMeVi[NHiPr]2), bis(di- isopropylamino)silane (SiH2[NiPr2]2), bis(di-isopropylamino)dimethylsilane (SiMe2[NiPr2]2), bis(di-isopropylamino)diethylsilane (SiEt2[NiPr2]2), bis(di-isopropylamino)methylvinylsilane (SiMeVi[NiPr2]2), bis(methylamino)silane (SiH2[NHMe]2), bis(sec-butylamino)silane (SiH2[NHsBu]2), bis(sec-butylamino)methylsilane (SiHMe[N 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 Im 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, CH 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 ([Me2N]2MeSi-SiMe[NMe2]2), 1,2-dimethyl-tetrakis(diethylamino)disilane ([Et2N]2MeSi-SiMe[NEt2]2), hexakis(methylamino)disilane ([MeHN]3Si-Si[NHMe]3), hexakis(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3), hexakis(dimethylamino)disilazane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), etc.

[0071] In some embodiments, the silane precursor is a halosilane precursor. A halosilane precursor is defined as a precursor having at least one halogen-containing atom and at least one silicon atom. Halogen includes chlorine, fluorine, bromine, and iodine. In some embodiments, the halosilane precursor comprises the structure of formula (I): Si(X)4, where at least one X comprises a halogen atom.

[0072] For example, one halosilane is tetrachlorosilane (SiCl4). Another example of the chemical formula for a halosilane is Si n X y H z where X is a halogen, H is hydrogen, n is an integer equal to or greater than 1 and equal to the number of Si atoms in the molecule, and in some embodiments, y is from about 1 to about 4, and z is 4-y. Additional examples include, but are not limited to, SiHCl3, SiH2Cl2, and SiH3Cl.

[0073] Examples of halosilanes are iodosilane, bromosilane, chlorosilane, and fluorosilane. Specific chlorosilanes include, but are not limited to, tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like.

[0074] In some embodiments, the halosilane does not contain carbon, hi some embodiments, the halosilane is an organosilicon-containing precursor.

[0075] In some embodiments, the halosilane precursor (e.g., of formula (I)) comprises at least one optionally substituted C 1-2 Non-limiting examples of haloaliphatic groups include -CX y H 3-y wherein y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), -CX z H 2-z CX y H 3-y wherein z is 0, 1, or 2, y is 0, 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I), and at least one of z or y is not 0; or -CHCX y H 3-ywhere y is 1, 2, or 3, and each X is independently halo (F, Cl, Br, or I). Still other non-limiting haloalkyl groups include fluoromethyl (-CH2F), difluoromethyl (-CHF2), trifluoromethyl (-CF3), chloromethyl (-CH2Cl), dichloromethyl (-CHCl2), trichloromethyl (-CCl3), bromomethyl (-CH2Br), dibromomethyl (-CHBr2), tribromomethyl (-CBr3), iodomethyl (-CH2I), diiodomethyl (-CHI2), triiodomethyl (-CI3), bromofluoromethyl (-CHFBr), chloro ... methyl (-CHFCl), fluoroiodomethyl (-CHFI), 2-fluoroethyl (-CHCHF), 2-chloroethyl (-CHCHCl), 2-bromoethyl (-CHCHBr), 2-iodoethyl (-CHCHI), 2,2-difluoroethyl (-CHCHF), 2,2-dichloroethyl (-CHCHCl), 2,2-dibromoethyl (-CHCHBr), 2,2-diiodoethyl (-CHCHI), 2,2-fluoroiodoethyl (-CHCHFI), and the like. In certain embodiments, C 1-2 Haloalkyl includes β-halo substituted ethyl. Further haloaliphatic groups include C 1-4 Haloalkyl, C 2-4 Haloalkenyl, and C 2-4 Haloalkynyl is mentioned.

[0076] The flow rate of the halosilane precursor in act 104 may range from about 100 sccm to about 2000 sccm. The exposure in act 104 may range from about 0.1 seconds to about 100 seconds.

[0077] During operation 104, the chamber pressure may be from about 1 Torr to about 25 Torr.

[0078] In some embodiments, a carrier gas may be flowed during operation 104. The carrier gas may be an inert gas, such as argon, hydrogen, helium, neon, nitrogen, and combinations thereof. The carrier gas may be diverted to be used to deliver ammonia and / or nitrogen gas to the process chamber. In some embodiments, the carrier gas may be provided to help control the pressure and / or temperature of the process chamber. In some embodiments, the carrier gas is used to ensure more rapid delivery of gas to the process chamber. In various embodiments, operation 104 is performed once prior to depositing the silicon-containing or metal-containing dielectric material on the substrate.

[0079] In some embodiments, a diluent gas is used and is co-flowed with the halosilane precursor. The diluent gas may be nitrogen gas in some embodiments. The flow rate of the diluent gas may be from about 500 sccm to about 20,000 sccm. The flow rate ratio of the diluent gas to the halosilane precursor may be from about 0.1:1 to about 10:1.

[0080] Operations 104, 106, 108, and 110 may constitute an atomic layer deposition cycle.

[0081] In operation 106, the chamber is optionally purged. Purging the chamber may include flowing a purge gas or sweep gas, which may be the carrier gas used in other operations or may be a different gas. In some embodiments, purging may include evacuating the chamber. Examples of purge gases include argon (Ar), nitrogen (N2), hydrogen (H2), helium (He), oxygen (O2), krypton (Kr), xenon (Xe), neon (Ne), and combinations thereof. In various embodiments, the purge gas is an inert gas. The purge gas may include one or more gases. In some embodiments, operation 106 may include one or more evacuation sub-stages to evacuate the process chamber. It will be understood that operation 106 may alternatively be omitted in some embodiments. In some embodiments, increasing the flow rate of one or more purge gases may reduce the duration of operation 106. For example, the flow rate of the purge gas may be adjusted depending on the thermodynamic and / or geometric properties of the various reactants in the process chamber and / or the process chamber plumbing to change the duration of operation 106. In one non-limiting example, the duration of the purge phase may be adjusted by adjusting the purge gas flow rate, which may reduce the deposition cycle time and increase substrate throughput. After purging, the halosilane molecules remain adsorbed on the substrate surface.

[0082] The flow rate of the purge gas may be from about 1000 sccm to about 40000 sccm. The duration of operation 106 may be from about 0.1 seconds to about 10 seconds. The chamber pressure during operation 106 may be from about 0.5 Torr to about 22 Torr.

[0083] In operation 108, an oxygen-containing switching gas is introduced into the process chamber without a plasma to form silicon oxide on the surface of the substrate. The oxygen-containing switching gas reacts with the halosilane to form silicon oxide. The oxygen-containing switching gas may be any one or more of oxygen (O2), nitrous oxide (NO), and ozone (O3). In various embodiments, the oxygen-containing switching gas is flowed using a flow rate of about 100 sccm to about 20,000 sccm. The oxygen-containing switching gas may optionally be flowed in parallel with an inert gas, such as hydrogen gas. The flow rate of the hydrogen gas may be 0 sccm to about 5,000 sccm. In some embodiments, the oxygen-containing gas is optionally diluted with a diluent gas, such as nitrogen gas. The flow rate of the nitrogen gas may be about 500 sccm to about 20,000 sccm.

[0084] Operation 108 may be performed for a period of about 1 second to about 30 seconds. The chamber pressure during operation 108 may be about 5 Torr to about 25 Torr. In various embodiments, a plasma is not ignited during operation 108. In various embodiments, a plasma is not used in any of operations 104, 106, 108, and 110.

[0085] In operation 110, the chamber is optionally purged. Purging may be performed using any of the chemicals, methods, and process conditions described above in connection with operation 106. In some embodiments, the chamber is purged using nitrogen as a purge gas. The nitrogen may be flowed at a flow rate of about 1000 sccm to about 40000 sccm. Operation 110 may be performed for a period of about 0.1 seconds to about 10 seconds. The chamber pressure may be about 0.5 Torr to about 25 Torr.

[0086] In operation 112, the substrate is optionally annealed. The annealing may be performed in situ. During the annealing, hydrogen gas, oxygen gas, or both may be flowed. The flow rate of hydrogen is about 0 sccm to about 5000 sccm. The flow rate of oxygen is about 0 sccm to about 20000 sccm.

[0087] In some embodiments, operation 112 includes extending operation 108 to perform for a longer period of time, such as performing operation 108 for a combined period of about 0.1 seconds to about 900 seconds. In some embodiments, operations 108 and 112 are performed at the same temperature.

[0088] In some embodiments, operation 112 includes separate thermal anneals using an oxygen-containing gas and a hydrogen gas. In some embodiments, operation 112 includes separate plasma-based anneals using an oxygen-containing gas and a hydrogen gas. The plasma may be generated using a single-wafer plasma power of about 100 W to about 10,000 W.

[0089] In some embodiments, the annealing in operation 112 is performed in an external chamber using nitrogen at a temperature of at least about 700° C. or at least about 800° C. In some embodiments, the annealing in an external chamber is performed in addition to performing an in situ anneal to further fine-tune the film properties.

[0090] In some embodiments, an optional purge operation 114 may occur after operation 112. Operation 114 may utilize chemistries, process conditions, and methods such as those described above in connection with operations 106 and 110.

[0091] In various embodiments, operations 104-110 are repeated periodically. It may be determined whether a silicon nitride film of the desired thickness has been deposited. If not, operations 104-110 are repeated a sufficient number of cycles to deposit a silicon oxide film of the desired thickness. Any suitable number of deposition cycles may be included in the ALD process to deposit a silicon oxide film of the desired thickness. For example, about 20 to about 40 deposition cycles may be performed to deposit a silicon nitride film on a substrate using the disclosed embodiments. In some embodiments, 20 to 40 depositions are performed.

[0092] In each cycle, the amount of thickness of the silicon oxide film formed may be from about 0.5 Å to about 2 Å. In various embodiments, operations 104-112 are performed cyclically. In some embodiments, operation 112 and optional operation 114 are performed after a number of cycles of operations 104-110. In various embodiments, operations 104-114 are performed cyclically.

[0093] The deposited silicon oxide films thus deposited using certain disclosed embodiments have very low hydrogen content, very low chlorine content, or both. For example, the atomic hydrogen content of silicon oxide deposited using certain disclosed embodiments may be less than about 0.5%, or less than about 0.3%. The atomic chlorine content of silicon oxide deposited using certain disclosed embodiments may be less than about 0.5%, or less than about 0.05%. The FTIR of silicon oxide films deposited using certain disclosed embodiments may not have visible -OH peaks. The hydrogen and chlorine content can be further reduced by annealing, or by annealing at higher temperatures, higher plasma power, or for longer periods of time. The silicon oxide films may exhibit a high concentration of Si-O bonds and a low concentration of carbon. The wet etch rate of silicon oxide films deposited using certain disclosed embodiments in 100:1 HF may be about 2:1 or less compared to thermal oxides grown at temperatures greater than about 1000°C.

[0094] The silicon oxide film may also be adjusted to have a desired stress. The stress may be adjusted to make it a tensile or compressive film. The stress may be from about +50 MPa to about -350 MPa.

[0095] In various embodiments, using certain disclosed embodiments, silicon oxide film has neutral stress. Process conditions that can be adjusted to change stress include, but are not limited to, annealing process conditions, whether annealing is performed, and temperature during deposition. Films deposited using certain disclosed embodiments may also exhibit high conformality, such as having a step coverage of at least about 80%, or at least about 90%, or at least about 95%, or at least about 99%.

[0096] Certain disclosed embodiments may be used to deposit high quality silicon oxide materials, such as silicon oxide liners used as tunnel oxides in 3D-NAND memory storage. Certain disclosed embodiments are useful for forming tunnel oxide layers in 3D-NAND memory fabrication instead of or in addition to silicon nitride deposition and subsequent silicon nitride to silicon oxide conversion, which may include multiple fabrication operations and involve multiple tools, and certain disclosed embodiments may be used to improve efficiency and increase throughput. Certain disclosed embodiments address the problem of silicon nitride to silicon oxide conversion, which may cause induced stress due to volumetric expansion of the film in features of a semiconductor substrate. Some current processes may be performed in furnaces and may also utilize very high temperatures, long cycle times, and limited tunability. In contrast, certain disclosed embodiments allow a wide tunability window to obtain different film properties.

[0097] Device FIG. 2 depicts a schematic diagram of one embodiment of an atomic layer deposition (ALD) process station 200 having a process chamber body 202 for maintaining a low pressure environment. In various embodiments, a single process station 200 is implemented in a tool such as that shown in FIG. 3. In some embodiments, multiple ALD process stations 200 may be included in a common low pressure process tool environment. For example, FIG. 4 depicts one embodiment of a multi-station processing tool 400. In some embodiments, one or more hardware parameters of the ALD process station 200, including those discussed in detail below, may be programmatically adjusted by one or more computer controllers 250.

[0098] The ALD process station 200 is in fluid communication with a reactant delivery system 201a for delivering process gases to a showerhead 206. The reactant delivery system 201a includes a mixing vessel 209 for combining and / or conditioning process gases, such as a silicon-containing precursor gas or an oxygen-containing gas, for delivery to the showerhead 206. One or more mixing vessel inlet valves 220 may control the introduction of process gases to the mixing vessel 204. One or more valves 205 may control the introduction of gases to the showerhead 206.

[0099] For example, the embodiment of FIG. 2 includes a vaporization point 203 for vaporizing a liquid reactant to be delivered to the mixing vessel 204. In some embodiments, the vaporization point 203 may be a heated vaporizer. Saturated reactant vapor generated from such a vaporizer may condense in downstream delivery piping. Exposure of incompatible gases to the condensed reactant may also generate small particles. These small particles may clog piping, interfere with valve operation, contaminate the substrate, etc. Some approaches to address these issues include purging and / or evacuating the delivery piping to remove residual reactants. However, purging the delivery piping may increase the cycle time of the process station and degrade the throughput of the process station. Thus, in some embodiments, the delivery piping downstream of the vaporization point 203 may be heat traced. In some examples, the mixing vessel (not shown) may also be heat traced. In one non-limiting example, the piping downstream of the vaporization point 203 has an increasing temperature profile extending from about 40° C. to about 55° C., or from about 60° C. to about 65° C. in the mixing vessel.

[0100] In some embodiments, the liquid precursor or liquid reactant may be vaporized in a liquid injector. For example, the liquid injector may inject a pulse of liquid reactant into the carrier gas stream upstream of the mixing vessel. In one embodiment, the liquid injector may vaporize the reactant by rapidly depressurizing the liquid from a higher pressure to a lower pressure. In another example, the liquid injector may atomize the liquid into dispersed microdroplets that are then vaporized in a heated delivery tubing. Smaller droplets may vaporize faster than larger droplets, reducing the delay between injection of the liquid and complete vaporization. Faster vaporization may reduce the length of tubing downstream from the vaporization point 203. In one scenario, the liquid injector may be attached directly to the mixing vessel. In another scenario, the liquid injector may be attached directly to the showerhead 206.

[0101] In some embodiments, a liquid flow controller (LFC) may be provided upstream of the vaporization point 203 to control the mass flow rate of liquid for vaporization and delivery to the ALD process station 200. 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-derivative (PID) controller in electrical communication with the MFM. However, it may take more than a second to stabilize the liquid flow using feedback control. This may extend the time to dose the liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, this may be done by disabling the sense tubes of the LFC and the PID controller.

[0102] The showerhead 206 distributes process gases toward the substrate 212. In the embodiment illustrated in Figure 2, the substrate 212 is located below the showerhead 206 and is shown resting on a pedestal 208. The showerhead 206 may have any suitable shape and any suitable number and arrangement of ports for distributing process gases to the substrate 212.

[0103] In some embodiments, the pedestal 208 may be raised or lowered to expose the substrate 212 to the volume between the substrate 212 and the showerhead 206. It will be appreciated that in some embodiments, the height of the pedestal may be programmatically adjusted by a suitable computer controller 250.

[0104] In another scenario, the height of the pedestal 208 may be adjusted to allow the plasma density to be varied during plasma activation in processes in which a plasma is ignited. At the end of a process step, the pedestal 208 may be lowered during a separate substrate transfer step to allow removal of the substrate 212 from the pedestal 208.

[0105] In some embodiments, the pedestal 208 may be temperature controlled via a heater 210. In some embodiments, the pedestal 208 may be heated to a temperature of about 25° C. to about 800° C., or about 200° C. to about 700° C. during deposition of the silicon oxide film as described in the disclosed embodiments. In some embodiments, the pedestal is set to a temperature of about 25° C. to about 800° C., or about 200° C. to about 300° C. In some embodiments, the same pedestal 208 is used for a subsequent annealing process.

[0106] Additionally, in some embodiments, pressure control of the ALD process station 200 may be provided by a butterfly valve 218. As shown in the embodiment of FIG. 2, the butterfly valve 218 throttles a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the ALD process station 200 may also be adjusted by varying the flow rates of one or more gases introduced to the ALD process station 200.

[0107] In some embodiments, the position of the showerhead 206 may be adjusted relative to the pedestal 208 to change the volume between the substrate 212 and the showerhead 206. Further, it will be appreciated that the vertical position of the pedestal 208 and / or the showerhead 206 may be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 208 may include a rotation axis for rotating the orientation of the substrate 212. It will be appreciated that in some embodiments, one or more of these exemplary adjustments may be performed programmatically by one or more suitable computer controllers 250.

[0108] In some embodiments that may use plasma as described above, the showerhead 206 and pedestal 208 are in electrical communication with a radio frequency (RF) power source 214 and matching network 216 to power the plasma. For example, the plasma may be used to treat a silicon oxide surface prior to silicon nitride deposition. In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and plasma power pulse timing. For example, the RF power source 214 and matching network 216 may be operated at any suitable power to form a plasma having a desired composition of radical species. An example of a suitable power is about 150 W to about 10,000 W for a single station chamber. For a four station chamber, the plasma power may include four generators, each provided with up to about 10,000 W of power, totaling about 40,000 W. For annealing of 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 a plasma is ignited using an RF power source 214 and a matching network 216.

[0109] In some embodiments, the substrate may be exposed to a nitrogen-containing gas while igniting a plasma to anneal the silicon oxide using a plasma power such as between about 500 W and about 10,000 W per surface area of ​​a 300 mm wafer. The plasma may be generated remotely (such as with a remote plasma generator) or directly in the chamber housing the substrate (in situ). The RF power source 214 may provide RF power at any suitable frequency. In some embodiments, the RF power source 214 may be configured to control high and low frequency RF power independently of each other. Examples of low frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Examples of high frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or greater than about 13.56 MHz, or greater than 27 MHz, or greater than 30 MHz, or greater than 60 MHz. It will be appreciated that any suitable parameter may be adjusted discretely or continuously to provide plasma energy for surface reactions.

[0110] In some embodiments, the plasma may be monitored in situ by one or more plasma monitors. In one scenario, the plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, the plasma density and / or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in situ plasma monitors. For example, an OES sensor may be used in a feedback loop to provide programmatic control of the plasma power. It will be appreciated that in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0111] In some embodiments, instructions to the controller 250 may be controlled via input / output control (IOC) sequencing instructions. In one example, instructions for setting the conditions of a process step may be included in a corresponding recipe step of a process recipe. In some cases, the process recipe steps may be sequentially arranged such that all instructions for a process step are executed simultaneously with that process step. In some embodiments, instructions for setting one or more reactor parameters may be included in a recipe step. For example, a first recipe step may include instructions for setting a flow rate of a halosilane gas, instructions for setting a flow rate of a carrier gas (such as argon), and a time delay instruction for the first recipe step. A second recipe step may include instructions for adjusting or stopping a flow rate of an inert gas and / or a reactive gas, instructions for setting a flow rate of a carrier gas (such as argon), and a time delay instruction for the second recipe step. A subsequent third recipe step may include instructions for adjusting or stopping a flow rate of an inert gas and / or a reactive gas, instructions for adjusting a flow rate of an oxygen-containing gas, and a time delay instruction for the third recipe step. The fourth recipe step may include instructions to adjust or stop the flow rate of the inert gas and / or reactive gas, instructions to adjust the flow rate of the carrier gas or purge gas, and a time delay instruction for the fourth recipe step. The subsequent fifth recipe step may include instructions to adjust or stop the flow rate of the inert gas and / or reactive gas, instructions to heat or ignite a plasma, instructions to adjust the flow rate of the carrier gas or purge gas, and a time delay instruction for the fifth recipe step. It will be understood that these recipe steps may be further subdivided and / or repeated in any suitable manner within the scope of the disclosed embodiments. In some embodiments, the controller 250 may include any of the features described below in connection with the system controller 350 of FIG. 3 and the system controller 450 of FIG. 4.

[0112] The process stations may be included in a single station chamber or a single chamber tool as shown in Figure 3. Figure 3 illustrates an example of a processing apparatus according to disclosed embodiments. The tool 300 includes a processing chamber 314, which may include a processing station 390 to process wafers. The processing chamber 314 is configured to deposit silicon oxide, deposit silicon nitride, anneal the substrate using thermal or plasma annealing, etc.

[0113] The tool 300 also includes a wafer transport unit configured to transfer wafers within the tool 300. Additional features of the tool 300 are discussed in greater detail below, with various features discussed herein in connection with some of the described techniques. In the depicted diagram, the wafer transport unit includes a first robot arm unit 326 in a first wafer transport module and a second robot arm unit 306 in a second wafer transport module, which may be considered an equipment front end module (EFEM) configured to receive a container for wafers, such as a front opening unified module (FOUP) 308. The first robot arm unit 326 is configured to transfer wafers between the processing chamber 314 and the second robot arm unit via a module 304, which may hold multiple wafers as shown in module 302 with substrate 312. The second robot arm unit 306 is configured to transfer wafers between the FOUP and module 304 or from module 302 to the FOUP. After the wafer is prepared in module 304, the wafer transport unit can transport the wafer to a first processing chamber 314 for deposition and optional in-situ annealing.

[0114] As above, the first wafer transfer module may be a vacuum transfer module (VTM). An airlock, also known as a loadlock, or module 304 is shown and may be individually optimized to perform various manufacturing processes. The tool 300 also includes a FOUP 308 configured to reduce the pressure of the tool 300 to a vacuum or low pressure, for example, between about 1 mTorr and about 10 Torr, and to maintain the tool 300 at this pressure. This includes maintaining the process chamber 314 and the first wafer transfer module at a vacuum or low pressure. The second wafer transfer module may be at a different pressure, such as atmospheric pressure. Thus, the wafer is maintained at a vacuum or low pressure as it is transferred through the tool 300.

[0115] In a further example, the substrate is placed in one of the FOUPs 308 and the second robot arm unit 306, or front-end robot, transfers the substrate from the FOUP 318 to an aligner so that the substrate can be properly centered before it is etched, has a film deposited thereon, or undergoes other processing. After being aligned, the substrate is transferred by the second robot arm unit 306 into the airlock module 304. The airlock module has the ability to match the environment between the ATM and the VTM so that the substrate can be moved between the two pressure environments without being damaged. From the airlock module 304, the substrate is transferred by the first robot arm unit 326 through the first wafer transfer module, or VTM, into the processing chamber 314. To accomplish this substrate transfer, the first robot arm unit 326 uses an end effector on each of its arms.

[0116] 3 also illustrates one embodiment of a system controller 350 employed to control process conditions and hardware states of the process tool 300. The system controller 350 may include one or more memory devices 356, one or more mass storage devices 354, and one or more processors 352. The processor 352 may include a CPU or computer, analog and / or digital input / output connections, stepper motor controller boards, etc. In some embodiments, the system controller 350 includes machine-readable instructions for performing operations such as those described above in connection with FIG. 2 and below in connection with FIG. 4.

[0117] As discussed above, one or more process stations may be included in a multi-station processing tool. FIG. 4 illustrates an example processing apparatus according to disclosed embodiments. The tool 400 includes a first processing chamber 402 and a second processing chamber 404. The first processing chamber 402 may include multiple processing stations, four stations 480A-D, each for processing a wafer. The first processing chamber 402 is configured to perform a plasma processing operation on the wafer. The second processing chamber 404 is configured to perform deposition on the wafer and may be considered a deposition chamber. The second processing chamber 404 may also include multiple processing stations, four stations 482A-D, each for processing a wafer. The first processing chamber 402 and the second processing chamber 404 may be considered a multi-station processing chamber.

[0118] The tool 400 also includes a wafer transport unit configured to transfer one or more wafers within the tool 400. Additional features of the tool 400 are discussed in greater detail below, and various features are discussed herein in connection with some of the described techniques. In the depicted diagram, the wafer transport unit includes a first robot arm unit 408 in a first wafer transport module 410 and a second robot arm unit 412 in a second wafer transport module 414, which may be considered an equipment front end module (EFEM) configured to receive a container for wafers, such as a front opening unified module (FOUP) 416. The first robot arm unit 408 is configured to transfer wafers between the first processing chamber 402 and the second processing chamber 404, and between the second robot arm unit 412. The second robot arm unit 412 is configured to transfer wafers between the FOUP and the first robot arm unit 408. After the wafer is processed in the first processing chamber 402, a wafer transport unit can transport the wafer from the first processing chamber 402 to a second processing chamber 404, where one or more layers of encapsulating material may be deposited on the one or more wafers.

[0119] As above, the first wafer transfer module 410 may be a vacuum transfer module (VTM). An airlock 420, also known as a loadlock or transfer module, is shown and may be individually optimized to perform various manufacturing processes. The tool 400 also includes a FOUP 416 configured to reduce the pressure of the tool 400 to a vacuum or low pressure, for example, between about 1 mTorr and about 10 Torr, and to maintain the tool 400 at this pressure. This includes maintaining the first processing chamber 402, the second processing chamber 404, and the first wafer transfer module 410 at a vacuum or low pressure. The second wafer transfer module 414 may be at a different pressure, such as atmospheric pressure. Thus, the wafer is maintained at a vacuum or low pressure as it is transferred through the tool 400. For example, as the wafer is transferred from the first processing chamber 402 into the first wafer transfer module 410 and to the second processing chamber 404, the wafer is maintained at a vacuum or low pressure and is not exposed to atmospheric pressure.

[0120] In a further example, the substrate is placed in one of the FOUPs 418 and the second robot arm unit 412, i.e., front-end robot, transfers the substrate from the FOUP 418 to an aligner so that the substrate can be properly centered before it is etched, has a film deposited thereon, or undergoes other processing. After being aligned, the substrate is transferred by the second robot arm unit 412 into the airlock 420. The airlock module has the ability to match the environment between the ATM and the VTM so that the substrate can be moved between the two pressure environments without being damaged. From the airlock 420, the substrate is transferred by the first robot arm unit 408 through the first wafer transfer module 410, i.e., the VTM 410, into the first processing chamber 402. To accomplish this substrate transfer, the first robot arm unit 408 uses end effectors on each of its arms.

[0121] 4 also illustrates one embodiment of a system controller 429 that is employed to control the process conditions and hardware states of the tool 400. The system controller 429 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, stepper motor controller boards, etc.

[0122] In some embodiments, the system controller 429 controls all of the activity of the tool 400. The system controller 429 executes system control software that is stored in mass storage devices, loaded into memory devices, and executed on a processor. Alternatively, the control logic may be hard-coded into the system controller 429. Application specific integrated circuits, programmable logic devices (e.g., field programmable gate arrays, or FPGAs), and the like may be used for these purposes. In the following discussion, wherever "software" or "code" is used, functionally equivalent hard-coded logic may be used instead. The system control software may include instructions for controlling the timing, mixture of gases, flow rates of gases, chamber and / or station pressures, chamber and / or station temperatures, wafer temperatures, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor positions, and parameters of the particular processes performed by the tool 400. The system control software may be configured in any suitable manner. For example, subroutines or control objects of various process tool components may be written to control the operation of the process tool components used to perform the processes of the various process tools. The system control software may be coded in any suitable computer readable programming language.

[0123] In some embodiments, the system control software may include input / output control (IOC) sequencing instructions for controlling the various parameters mentioned above. Other computer software and / or programs stored on mass storage and / or memory devices associated with the system controller 429 may be employed in some embodiments. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.

[0124] The substrate positioning program may include program code for process tool components used to load the substrate onto the pedestal and control the spacing between the substrate and other parts of the tool 400 .

[0125] The process gas control program may include code for controlling gas concentrations (e.g., silicon-containing precursor gases described herein, nitrogen-containing gases, carrier gases, inert gases, and / or purge gases) and flow rates, and optionally for flowing gases to one or more process stations prior to deposition to stabilize the pressure in the process station. The pressure control program may include code for controlling the pressure in the process station, for example, by adjusting a throttle valve in the exhaust system of the process station, gas flow into the process station, etc.

[0126] The heater control program may include code for controlling the current to a heating unit used to heat the substrate, or the heater control program may control the delivery of a heat transfer gas (such as helium or nitrogen) to the substrate.

[0127] The plasma control program may include code for setting RF power levels applied to process electrodes at one or more process stations in accordance with embodiments herein.

[0128] The pressure control program may include code for maintaining pressure in a reaction chamber according to embodiments herein.

[0129] In some embodiments, there may be a user interface associated with the system controller 429. The user interface may include a display screen, a graphical software display of equipment and / or process conditions, and user input devices such as a pointing device, keyboard, touch screen, microphone, etc.

[0130] In some embodiments, the parameters adjusted by the system controller 429 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (RF bias power levels), etc. These parameters may be provided to a user in the form of a recipe or may be entered using a user interface.

[0131] Signals for monitoring the process may be provided by analog and / or digital input connections of the system controller 429 from various process tool sensors. Signals for controlling the process may be output at analog and digital output connections of the tool 400. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with the data from these sensors to maintain process conditions.

[0132] The system controller 429 may provide program instructions for carrying out the deposition processes described above. The program instructions may control various process parameters such as DC power levels, RF bias power levels, pressure, temperature, etc. The instructions may control the parameters to manipulate the in situ deposition of film stacks according to various embodiments described herein.

[0133] The system controller 429 typically includes one or more memory devices and one or more processors configured to execute instructions for performing methods by the apparatus in accordance with the disclosed embodiments. A machine-readable medium containing instructions for controlling process operations in accordance with the disclosed embodiments may be coupled to the system controller 429.

[0134] In some implementations, the system controller 429 is part of a system, which may be part of the examples described above. Such a system may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (wafer pedestals, gas flow systems, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as a "controller" and may control various components or subparts of one or more systems. Depending on the processing conditions and / or type of system, the system controller 429 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow settings, fluid delivery settings, position and motion settings, loading and unloading of wafers into and out of the tool, and loading and unloading of wafers into and out of other transport tools and / or load locks connected or interlocked with the particular system.

[0135] Broadly speaking, the system controller 429 may be defined as electronic equipment having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute the program instructions (e.g., software). The program instructions may be instructions communicated to the system controller 429 in the form of various individual settings (or program files) that define the operating parameters for performing a particular process on or for a semiconductor wafer or for a system. The operating parameters may, in some embodiments, be part of a recipe defined by a process engineer to accomplish one or more processing steps during the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0136] The system controller 429 may be part of or connected to a computer that is integrated into the system, connected to the system, otherwise networked to the system, or a combination thereof, in some embodiments. For example, the system controller 429 may be all or part of a "cloud" or fab host computer system, which allows remote access of wafer processing. The computer may allow 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 from multiple manufacturing operations, change parameters of a current process, set processing steps to track a current process, or start a new process. In some examples, a remote computer (e.g., a server) may provide process recipes to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows for entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the system controller 429 receives instructions in the form of data that specify parameters for each of the processing steps to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process being performed and the type of tool that the system controller 429 is configured to interface with or control. Thus, as described above, the system controller 429 may be distributed, such as by including one or more individual controllers networked together and operating toward a common purpose, such as the processes and controls described herein. One example of a distributed controller for such purposes is one or more integrated circuits on the chamber that are located remotely (e.g., at the platform level or as part of a remote computer) and communicate with one or more integrated circuits that cooperatively control the processes at the chamber.

[0137] Examples of systems may include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an ALD chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing system associated with or used in the fabrication and / or manufacturing of semiconductor wafers.

[0138] As described above, depending on one or more steps being performed by the tool, the system controller 429 may communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used to transport materials to and from containers of wafers to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0139] Suitable apparatus for carrying out the methods disclosed herein are further discussed and described in U.S. patent application Ser. No. 13 / 084,399 (now U.S. Patent No. 8,728,956), filed Apr. 11, 2011, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION," and U.S. patent application Ser. No. 13 / 084,305, filed Apr. 11, 2011, entitled "SILICON NITRIDE FILMS AND METHODS," each of which is incorporated herein in its entirety.

[0140] The apparatus and processes described herein may be used in conjunction with lithographic patterning tools or processes, for example, for the manufacture or production of semiconductor devices, displays, LEDs, solar panels, and the like. Typically, but not necessarily, such tools / processes are used or performed together in a common manufacturing facility. Lithographic patterning of a film typically includes some or all of the following operations, each effected by several possible tools: (1) applying photoresist onto a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing the photoresist using a hotplate, furnace, or UV curing tool; (3) exposing the photoresist to visible, UV, or X-ray light using a tool such as a wafer stepper; (4) developing the resist and selectively removing the resist, thereby patterning, using a tool such as a wet bench; (5) transferring the resist pattern to an underlying film or workpiece using a dry etch or plasma-assisted etch tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper.

[0141] experiment Silicon oxide was deposited on the substrate using an atomic layer deposition cycle including exposure to dichlorosilane, purge, oxygen gas, and purge at 650° C. The silicon oxide thus deposited was characterized by FTIR to produce FIG. 5, which shows no visible –OH peaks, but does show a peak at 1072 cm for the Si–O bond. -1 The results show a strong peak at 1000 nm, indicating the formation of high quality silicon oxide.

[0142] The atomic content of silicon, oxygen, carbon, hydrogen, chlorine, and fluorine was evaluated at various depths in the silicon oxide deposition film, with the fluorine impurity level being 0.001%, the chlorine impurity level being 0.1%, and the hydrogen impurity level being 0.2%.

[0143] definition The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms in a linear, branched, or cyclic configuration, saturated, unsaturated, and aromatic, and combinations thereof, or hydrogen attached to the parent molecular group through a carbonyl group, as defined herein. This group is exemplified by formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0144] "Alkanoyloxy" means an alkanoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. This group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, an alkanoyloxy group is -OC(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0145] "Aliphatic" refers to compounds with at least 1 to 5 carbon atoms (C 1-50 ), for example, carbon numbers 1 to 25 (C 1-25 ) or carbon number 1 to 10 (C 1-10 Aliphatic groups refer to hydrocarbon groups such as aryl, arylalkyl, arylsulfates, arylalkyls, and arylalkyls, including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, as well as straight and branched chain configurations, and all stereoisomers and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups can be substituted with one or more substituents as described herein for alkyls.

[0146] "Aliphatic-carbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0147] "Aliphatic-carbonyloxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aliphatic group as defined herein.

[0148] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the aliphatic-oxy ​​group is -OR, where R is an optionally substituted aliphatic group as defined herein.

[0149] "Aliphatic-oxycarbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, where the aliphatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted aliphatic group as defined herein.

[0150] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" refer to an alkyl group, an alkenyl group, or an alkynyl group, respectively, as defined herein, that is or can be coupled (or bonded) to a parent molecular group via an aryl group, as defined herein. The alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl group, the alkenyl-aryl group, and / or the alkynyl-aryl group can be substituted with one or more substituents as described herein for the alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups include those containing 7 to 16 carbon atoms (C 7-16 alkyl-aryl), and those having an alkyl group having 1 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups are those containing 7 to 16 carbon atoms (C 7-16 alkenyl-aryl), and those having an alkenyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups are those containing 7 to 16 carbon atoms (C 7-16 alkynyl-aryl), and those having an alkynyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, the alkyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkyl group as defined herein. In some embodiments, the alkenyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkenyl group as defined herein. In some embodiments, the alkynyl-aryl group is -LR, where L is an aryl or arylene group as defined herein, and R is an alkynyl group as defined herein.

[0151] "Alkenyl" means an alkyl group having at least 2 to 50 carbon atoms (C 2-50 ), for example, carbon numbers of 2 to 25 (C 2-25 ) or carbon number 2 to 10 (C 2-10 Alkenyl groups refer to unsaturated monovalent hydrocarbons having at least one carbon-carbon double bond, such as alkoxy, ... 2-24 Alkyl groups include. Alkenyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more substituents as described herein for alkyl. Non-limiting alkenyl groups include allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, and the like.

[0152] "Alkoxy" refers to -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. An alkoxy group can be substituted or unsubstituted. For example, an alkoxy group can be substituted with one or more substituents as described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 Examples of the alkyl group include alkoxy groups.

[0153] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups include those having 2 to 12 carbon atoms (C 2-12 alkoxyalkyl), and those having an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl group is -LOR, where each of L and R is independently an alkyl group, as defined herein.

[0154] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In certain embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group can be substituted or unsubstituted. For example, the alkoxycarbonyl group can be substituted with one or more 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 An example of such a group is an alkoxycarbonyl group.

[0155] "Alkyl" means a group having at least 1 to 50 carbon atoms (C 1-50 ), for example, carbon numbers 1 to 25 (C 1-25 ) or carbon number 1 to 10 (C 1-10), which may be derived by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). An alkyl group may be branched, straight-chained, or cyclic (e.g., cycloalkyl). Exemplary alkyls include branched or unbranched saturated hydrocarbon groups having 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), iso-propyl (iPr), n-butyl (nBu), iso-butyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), s-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. Additionally, alkyl groups can be substituted or unsubstituted. An alkyl group can be made monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group can be substituted with one, two, three, or, in the case of alkyl groups having two or more carbon atoms, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (2) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (4) amino (e.g., -NR 1 R 2 , where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2may form a heterocyclyl group as defined herein together with the nitrogen atom to which each is attached), (5) aryl, (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl), (7) aryloyl (e.g., -C(O)-R, where R is aryl), (8) azido (e.g., -N), (9) cyano (e.g., -CN), (10) aldehyde (e.g., -C(O)H), (11) C 3-8 cycloalkyl, (12) halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein), (15) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (16) hydroxyl (e.g., -OH), (17) N-protected amino, (18) nitro (e.g., -NO), (19) oxo (e.g., =O), (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl), (21) thiol (e.g., -SH), (22) -COR 1 , where R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (23) -C(O)NR aryl 1 R 2 , where R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18(24) -SO2R 1 , where R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (25)-SONR 1 R 2 , where R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), and (26) -NR 1 R 2 , where R 1 and R 2 each independently represents (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl, (e) C 2-6 Alkynyl, (f) C 4-18 Aryl, (g) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8In one embodiment, there are no two groups attached to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl groups can be primary, secondary, or tertiary alkyl groups substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl groups are selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0156] "Alkylene," "alkenylene," or "alkynylene" refer to the polyvalent (e.g., divalent) form of an alkyl, alkenyl, or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, an alkylene group is an alkyl group selected from the group consisting of C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 In another embodiment, the alkylene group is 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 , or C 2-24 It is an alkenylene group or an alkynylene group. The alkylene group, the alkenylene group, or the alkynylene group may be branched or unbranched. The alkylene group, the alkenylene group, or the alkynylene group may also be substituted or unsubstituted. For example, the alkylene group, the alkenylene group, or the alkynylene group may be substituted with one or more substituents as described herein for alkyl.

[0157] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is 1-6 Or C 1-12 In another embodiment, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0158] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, an unsubstituted alkylsulfinylalkyl group is C 2-12 Or C 2-24 Alkyl sulfinyl alkyl groups (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In another embodiment, the alkylsulfinylalkyl group is -LS(O)-R, where each of L and R is independently an alkyl group, as defined herein.

[0159] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO- group. In some embodiments, an unsubstituted alkylsulfonyl group is 1-6 Or C 1-12 In other embodiments, the alkylsulfonyl group is -SO-R, where R is an optionally substituted alkyl (e.g., an optionally substituted C alkyl group, as described herein). 1-12 alkyl, haloalkyl, or perfluoroalkyl).

[0160] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, an unsubstituted alkylsulfonylalkyl group is a C2-12 Or C 2-24 Alkylsulfonylalkyl groups (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In another embodiment, the alkylsulfonylalkyl group is -L-SO2-R, where each of L and R is independently an alkyl group, as defined herein.

[0161] "Alkynyl" means an alkyl group having at least 2 to 50 carbon atoms (C 2-50 ), for example, carbon numbers of 2 to 25 (C 2-25 ) or carbon number 2 to 10 (C 2-10 Alkynyl groups may be branched, straight-chained, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls include optionally substituted C alkyl groups having one or more triple bonds, such as alkynyl groups having one or more triple bonds, and alkynyl groups having one or more triple bonds, such as alkynyl groups having one or more triple bonds, and alkynyl groups having one or more triple bonds. 2-24 Examples of alkynyl groups include alkyl groups. Alkynyl groups can be cyclic or non-cyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents as described herein for alkyl.

[0162] "Ambient temperature" means a temperature in the range of 16°C to 26°C, such as, for example, 19°C to 25°C or 20°C to 25°C.

[0163] "Amide" is -C(O)NR 1 R 2 or -NHCOR 1 where R 1 and R 2is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 together with the nitrogen atom to which they are attached can form a heterocyclyl group, as defined herein.

[0164] "Amino" is -NR 1 R 2 where R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted silyloxy, or any combination thereof, as defined herein; or R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a heterocyclyl group, as defined herein. In certain embodiments, R 1 and R 2 Each of R is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted silyloxy. 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0165] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 where L is an alkyl group as defined herein and R 1 and R 2is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a heterocyclyl group, as defined herein. In other embodiments, an aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 can form, together with the nitrogen atom to which they are attached, a heterocyclyl group, as defined herein; R 3 and R 4 Each of is independently H or alkyl as defined herein.

[0166] "Aminoxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, the aminooxy group is -O-NR 1 R 2 where R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted silyloxy, or any combination thereof, as defined herein; or R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a heterocyclyl group, as defined herein. In certain embodiments, R 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 silyloxy.

[0167] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5-15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., at least one ring, and optionally multiple fused rings, have a contiguous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Huckel's rule (4n+2). The point of attachment to the parent structure is usually through the aromatic portion of the fused ring system. The aromatic group is unsubstituted or substituted, for example, with functional groups as described herein. For example, the aromatic group can be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0168] "Aromatic-carbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl group is -C(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0169] "Aromatic-carbonyloxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted aromatic group as defined herein.

[0170] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via an oxy group (-O-). In some embodiments, the aromatic-oxy ​​group is -OR, where R is an optionally substituted aromatic group as defined herein.

[0171] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, where the aromatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the aromatic-carbonyl group is -C(O)OR, where R is an optionally substituted aromatic group as defined herein.

[0172] "Aryl" means an alkyl group having at least 5 to 15 carbon atoms (C 5-15 ), for example, carbon numbers of 5 to 10 (C 5-10), the fused rings may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also encompasses heteroaryl, which is defined as a group that contains an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl is also encompassed by the term aryl, defining a group that contains an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 (2) C 1-6 Alkyl, (3) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, where L and R are each independently 1-6 (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, where L and R are each independently 1-6 (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (8) C 1-6 Alkylsulfonyl-C1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently 1-6 (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 may form, together with the nitrogen atom to which each is attached, a heterocyclyl group as defined herein; (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 Or -L 2 -C(NR 1 R 2 )R 3 )-R 4 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 is alkyl, R 1 and R 2 is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein; or R 1 and R 2 can form, together with the nitrogen atom to which they are attached, a heterocyclyl group, as defined herein; R 3 and R 4 Each of is independently H or C 1-6 (12) heteroaryl, (13) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (14) aryloyl (e.g., -C(O)-R, where R is aryl), (15) azido (e.g., -N), (16) cyano (e.g., -CN), (17) C1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 (18) aldehyde (e.g., —C(O)H), (19) aldehyde-C 1-6 Alkyl (e.g., -LC(O)H, where L is C 1-6 (20) C 3-8 Cycloalkyl, (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8 (22) halo, (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or C 1-6 alkyl, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is independently H or C 1-6 (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein), (25) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein), (26) heterocyclyloyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein), (27) hydroxyl (-OH), (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein.1-6 (29) nitro, (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 is C 1-6 is alkyl, and L 2 is a covalent bond or an alkyl; R 1 and R 2 Each of is independently H or C as defined herein. 1-6 (31) N-protected amino, (32) N-protected amino-C 1-6 Alkyl, (33) oxo (e.g., =O), (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, where L and R are each independently 1-6 (36)-(CH2) r CO2R 1 where r is an integer from 0 to 4, and R 1 is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (37)-(CH2) r CONR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18(38)-(CH2) r SO2R 1 where r is an integer from 0 to 4, and R 1 (a)C 1-6 Alkyl, (b) C 4-18 aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (39)-(CH2) r SO2NR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently is (a) hydrogen, (b) C 1-6 Alkyl, (c) C 4-18 aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 (40)-(CH2) r NR 1 R 2 where r is an integer from 0 to 4, and R 1 and R 2 each independently represents (a) hydrogen, (b) an N-protecting group, (c) C 1-6 Alkyl, (d) C 2-6 alkenyl, (e) C 2-6 Alkynyl, (f) C 4-18 Aryl, (g) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 4-18 aryl), (h) C 3-8 cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 alkyl and R is C 3-8(41) thiol (e.g., -SH), (42) perfluoroalkyl (e.g., -(CF2) n CF3, where n is an integer from 0 to 10), (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, where n is an integer from 0 to 10), (44) aryloxy (e.g., -OR, where R is aryl), (45) cycloalkoxy (e.g., -OR, where R is cycloalkyl), (46) cycloalkylalkoxy (e.g., -OLR, where L is alkyl and R is cycloalkyl), and (47) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 It is an aryl group.

[0173] "Aryl-alkyl", "aryl-alkenyl", and "aryl-alkynyl" refer to an aryl group, as defined herein, that is or can be coupled (or attached) to a parent molecular group via an alkyl group, an alkenyl group, or an alkynyl group, as defined herein, respectively. The aryl-alkyl group, the aryl-alkenyl group, and / or the aryl-alkynyl group can be substituted or unsubstituted. For example, the aryl-alkyl group, the aryl-alkenyl group, and / or the aryl-alkynyl group can be substituted with one or more substituents as described herein for aryl and / or alkyl. Exemplary unsubstituted aryl-alkyl groups include those having 7 to 16 carbon atoms (C 7-16 aryl-alkyl), and those having an aryl group having 4 to 18 carbon atoms and an alkyl group having 1 to 6 carbon atoms (i.e., C 4-18 Aryl-C 1-6Exemplary unsubstituted aryl-alkenyl groups are those having 7 to 16 carbon atoms (C 7-16 aryl-alkenyl), and those having an aryl group having 4 to 18 carbon atoms and an alkenyl group having 2 to 6 carbon atoms (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups are those containing 7 to 16 carbon atoms (C 7-16 aryl-alkynyl), and those having an aryl group having 4 to 18 carbon atoms and an alkynyl group having 2 to 6 carbon atoms (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, where L is an alkyl or alkylene group as defined herein and R is an aryl group as defined herein. In some embodiments, the aryl-alkenyl group is -LR, where L is an alkenyl or alkenylene group as defined herein and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -LR, where L is an alkynyl or alkynylene group as defined herein and R is an aryl group as defined herein. In some embodiments, the aryl-alkynyl group is -LR, where L is an alkynyl or alkynylene group as defined herein and R is an aryl group as defined herein.

[0174] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenylether, acenaphthenylene, anthrylene, or phenanthrylene. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C 6-10 It is an arylene group. The arylene group can be branched or unbranched. The arylene group can also be substituted or unsubstituted. For example, the arylene group can be substituted with one or more substituents as described herein for aryl.

[0175] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0176] "Aryloxy" refers to -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is C 4-18 Or C 6-18 In other embodiments, R is an aryl group optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0177] "Aryloxycarbonyl" means an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloxycarbonyl group is 5-19 In another embodiment, the aryloxycarbonyl group is -C(O)OR, where R is an aryl group, as defined herein.

[0178] "Aryloyl" refers to an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is 7-11 Aryloyl or C 5-19 In another embodiment, the aryloyl group is -C(O)-R, where R is an aryl group, as defined herein.

[0179] "Aryloyloxy" refers to an aryloyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, an unsubstituted aryloyloxy group is 5-19In another embodiment, an aryloyloxy group is -OC(O)-R, where R is an aryl group, as defined herein.

[0180] "Azido" refers to the group --N3.

[0181] "Azidoalkyl" means an azido group attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group, as defined herein.

[0182] "Azo" means the -N=N- group.

[0183] "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 is a group, where R 1 and R 2 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted silyloxy, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which they are attached can form a heterocyclyl group, as defined herein.

[0184] "Carbamoyloxy" means a carbamoyl group, as defined herein, attached to the parent molecular group through an oxy group, as defined herein. In some embodiments, carbamoyl is -OC(O)NR 1 R 2 is a group, where R 1 and R 2is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted silyloxy, or any combination thereof, as defined herein; or R 1 and R 2 together with the nitrogen atom to which they are attached can form a heterocyclyl group, as defined herein.

[0185] "Carbonimidoyl" refers to a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein.

[0186] "Carbonyl" means the group -C(O)-, which also can be represented as >C=O.

[0187] "Carboxyl" means the -CO2H group or the anion thereof.

[0188] "Catalyst" means a compound, usually present in small amounts relative to the reactants, capable of catalyzing a synthesis reaction, as would be readily understood by one of ordinary skill in the art. In some embodiments, the catalyst may include a transition metal coordination compound.

[0189] "Cyanato" refers to the group -OCN.

[0190] "Cyano" refers to the radical -CN.

[0191] "Cycloaliphatic" means an aliphatic group, as defined herein, that is cyclic.

[0192] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group, as defined herein.

[0193] "Cycloalkylalkoxy" means a radical -OLR where L is an alkyl or alkylene group as defined herein and R is a cycloalkyl group as defined herein.

[0194] "Cycloalkyl", unless otherwise specified, means a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group having 3 to 8 carbon atoms, exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyl groups can also be substituted or unsubstituted. For example, cycloalkyl groups can be substituted with one or more groups, including those described herein for alkyl. Additionally, cycloalkyl groups can include one or more double and / or triple bonds.

[0195] "Cycloheteroaliphatic" means a heteroaliphatic group, as defined herein, that is cyclic.

[0196] "Disilanyl" refers to a group that contains a Si-Si bond. In some embodiments, the disilanyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 or -SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 , and R S5Each of is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0197] "Disulfide" means -SSR, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0198] "Electron donating group" means a functional group capable of donating at least a portion of its electron density, such as by resonance, to the ring to which it is directly attached.

[0199] "Electron-withdrawing group" means a functional group that can accept electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

[0200] "Halo" means F, Cl, Br, or I.

[0201] "Haloaliphatic" means an aliphatic group, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0202] "Haloalkyl" means an alkyl group, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In one independent embodiment, a haloalkyl can be a -CX group, where each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, a haloalkyl group is -LX, where L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, a haloalkyl group is -LC(X)(R 1 )-R 2where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0203] "Haloheteroaliphatic" means heteroaliphatic, as defined herein, where one or more hydrogen atoms, such as 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0204] "Heteroaliphatic" refers to an aliphatic group as defined herein that contains at least one heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms or 1 to 5 heteroatoms, where the heteroatoms may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. Heteroaliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaliphatic groups may be substituted with one or more substituents as described herein for alkyl.

[0205] "Heteroaliphatic-carbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0206] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaliphatic group as defined herein.

[0207] "Heteroaliphatic-oxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0208] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, where the heteroaliphatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaliphatic-oxycarbonyl group is -C(O)OR, where R is an optionally substituted heteroaliphatic group as defined herein.

[0209] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" mean an alkyl, alkenyl, or alkynyl group, as defined herein, which may be branched, straight-chained, or cyclic, containing at least one heteroatom to 20 heteroatoms, such as, for example, 1 to 15 heteroatoms or 1 to 5 heteroatoms, and the heteroatoms may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, within the group.

[0210] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to the polyvalent (e.g., divalent) forms of a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as described herein.

[0211] "Heteroaromatic" means an aromatic group as defined herein, containing at least one heteroatom to 20 heteroatoms, such as 1 to 15 heteroatoms or 1 to 5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof within the group. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups may be substituted with one or more substituents as described herein for alkyl and / or aryl.

[0212] "Heteroaromatic-carbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0213] "Heteroaromatic-carbonyloxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, where R is an optionally substituted heteroaromatic group as defined herein.

[0214] "Heteroaromatic-oxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​group is -OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0215] "Heteroaromatic-oxycarbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, where the heteroaromatic group is or becomes coupled via an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl group is -C(O)OR, where R is an optionally substituted heteroaromatic group as defined herein.

[0216] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms, such as 1 to 4 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof in the ring. Such heteroaryl groups may have a single ring or multiple fused rings, which may or may not be aromatic and / or may contain heteroatoms, provided that the point of attachment is through an atom of the aromatic heteroaryl group. The heteroaryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryls include a subset of heterocyclyl groups as defined herein that are aromatic, i.e., contain 4n+2 pi-electrons in a monocyclic or polycyclic ring system.

[0217] "Heteroarylene" means a polyvalent (eg, divalent) form of a heteroaryl group, as described herein.

[0218] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, heteroatoms do not include halogen atoms, such as when not permitted by valence constraints.

[0219] "Heterocyclyl" means, unless otherwise specified, a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Five-membered rings have 0 to 2 double bonds, and 6- and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocycles are fused to 1, 2, or 3 rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and other monocyclic heterocycles, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, and the like. Heterocycles include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, nyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, urisyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0220] "Heterocyclyloxy" means a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group, as defined herein.

[0221] "Heterocyclyl" means a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group, as defined herein.

[0222] "Hydrazino" is -NR 1 -NR 2 R 3 means R 1 , R 2 , and R 3 is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted silyloxy, or any combination thereof, as defined herein; or R 1 and R 2 A combination of or R 2 and R 3 The combination of, together with the nitrogen atom to which each is attached, can form a heterocyclyl group, as defined herein. In some embodiments, R 1 , R 2 , or R 3 is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl. In certain embodiments, R 2 and R 3 together with the nitrogen atom to which they are attached can form an optionally substituted heterocyclyl.

[0223] "Hydroxyl" means --OH.

[0224] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with one to three hydroxyl groups, provided that only one hydroxyl group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, a hydroxyalkyl group is -L-OH, where L is an alkyl group, as defined herein. In other embodiments, a hydroxyalkyl group is -LC(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0225] "Imidoyl" refers to a moiety that contains a carbonimidoyl group. In some embodiments, the imidoyl group is C(NR 1 )R 2 and R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyloxy, or any combination thereof, as defined herein. In other embodiments, the imidoyl group is -C(NR 1 )H, -C(NR 1 )R Ak , or -C(NR N1 )R Ar where R 1is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted silyloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic, R Ar is an optionally substituted aryl, or an optionally substituted aromatic.

[0226] "Imino" refers to the group -NR-. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In certain embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0227] "Isocyanato" refers to a -NCO group.

[0228] "Isocyano" refers to the group -NC.

[0229] "Ketone" means a compound containing -C(O)R, or such a group, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein. An example of a ketone is R 1 C(O)R, where R and R 1 Each of is independently selected from aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, as defined herein.

[0230] "Nitro" refers to the radical --NO2.

[0231] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with one to three nitro groups. In some embodiments, a nitroalkyl group is -L-NO, where L is an alkyl group, as defined herein. In other embodiments, a nitroalkyl group is -LC(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0232] "Oxo" means the group ═O.

[0233] "Oxy" means --O--.

[0234] "Perfluoroalkyl" means an alkyl group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer from 0 to 10.

[0235] "Perfluoroalkoxy" refers to an alkoxy group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group, as defined herein.

[0236] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein), including cationic or anionic compounds to form electrically neutral compounds or structures. Salts are well known in the art. For example, non-toxic salts are described in "Pharmaceutical salts" (Berge SM et al., J.Pharm.Sci. January 1977;66(1):1-19) and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use" (Wiley-VCH, April 2011, 2nd Revised Edition, edited by PH Stahl and CG Wermuth). Salts can be prepared in situ during the final isolation and purification of the compounds of the present invention, or separately by reacting the free base with a suitable organic acid (thereby producing an anionic salt) or by reacting an acidic group with a suitable metal or organic acid salt (thereby producing a cationic salt).Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobisulfate, and the like. Examples of the salts include acetate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, basic acetate, succinate, sulfate, tannate, tartrate, theophylline, thiocyanate, triethiodide, toluenesulfonate, undecanoate, and valerate. Representative cationic salts include metal salts such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts such as aluminum, bismuth, iron, and zinc; as well as non-toxic ammonium, quaternary ammonium, and amine cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, substituted and optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prenium).

[0237] "Silyl" is -SiR 1 R 2 R 3 or -SiR 1 R2 In some embodiments, R 1 , R 2 , and R 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3 Each of is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyl group is -Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, and each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0238] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, the silyloxy group is -O-SiR 1 R 2 R 3 where R 1 , R 2 , and R 3 Each of R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. 1 , R 2 , and R 3Each of is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, the silyloxy group is -O-Si(R) a (OR) b (NR2) c wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic, each of a, b, and c is > 0, and a + b + c = 3. In certain embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0239] "Sulfinyl" means the group -S(O)-.

[0240] "Sulfo" refers to the group -S(O)2OH.

[0241] "Sulfonyl" or "sulfonate" means a -S(O)- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0242] "Thioalkyl" means an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include, but are not limited to, C 1-6 In some embodiments, the thioalkyl group is -SR, where R is an alkyl group, as defined herein.

[0243] "Thiol" refers to a -SH group.

[0244] Those skilled in the art will recognize that the above definitions are not intended to include impermissible substitution patterns (e.g., methyl substituted with five different groups). Such impermissible substitution patterns are readily recognized by those skilled in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise indicated.

[0245] As used herein, the term "about" means ±10% of any recited value. As used herein, the term modifies any recited value, range of values, or one or more of the endpoints of a range.

[0246] As used herein, the terms "top," "bottom," "upper," "lower," "above," and "below" are used to provide relative relationships between structures. Use of these terms does not indicate or require that a particular structure must be located in a particular location within the device.

[0247] conclusion Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be 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 of implementing the processes, systems, and apparatus of the present embodiments. Thus, the present embodiments are to be considered as illustrative and not restrictive, and the present embodiments are not to be limited to the details given herein.

Claims

1. 1. A method for processing a substrate, comprising: Introducing a substrate having features; exposing the substrate to a silicon-containing precursor for a period of time sufficient to cause at least a portion of the silicon-containing precursor to adsorb onto a surface of the substrate; exposing the surface of the substrate to an oxygen-containing gas without igniting a plasma to form a silicon oxide film; annealing the silicon oxide film to form an annealed silicon oxide film; Including, the silicon-containing precursor is selected from the group consisting of a halosilane precursor and an aminosilane precursor; method.

2. 10. The method of claim 1, wherein the silicon-containing precursor is dichlorosilane.

3. 2. The method of claim 1, wherein the silicon-containing precursor is diisopropylaminosilane (DIPAS).

4. The method of claim 1 , wherein the annealing is performed at a temperature of at least about 500° C.

5. 10. The method of claim 1, wherein annealing comprises exposing the silicon oxide film to a plasma generated by igniting hydrogen gas and oxygen gas.

6. 10. The method of claim 1, wherein annealing comprises exposing the silicon oxide film to a plasma generated by igniting nitrogen gas.

7. 10. The method of claim 1, wherein the annealed silicon oxide film has a chlorine content of less than about 0.5%.

8. 10. The method of claim 1, wherein the annealed silicon oxide film has a hydrogen content of less than about 0.5%.

9. 10. The method of claim 1, wherein the silicon oxide film is conformal.

10. 1. An apparatus for processing a substrate, comprising: one or more process chambers, each process chamber including a chuck; one or more gas inlets and associated flow control hardware to the process chamber; a controller having at least one processor and a memory; Including, the at least one processor and the memory are communicatively coupled to each other; the at least one processor is operatively connected to the flow control hardware; and the memory controls the at least one processor to control at least the flow control hardware; introducing an aminosilane or halosilane precursor into the one or more process chambers for a period of time sufficient to allow at least a portion of the aminosilane or halosilane precursor to adsorb onto a surface of the substrate; introducing an oxygen-containing gas without igniting a plasma to form a silicon oxide film; Annealing the silicon oxide film to form an annealed silicon oxide film. storing computer executable instructions for: Device.

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