Deposition and etch of silicon-containing layers

Abstract

A silicon-based film is conformally deposited in a feature and controlled etching is performed using a remote plasma. The silicon-based film may be an amorphous silicon layer or a doped silicon layer, including silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride. The silicon-based film may be partially etched using remote plasma according to a desired depth and geometry by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, RF power, gas composition, and relative concentration of gas composition. Also provided are methods and apparatus for depositing a silicon-containing film having an adjustable film composition and density, in which the silicon-containing film is formed by thermal atomic layer deposition or thermal chemical vapor deposition, and the silicon-containing film is treated with a densifying gas plasma.

Description

Incorporated by Reference

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

[0002] Many semiconductor device manufacturing processes involve forming silicon-based dielectric films. Silicon-based dielectric films may include films containing one element, silicon; or two elements, such as silicon oxide, silicon carbide, or silicon nitride; or three elements, such as silicon oxynitride, silicon oxycarbide, silicon carbonitride; or four elements, such as silicon carbon oxynitride. Depositing and etching silicon-based dielectric films according to target depths and profiles can be particularly challenging. Challenges may also include gap filling of high aspect ratio features using silicon-based dielectric films.

[0003] Some deposition of silicon-based dielectric films involves thermal chemical vapor deposition (CVD) and / or thermal atomic layer deposition (ALD). In certain applications, thermal deposition is required, but deposition conditions may be limited to the use of certain deposition precursors.

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

[0005] One aspect relates to a method of processing a substrate, the method comprising: conformally depositing a silicon-containing film in one or more recessed features of the substrate; and etching at least a portion of the silicon-containing film to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma.

[0006] In various embodiments, the silicon-containing film includes an amorphous silicon layer. In various embodiments, conformally depositing the silicon-containing film includes flowing a silicon-containing precursor to adsorb on a surface of the substrate, and thermally decomposing the silicon-containing precursor to form the amorphous silicon layer.

[0007] In various embodiments, the silicon-containing film comprises silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbonitride. In various embodiments, conformally depositing the silicon-containing film comprises: flowing a silicon-containing precursor to adsorb onto the surface of the substrate; thermally decomposing the silicon-containing precursor to form an amorphous silicon layer; and exposing the amorphous silicon layer to a plasma to convert the amorphous silicon layer into silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbonitride.

[0008] In various embodiments, conformally depositing a silicon-containing film includes: depositing the silicon-containing film by thermal ALD or thermal CVD; and treating the silicon-containing film with a densifying gas plasma.

[0009] In various embodiments, the remote plasma includes one or more plasma activated species including radicals of hydrogen, halogen, hydrocarbon, fluorocarbon, or combinations thereof. In various embodiments, the one or more plasma activated species include hydrogen radicals.

[0010] In various embodiments, the at least one of the desired depth and the desired profile of the etch is based on one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition, relative concentrations of the gas composition, and RF power. In various embodiments, the desired depth of the etch is adjusted according to chamber pressure. In various embodiments, the desired depth of the etch is adjusted according to substrate temperature. In various embodiments, the desired depth of the etch is adjusted according to RF power. In various embodiments, the desired profile of the etch is adjusted according to relative concentrations of gas compositions.

[0011] In various embodiments, depositing the silicon-containing film and etching at least a portion of the silicon-containing film occur in the same reaction chamber.

[0012] In various embodiments, the method further includes repeating the deposition and etching operations to partially fill or completely fill the one or more recessed features of the substrate with the silicon-containing gap-fill material.

[0013] Another aspect relates to a method of processing a substrate, the method comprising: flowing a silane-based precursor into a reaction chamber to adsorb into one or more recessed features of the substrate, wherein the substrate is at an elevated temperature to thermally decompose the silane-based precursor and conformally deposit an amorphous silicon layer in the one or more recessed features of the substrate. The method further comprises generating a remote plasma in a remote plasma chamber upstream of the reaction chamber, the remote plasma comprising radicals of hydrogen, halides, hydrocarbons, fluorocarbons, or combinations thereof; and exposing the substrate to the remote plasma in the reaction chamber to etch at least a portion of the silicon-containing layer in the one or more recessed features to at least one of a desired depth and a desired profile by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentrations of the gas composition, and RF power.

[0014] In various embodiments, the silicon-containing layer includes an amorphous silicon layer.

[0015] In various embodiments, the silicon-containing layer includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxycarbonitride.

[0016] In various embodiments, the remote plasma includes hydrogen radicals.

[0017] In various embodiments, the silane-based precursor includes silane, disilane, or trisilane.

[0018] In various embodiments, the method further includes repeating the deposition and etching operations to partially fill or completely fill the one or more recessed features of the substrate with the silicon-containing gap-fill material.

[0019] Another aspect relates to a method of processing a substrate contained in a processing chamber, the method comprising: introducing a silicon-containing precursor and a reactant into the processing chamber at a substrate temperature of less than about 700° C. to form a silicon-containing film over the substrate without igniting a plasma; after forming the silicon-containing film, performing a plasma treatment operation, the plasma treatment operation comprising: stopping the flow of the silicon-containing precursor and the flow of the reactant; introducing a densification gas into the processing chamber; and igniting a plasma to treat the silicon-containing film; and adjusting at least one of the silicon-containing precursor, the reactant, or a process condition during the plasma treatment operation to at least change a composition or density of the silicon-containing film to form a treated silicon-containing film.

[0020] In various embodiments, the silicon-containing film is formed to about to about or about to about The thickness is then followed by a plasma treatment operation.

[0021] In various embodiments, the method may further include stopping the plasma treatment operation and introducing a silicon-containing precursor and a reactant to form an additional silicon-containing film over the treated silicon-containing film.

[0022] In various embodiments, the silicon-containing precursor and the reactant are introduced simultaneously.

[0023] In various embodiments, the silicon-containing precursor and the reactant are introduced in time-separated pulses.

[0024] In various embodiments, the method may further include purging the processing chamber between forming the silicon-containing film and performing the plasma treatment operation.

[0025] In various embodiments, the silicon-containing film is selected from the group consisting of silicon carbide, silicon oxycarbide, silicon oxynitride, silicon oxycarbonitride, silicon carbonitride, and combinations thereof.

[0026] In various embodiments, the method further includes etching at least a portion of the silicon-containing film by exposing the substrate to a remote plasma.

[0027] In various embodiments and some of any of the above embodiments, the plasma is generated in situ.

[0028] In various embodiments and some of any of the above embodiments, the first plasma and the second plasma are ignited using a single frequency plasma generator.

[0029] In various embodiments and some of any of the above embodiments, the plasma is ignited using a dual frequency plasma generator.

[0030] In various embodiments and some of any of the above embodiments, the reactant is selected from the group consisting of oxygen, ozone, peroxide, nitrous oxide, nitric oxide, nitrogen, ammonia, hydrazine, and combinations thereof.

[0031] In various embodiments and some of any of the above embodiments, the density of the silicon-containing film is at least about 2.0 g / cm 3 To about 2.6g / cm 3 .

[0032] In various embodiments and some of any of the above embodiments, the plasma treatment operation is performed at a temperature below about 700° C. In various embodiments and some of any of the above embodiments, the plasma treatment operation is performed at a temperature below about 650° C.

[0033] In various embodiments and some of any of the above embodiments, the silicon-containing film is formed in a feature having an aspect ratio of at least about 5:1.

[0034] In various embodiments and some of any of the above embodiments, the silicon-containing film is deposited using thermal atomic layer deposition.

[0035] In various embodiments and some of any of the above embodiments, the silicon-containing film is deposited using thermal chemical vapor deposition.

[0036] Another aspect relates to an apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber comprising a chuck; one or more gas inlets leading to the processing chamber and associated flow control hardware; and a controller having at least one processor and a memory, wherein the at least one processor is communicatively connected to the memory, the at least one processor is at least operably connected to the flow control hardware, and the memory stores computer executable instructions for controlling the at least one processor to control at least the flow control hardware to: cause a silicon-containing film to be formed over the substrate when the substrate temperature is less than about 700° C. and without igniting a plasma; and cause the silicon-containing film to be processed using a densification gas plasma.

[0037] These and other aspects are further described below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figures 1A-1C Schematic cross-sectional view showing exemplary substrate features for gap filling using directional etching in a deposition-etch-deposition process.

[0039] Figures 2A-2C Schematic cross-sectional view showing exemplary substrate features for gap filling using inhibited chemistry in a deposition-etch-deposition process.

[0040] Figure 3 A flow chart illustrating an example method of performing deposition and etching in substrate features according to some implementations.

[0041] Figure 4A-4B Schematic cross-sectional view showing an exemplary substrate feature partially etched to a shallow depth using a remote plasma according to some implementations.

[0042] Figure 5A-5B Schematic cross-sectional view showing an exemplary substrate feature partially etched to a deep depth using a remote plasma according to some implementations.

[0043] Figure 6A-6B Schematic cross-sectional view showing an exemplary substrate feature partially etched at a top surface using a remote plasma according to some implementations.

[0044] Figures 7A-7C Schematic cross-sectional view showing exemplary substrate features undergoing gap filling in a dep-etch-dep process according to some implementations.

[0045] Fig. 8A and 8B A process flow diagram is provided that depicts the operations of an exemplary method that may be performed in accordance with certain disclosed embodiments.

[0046] Fig. 9 A timing diagram illustrating an example of a method according to certain disclosed implementations.

[0047] Fig.10 FTIR spectra of films deposited using the deposition precursors with and without plasma treatment.

[0048] Fig.11 FTIR spectra of films deposited using the deposition precursors with oxygen and with and without plasma treatment.

[0049] Fig.12 A schematic diagram of an exemplary plasma processing apparatus with a remote plasma source is shown according to some implementations.

[0050] Fig.13 A schematic diagram of an exemplary plasma processing apparatus with a remote plasma source is shown according to some implementations. Specific implementation plan

[0051] In the following description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be practiced without some or all of these specific details. In other cases, well-known process operations are not described in detail to avoid unnecessarily obscuring the disclosed embodiments. Although the disclosed embodiments will be described in conjunction with specific embodiments, it should be understood that they are not intended to limit the disclosed embodiments.

[0052] In the present disclosure, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate" and "partially manufactured integrated circuit" are used interchangeably. It should be understood by a person skilled in the art to which the present invention belongs that the term "partially manufactured integrated circuit" can refer to a silicon wafer during any of the many stages of integrated circuit manufacturing. Wafers or substrates used in the semiconductor equipment industry typically have a diameter of 200 mm, 300 mm or 450 mm. The following embodiments assume that the present disclosure is implemented on a wafer. However, the present disclosure is not limited to this. The workpiece can be of various shapes, sizes and materials. In addition to semiconductor wafers, other workpieces that can also utilize the present disclosure include various articles, such as printed circuit boards, etc.

[0053] The substrate may include a plurality of "features" or "grooves". As used herein, a "feature" may refer to a non-planar structure of a substrate, typically a surface that is modified during a semiconductor device manufacturing operation. Examples of features (which may also be referred to as "negative features" or "recessed features") include grooves, holes, vias, gaps, recessed areas, and the like. These terms are used interchangeably in the present invention. An example of a feature is a hole or via in a layer within or on a semiconductor substrate. Another example is a groove in a substrate or layer. Features typically have an aspect ratio (depth to lateral dimension). Features may be characterized as one or more of narrow and / or concave openings, narrowing within features, and a high aspect ratio. Features with a high aspect ratio may have a depth to lateral dimension of equal to or greater than about 10:1, equal to or greater than about 15:1, equal to or greater than about 20:1, equal to or greater than about 25:1, equal to or greater than about 30:1, equal to or greater than about 40:1, equal to or greater than about 50:1, or equal to or greater than about 100:1. In various embodiments, the features can have an underlying layer, such as a barrier layer or an adhesion layer. Non-limiting examples of underlying layers include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, undoped silicon carbide, oxygen-doped silicon carbide, nitrogen-doped silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers.

[0054] The features of the substrate can be of various types. In some embodiments, the features can have straight sidewalls, positively sloped sidewalls, or negatively sloped sidewalls. In some embodiments, the features can have sidewall topography or sidewall roughness, which can occur due to the etching process used to form the features. In some embodiments, the features can have a feature opening that is larger at the top of the feature than at the bottom, or the features can have a feature opening that is larger at the bottom of the feature than at the top.

[0055] Semiconductor manufacturing processes often involve the manufacture of silicon-containing films, such as silicon carbonitride, silicon carbonitride oxides, silicon carbide, and silicon oxynitride. Such films are sometimes deposited onto patterned substrates to form conformal films for various applications. Sometimes, such films are deposited in a furnace. As devices shrink and technology becomes more advanced, higher quality, denser, and more conformal films are needed. Certain silicon-containing films can be deposited into high aspect ratio features on a substrate. In some cases, deposition is performed thermally for a variety of reasons, including but not limited to reducing or eliminating damage to existing structures and / or materials on the substrate.

[0056] One technique for depositing films is chemical vapor deposition (CVD), which may be thermal or may be plasma-enhanced (e.g., plasma-enhanced CVD, sometimes referred to as PECVD). In CVD, the deposition reactants are reacted together, typically in the gas or vapor phase, above the substrate surface, thereby resulting in the formation of a film on the substrate.

[0057] Another technique for depositing films is atomic layer deposition (ALD), which may also be thermal or may be plasma enhanced (e.g., plasma enhanced ALD, sometimes referred to as PEALD). ALD is a technique for depositing thin layers of material using a continuous self-limiting reaction. Unlike CVD, the ALD process utilizes a surface-mediated deposition reaction to deposit films in a layer-by-layer manner. As an example, a thermal ALD cycle may include the following operations: (i) delivering / adsorbing a precursor, (ii) purging the precursor from the chamber, (iii) delivering a second reactant, and (iv) purging byproducts from the chamber. The reaction between the second reactant and the adsorbed precursor to form a film on the surface of the substrate affects the film composition and properties, such as non-uniformity, stress, wet etch rate, dry etch rate, electrical properties (e.g., breakdown voltage and leakage current), etc.

[0058] In one example of an ALD process, a substrate surface including a large number of surface active sites is exposed to a gas phase distribution of a first precursor, such as a silicon-containing precursor, which is provided in a certain dosage to a chamber containing the substrate. Molecules of the first precursor (including chemically adsorbed substances and / or physically adsorbed molecules of the first precursor) are adsorbed onto the substrate surface. It should be understood that when a compound is adsorbed onto the substrate surface as described herein, the adsorption layer may include the compound and derivatives of the compound. For example, the adsorption layer of a silicon-containing precursor may include a silicon-containing precursor and a derivative of the silicon-containing precursor. After the first precursor is dosed, the chamber is then evacuated to remove most or all of the first precursor remaining in the gas phase, so that most or only the adsorbed substances remain. In some implementations, the chamber may not be completely evacuated. For example, the reactor may be evacuated so that the partial pressure of the first precursor in the gas phase is low enough to slow down the reaction. A second reactant (e.g., a carbon-containing gas) is introduced into the chamber so that a portion of these molecules react with the first precursor adsorbed on the surface. In some processes, the second precursor reacts immediately with the adsorbed first precursor. In other embodiments, the second reactant reacts only after applying an activation source (e.g., heat). In some embodiments, the activation source is applied only when the second precursor is introduced. Exposure to the second reactant and deposition of the precursor can be separated in time; that is, one after another, but not performed simultaneously. After exposure to the second reactant, the flow of the second reactant can be stopped and the chamber can then be evacuated again to remove unbound second reactant molecules. As described above, in some embodiments, the chamber may not be completely evacuated. Additional ALD cycles can be used to establish film thickness.

[0059] In a PEALD implementation, the method includes plasma activation during exposure to the second reactant. As described herein, the ALD methods and apparatus described herein can be conformal film deposition (CFD) methods, which are summarized in U.S. Patent Application No. 13 / 084,399, filed on April 11, 2011, entitled "PLASMA ACTIVATED CONFORMAL FILM DEPOSITION" (now U.S. Patent No. 8,728,956) and U.S. Patent Application No. 13 / 084,305, filed on April 11, 2011, entitled "SILICON NITRIDE FILMS AND METHODS", the entire contents of which are incorporated herein by reference.

[0060] Although ALD processes can be used to deposit certain films, certain processes involve the use of halogen-containing precursors, which may limit the process conditions under which the film can be deposited. For example, in some embodiments, deposition may only occur at temperatures greater than about 700° C. or greater than about 650° C. due to thermodynamic limitations.

[0061] Provided herein are methods and apparatus for depositing silicon-containing dielectric films by thermal ALD and / or CVD with halogen-free deposition precursors and adjustable film composition and densification. The silicon-containing films deposited using certain disclosed embodiments are high quality films. The silicon-containing film is deposited on a substrate, which may be a silicon wafer, such as a 200 mm wafer, a 300 mm wafer, or a 450 mm wafer, including a wafer having one or more layers of material, such as a dielectric, conductive, or semiconductor material deposited thereon. Non-limiting examples of layers that may be deposited on a substrate include dielectric layers and conductive layers, such as silicon oxide, silicon nitride, silicon carbide, metal oxides, metal nitrides, metal carbides, and metal layers. The substrate may be patterned to form features having aspect ratios between about 1:1 and about 60:1, or greater than about 1.5:1, or greater than about 4:1, or between about 1.5:1 and 60:1, or between about 1.5:1 and 40:1, or between about 1.5:1 and 20:1 (e.g., about 5:1).

[0062] Films deposited according to certain disclosed embodiments may be conformal. Conformality may be determined by step coverage. As used herein, "step coverage" may be calculated by dividing the average thickness of the deposited film on the sidewalls by the average thickness of the deposited film at the top of the feature and multiplying it by 100 to obtain a percentage. For features having an aspect ratio of about 1:5 to about 1:50, films deposited using certain disclosed embodiments may achieve step coverage of about 70% to about 120%.

[0063] The methods described herein are performed at a temperature below about 700° C. (e.g., below about 650° C.), between about 250° C. and about 350° C. (e.g., about 275° C.). It should be understood that the temperatures described herein may refer to a temperature at which a pedestal holding a substrate can be set. The terms "substrate temperature," "pedestal temperature," and "temperature" may all refer to a temperature at which the pedestal is set. The temperature may also depend on the pressure of the chamber containing the semiconductor substrate. The methods may also be performed in a processing chamber having a chamber pressure of less than about 10 Torr (e.g., between about 2 Torr and about 10 Torr).

[0064] The manufacture of semiconductor devices generally involves forming one or more silicon-based films on a semiconductor substrate in an integrated manufacturing process. Silicon-based films may include doped or undoped silicon oxide, doped or undoped silicon nitride, or doped or undoped silicon carbide. The technology nodes of the integrated circuit manufacturing industry continue to shrink. With each technology node, the geometry of the device also shrinks, and the pitch becomes smaller. High aspect ratio gaps in such technology nodes may need to be filled with insulating materials, such as insulating materials with low dielectric constants (low-k). Semiconductor integration operations may involve filling high aspect ratio gaps with low-k dielectric materials. This is the case with shallow trench isolation, intermetallic dielectric layers, passivation layers, etc. In another example, as device features shrink laterally, undesirable conductive coupling may occur due to the conductive materials becoming closer and closer, which may cause parasitic capacitance, signal propagation delays, and signal crosstalk due to capacitive effects. Low-k materials as interlayer dielectrics (ILDs) for conductive interconnects can reduce parasitic capacitance, signal delays, and signal crosstalk. Some applications, including fin field effect transistor (finFET) structures and dynamic random access memory (DRAM) bit structures, require low-k materials as sidewall spacer materials.

[0065] Silicon nitride is often used as an insulating material in many integrated circuit applications due to its step coverage, thermal stability, etch capability and etch resistance, and high breakdown voltage.

[0066] Silicon oxide has a relatively low dielectric constant, approximately 4.0, and can provide a significant reduction in capacitance as an interlayer dielectric for conductive interconnects.

[0067] Silicon carbide materials (including doped and undoped silicon carbide materials) can be used as insulating materials in integrated circuit applications, which not only provide low dielectric constants, but also provide step coverage, thermal stability, wet etch resistance, dry etch selectivity to oxides / nitrides, and high breakdown voltage. For example, the incorporation of oxygen atoms and / or nitrogen atoms can tune the properties of silicon carbide materials. In some embodiments, oxygen-doped silicon carbide films can be used as insulating materials in integrated circuit applications, which provide low dielectric constants, wet etch resistance to withstand device integration operations, and dry etch selectivity to oxides / nitrides.

[0068] There may be certain challenges in forming high-quality silicon-based films, such as providing films with excellent step coverage, low dielectric constants, and / or high breakdown voltages. Once a silicon-based film having the desired properties and composition is formed, there may be additional challenges for conformally depositing silicon-based films in high aspect ratio features. Conformal deposition may be ideal in gap filling of high aspect ratio features. Semiconductor manufacturing processes typically involve gap filling processes or dielectric gap filling processes. Typically, CVD and / or ALD methods are used to fill features. However, conventional techniques often result in the formation of undesirable seams or voids within the features. In some cases, the presence of seams and / or voids in the gap fill may result in high resistance, contamination, loss of filling material, performance degradation, and even device failure.

[0069] To avoid the formation of seams and voids during gap filling, features can be filled by a bottom-up filling process. Bottom-up filling can be performed with silicon oxide films, but it is more challenging for other silicon-based films. Silicon-based films can be deposited in features using conventional vapor deposition techniques (such as CVD and ALD). As the feature aspect ratio increases, the mass transport limitations of the CVD gas phase reaction may lead to a "bread-loafing" deposition effect, which presents a thicker deposition on the top surface and a thinner deposition on the concave surface, which causes the top of the feature opening to close before the feature can be completely filled. Unlike the CVD process, the ALD process uses a surface-mediated deposition reaction to deposit films in a layer-by-layer manner, and such films are generally conformal. Although ALD can deposit highly conformal films, it may be difficult to deposit films into high aspect ratio features. The step coverage and uniformity of the film along the sidewalls depend on, for example, the delivery of deposition precursors, reactant ions and / or radicals, and byproducts. As the lateral dimensions of features shrink, delivery and diffusion of the deposition precursors and any reactant species in the feature becomes progressively more difficult. As a result, the top of the feature is exposed to more precursor and reactant species, while the bottom of the feature is exposed to less precursor and reactant species due to diffusion limitations. This can lead to the formation of seams and voids in high aspect ratio features. A variety of methods can be used to gap fill features with silicon-containing materials to avoid the formation of seams and / or voids.

[0070] Figures 1A-1C A schematic cross-sectional view of an exemplary substrate feature being gap filled using directional etching in a de-etch-deposition process is shown. The de-etch-deposition (de-etch, de-deposition) technique involves depositing a gap fill material, then etching some of the gap fill material to open a feature opening, and then depositing the gap fill material again to complete the gap fill or at least advance the gap fill process. Figure 1AAn example of a feature 101 of a substrate 100 is shown with a gap fill material 102a deposited in the feature 101. The gap fill material 102a can be conformally deposited along a top surface, sidewalls, and a bottom surface of the feature 101. In some embodiments, the gap fill material 102a can be deposited using ALD.

[0071] Figure 1B An example of a feature 101 of a substrate 100 in which a gap fill material 102a is etched back is shown. For example, the gap fill material 102a may be etched back to form a tapered profile. Thus, more gap fill material 102a is removed near the top of the feature 101 than at the bottom of the feature 101. The etch is configured to shape the gap fill material 102a so that more material can be filled into the feature 101. In this way, the profile of the feature 101 does not restrict the diffusion of precursor and / or reactant species to the bottom and sidewalls of the feature 101 during subsequent deposition processes.

[0072] In order to reduce or eliminate the presence of voids and seams in the gap filling, different types of etching can be applied between deposition cycles. Etching conditions and chemicals can be tuned to provide non-conformal etching. In some cases, non-conformal etching preferentially removes more gap filling material 102a near the top surface of feature 101 than at the bottom surface of feature 101. Etching chemicals typically include fluorine-containing substances, wherein the fluorine-containing etchant may include xenon difluoride (XeF2), molecular fluorine (F2) or nitrogen trifluoride (NF3). Other fluorine-containing etchants may include tetrafluoromethane (CF4), fluoromethane (CH3F), difluoromethane (C2H6), tetrafluoroethylene (C2F4), hexafluoroethane (C2F6), octafluoropropane (C3F8) and sulfur hexafluoride (SF6). In some embodiments, fluorine-based etching can be plasma etching, so that radicals and / or ions of the fluorine-containing substance can react with the gap filling material 102a to remove the gap filling material 102a. The fluorine-based etch may be controlled to etch the silicon-based film and to shape the profile of the etched silicon-based film.

[0073] Figure 1C An example of a feature 101 of a substrate 100 is shown in which a gap filler material 102b is deposited to fill or substantially fill the feature 101. Although the deposition of the gap filler material 102b may result in the formation of a void 103, the size of the void 103 may be minimized by interrupting the deposition with one or more etching operations. The gap filler material 102b may be the same as the gap filler material 102a, wherein the feature 101 is filled or substantially filled by the combined gap filler materials 102a, 102b. In some embodiments, one or both of the gap filler material 102a and the gap filler material 102b include a silicon-based dielectric material, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon carbon oxynitride.

[0074] Fluorine-based etchants (e.g., fluorine radicals) can chemically react with silicon in silicon-based films to selectively remove silicon-based films. Therefore, fluorine-based etching is commonly used to etch silicon-containing layers. However, fluorine-based etching may be undesirable for several reasons. First, fluorine-based chemicals may be incompatible with certain materials and layers in semiconductor manufacturing processes, resulting in undesirable reactions with fluorine-containing substances. Second, fluorine-based etchants may leave residues on the sidewalls and other surfaces of the patterned substrate. Fluorine residues may unexpectedly enter subsequent processing steps. Third, fluorine-based plasmas may leave etched surface roughness, which may adversely affect device performance.

[0075] Figures 2A-2C Schematic cross-section of an exemplary substrate feature for gap filling using an inhibiting chemistry in a deposition-etch-deposition process. Inhibiting chemistry can be used so that gap filling material grows or otherwise forms in a feature in a topographically different manner. For example, an inhibitor can react with the material and produce a passivated surface that inhibits growth. The surface of the substrate can be more passivated in the field and upper regions of the feature, and less passivated as the distance into the feature increases. Thus, deposition at the top of the feature is selectively inhibited, while deposition in the lower portion of the feature can proceed with less inhibition or no inhibition. Figure 2A An example of a feature 201 of a substrate 200 is shown where at least the field region and upper region of the feature 201 are exposed to a reactant that inhibits the deposition / growth of a gap fill material. The reactant reacts with the substrate material to form a passivation layer 205 on the substrate 200. As an example, nitrogen (N2) or ammonia (NH3) can be used to form the passivation layer 205 composed of a nitride. The gap fill material, such as silicon dioxide (SiO2), nucleates at a slower rate on the nitride surface.

[0076] Figure 2B An example of a feature 201 of a substrate 200 is shown in which a gap fill material 202a is deposited in the feature 201. The gap fill material 202a may be deposited along a top surface, sidewalls, and bottom surface of the feature 201. The passivation layer 205 selectively inhibits the deposition / growth of the gap fill material 202a in the field region and upper region of the feature 201, such that more gap fill material 202a is deposited in the sidewalls and bottom surface of the feature 201 than in the field region and upper region of the feature 201.

[0077] Figure 2CAn example of a feature 201 of a substrate 200 is shown in which a gap fill material 202b is deposited to fill or substantially fill the feature 201. Deposition of the gap fill material 202b may result in the formation of a void 203, but the void 203 may be smaller by an inhibited chemistry that promotes bottom-up fill in the feature 201. The gap fill material 202b may be the same as the gap fill material 202a, wherein the feature 201 is filled or substantially filled by the combined gap fill materials 202a, 202b. In some embodiments, one or both of the gap fill material 202a and the gap fill material 202b include a silicon-based dielectric material, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon carbon oxynitride.

[0078] While inhibition chemistries can reduce the formation of seams and voids, inhibition chemistries are generally limited to certain types of chemistries and processes. In other words, different processes require different inhibition chemistries. In addition to silicon oxide films, many inhibition chemistries are generally not suitable for limiting the deposition / growth of silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, and silicon carbon oxynitride films. In some cases, certain inhibition chemistries may not be suitable for specific deposition techniques, such as remote plasma CVD. Therefore, the application of inhibition chemistries in gapfill may be limited to certain gapfill chemistries, deposition techniques, and even film characteristics.

[0079] Provided herein is a method and apparatus for controllably etching a silicon-based film using remote plasma etching, wherein the silicon-based film is conformally deposited in a high aspect ratio feature of a substrate. The geometry and depth of etching can be controlled by regulating process parameters (e.g., pressure, temperature, exposure time, gas flow, gas composition, and plasma power and other process parameters). In some implementations, remote plasma etching uses a remote plasma gas flow including one or more gaseous substances, wherein the one or more gaseous substances include hydrogen (H2). In some implementations, the silicon-based film includes amorphous silicon (a-Si), or the silicon-based film includes silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxynitride. After conformally depositing a silicon-based film, the silicon-based film is exposed to a remote plasma to controllably etch at least some of the silicon-based films. In some embodiments, the remote plasma removes a portion of the silicon-based film at the top and sidewall regions of the silicon-based film to reach a certain depth and / or profile. In some cases, conformal deposition and controlled etching operations are repeated to fill high aspect ratio features in a gap fill process.

[0080] Figure 3A flow chart of an exemplary method for performing deposition and etching in a substrate feature according to some implementations is shown. The operations of process 300 may be performed in a different order and / or using different, fewer, or additional operations. One or more operations of process 300 may be performed using Fig.12 1 or 13. In some implementations, the operations of process 300 may be performed at least in part according to software stored in one or more non-transitory computer-readable media.

[0081] In block 310 of process 300, a substrate is optionally provided in a processing chamber. The substrate may be supported on a substrate support or pedestal in the processing chamber. The substrate may be any wafer, semiconductor wafer, partially manufactured integrated circuit, printed circuit board, display screen, or other suitable workpiece. The substrate may be a patterned substrate having features. The one or more features may be high aspect ratio features, wherein the high aspect ratio features have a depth-to-width aspect ratio of equal to or greater than about 10:1, equal to or greater than about 15:1, equal to or greater than about 20:1, equal to or greater than about 25:1, equal to or greater than about 30:1, equal to or greater than about 40:1, equal to or greater than about 50:1, or equal to or greater than about 100:1. For some embodiments, the one or more recessed features include high aspect ratio trenches in 3D-NAND or logic devices. Before or after providing the substrate in the processing chamber, the substrate may optionally be cleaned before depositing and etching a silicon-containing layer on the substrate. For example, diluted hydrogen fluoride (HF) may be used to remove any contaminants or thin oxide layers on the substrate.

[0082] The processing chamber provides an enclosed space for depositing a silicon-containing layer on a substrate. In some cases, the processing chamber is also used to etch the silicon-containing layer using remote plasma. Using the same processing chamber for deposition and etching can minimize substrate transfer and limit air breaks between operations. The chamber walls in the processing chamber can be made of stainless steel, aluminum, plastic, ceramic or other suitable materials. The processing chamber may include a substrate support (e.g., a pedestal or an electrostatic chuck) on which the substrate is supported. In some embodiments, the processing chamber may include one or more heating elements for controlling the temperature of the substrate, wherein the one or more heating elements may be an infrared (IR) lamp, a light emitting diode (LED), or a resistive heater located in the substrate support. The processing chamber may include one or more gas pipelines for delivering gas to the processing chamber. For example, the one or more gas pipelines may include a showerhead for supplying process gas toward the substrate in the processing chamber. In some implementations, the processing chamber may be coupled to a plasma generation chamber separated from the processing chamber. The plasma generation chamber (e.g., a remote plasma chamber) may be an inductively coupled plasma (ICP) reactor, a transformer coupled plasma (TCP) reactor, or a capacitively coupled plasma (CCP) reactor. In some cases, the processing chamber further includes one or more gas outlets for exhausting gas, which may or may not be coupled to a vacuum pump to maintain a desired pressure within the processing chamber. The processing chamber used to deposit the silicon-containing film (e.g., an amorphous silicon layer) may be the same as the processing chamber used to etch the silicon-containing film.

[0083] In block 320 of process 300, an amorphous silicon layer is optionally deposited in the recessed features of the substrate. Amorphous silicon (a-Si), in contrast to crystalline silicon, is non-crystalline and lacks long range order. Techniques for depositing an amorphous silicon layer may include CVD, PECVD, ALD, PEALD or other suitable deposition techniques. In some embodiments, the amorphous silicon layer is deposited by CVD via a thermal decomposition process. The thermal decomposition process is initiated by activating a precursor gas species at an elevated temperature, wherein the precursor gas species thermally decomposes into atoms and / or molecules to be deposited by CVD.

[0084] In some embodiments, the thickness of the amorphous silicon layer can be controlled according to a predetermined deposition time to achieve a desired thickness. In some embodiments, the deposition time can be between about 5 seconds and about 500 seconds, or between about 10 seconds and about 200 seconds. In some embodiments, the desired thickness of the amorphous silicon layer can be between about 0.5 nm and about 50 nm, or between about 1 nm and about 20 nm. The deposition time can correspond to the desired thickness of the amorphous silicon layer. The thickness can be controlled so that free radicals and / or ions from subsequent remote plasma etching or plasma treatment can fully penetrate into the amorphous silicon layer.

[0085] For some embodiments, the deposition of the amorphous silicon layer can be performed by flowing one or more silicon-containing precursors into the processing chamber and toward the substrate. The silicon-containing precursor is delivered to the substrate surface, where it is adsorbed by the substrate to form a highly conformal amorphous silicon layer. In some embodiments, the formation of the amorphous silicon layer by CVD may require the deposition pressure to be controlled within the range of 0.1 Torr to 30 Torr or 0.5 Torr to about 10 Torr. The substrate temperature during the deposition of the amorphous silicon layer can be controlled between about 300°C and about 700°C or between about 400°C and about 650°C. After deposition, the step coverage of the amorphous silicon layer can be at least about 85%. In some embodiments, the step coverage can be at least about 90% or at least about 95%.

[0086] For some embodiments of CVD or PECVD, the silicon-containing precursor may be continuously delivered to the substrate until a desired thickness is obtained. In other embodiments of ALD or PEALD, the amorphous silicon layer may be formed by repeating the following operations: (1) pulsing one or more silicon-containing precursors for a predetermined time, followed by (2) purging excess precursors. In some embodiments, the amorphous silicon layer may not include long-range order, but rather, the amorphous silicon layer may have a continuous random network of silicon atoms.

[0087] As previously mentioned, the amorphous silicon layer can be highly conformal. Without being limited by any theory, a silicon-containing precursor having a low sticking coefficient may be able to produce a highly conformal amorphous silicon layer. "Stickness coefficient" is a term used to describe the ratio of the number of adsorbed species (e.g., fragments or molecules) adsorbed / adhered to a surface compared to the total number of species that impinge on the surface in the same period of time. Symbol S c Sometimes used to refer to the adhesion coefficient. S c The value of is between 0 (meaning no material adheres) and 1 (meaning all of the impinging material adheres). Various factors affect the adhesion coefficient, including the type of impinging material, the surface temperature, the surface coverage, the structural details of the surface, and the kinetic energy of the impinging material. Some materials are inherently more "sticky" than others, making them more likely to adsorb to the surface each time they impact the surface. These more sticky materials have larger adhesion coefficients (all other factors being equal). In some cases, the adhesion coefficient of the precursor (under relevant deposition conditions) can be about 0.05 or less, such as about 0.001 or less.

[0088] In some embodiments, the silicon-containing precursor may contain at least one or more Si-Si bonds and / or one or more Si-H bonds. Silicon-containing precursors suitable for use according to the disclosed embodiments may include polysilane (H3Si-(SiH2) n--SiH3), wherein n≥0. Examples of silanes are silane (SiH4), disilane (Si2H6), trisilane (Si3H8), and organosilanes, such as methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, dimethylsilane, diethylsilane, di-tert-butylsilane, allylsilane, sec-butylsilane, tert-hexylsilane (thexylsilane), isopentylsilane, tert-butyldisilane, di-tert-butyldisilane, and the like. In some embodiments, the one or more silicon-containing precursors include silane, disilane, or trisilane.

[0089] In some embodiments, the silicon-containing precursor may also include halosilanes. Halosilanes include at least one halogen group and may or may not include hydrogen and / or carbon groups. Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Specific chlorosilanes are tetrachlorosilane, trichlorosilane, dichlorosilane, monochlorosilane, chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, tert-butylchlorosilane, di-tert-butylchlorosilane, chloroisopropylsilane, chlorosec-butylsilane, tert-butyldimethylchlorosilane, tert-hexyldimethylchlorosilane (thexyldimethylchlorosilane) and the like.

[0090] In some embodiments, the silicon-containing precursor may also include aminosilanes. Aminosilanes include at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), and substituted mono-, di-, tri-, and tetra-aminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butyl silylcarbamate (tert-butyl silylcarbamate), and tert-butyl silylcarbamate. 1silylcarbamate), SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, diisopropylaminosilane, di-sec-butylaminosilane and the like. A further example of an aminosilane is trisilylamine (N(SiH3)). In some embodiments, aminosilanes having two or more amine groups attached to the central Si atom may be used. These may cause less damage than aminosilanes having only a single amine group attached.

[0091] Further examples of silicon-containing precursors include trimethylsilane (3MS); ethylsilane; butasilane; pentasilane; octasilane; heptasilane; hexasilane; cyclobutasilane; 1-dimethylamino-1,1,5,5,5-pentamethyldisiloxane; cycloheptasilane; cyclohexasilane; cyclooctasilane; cyclopentasilane; 1,4-dioxa-2 ,3,5,6-tetrasilacyclohexane (1,4-dioxa-2,3,5,6-tetrasilacyclohexane); diethoxymethylsilane (DEMS); diethoxysilane (DES); dimethoxymethylsilane (dimethoxymethylsilane); dimethoxysilane (DMOS); methyl-diethoxysilane (MDES); methyl-dimethoxysilane (MDMS); octamethoxydodecylsiloxane (OMODDS); tert-butoxydisilane (tert-butoxydisilane); tetramethylcyclotetrasiloxane (TMCTS); tetraoxymethylcyclotetrasiloxane (tetraoxymethylcyclotetrasiloxane: TOMCTS); triethoxysilane (TES); triethoxysiloxane (TRIES); and trimethoxysilane (TMS or TriMOS).

[0092] In addition to the precursor gases, an inert carrier or diluent gas may be flowed to the substrate. Examples of inert carrier or diluent gases include, but are not limited to, helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), and nitrogen (N2). In some embodiments, a gas mixture of one or more source gases and one or more inert carrier or diluent gases may be provided in a remote plasma source.

[0093] For example, the one or more silicon-containing precursors include silane, disilane, trisilane, or other silane-based precursors. The silane-based precursor may flow into the processing chamber and adsorb on the exposed surface of the substrate. The silane-based precursor may be thermally decomposed under certain CVD operating conditions (e.g., 400° C.-650° C., 0.1 Torr-30 Torr) to form an amorphous silicon layer. Thermal decomposition cracks the silane-based precursor into atoms and / or molecules to be deposited on the substrate surface at elevated temperatures. Plasma-based deposition processes may result in non-conformal deposition of amorphous silicon, but thermal decomposition of silane-based precursors at sufficiently high temperatures provides highly conformal deposition of amorphous silicon.

[0094] At frame 330 of process 300, a conformal silicon-containing film is formed in the recessed features of the substrate. In some embodiments, the silicon-containing film is an amorphous silicon layer. Therefore, the formation of a conformal silicon-containing film in the recessed features of the substrate at frame 330 has been completed by depositing an amorphous silicon layer at frame 320. In some other embodiments, the silicon-containing film comprises two elements, three elements, four elements, or five or more elements. For example, the silicon-containing layer comprises silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or silicon oxynitride. The formation of a multi-element silicon-containing film can be carried out by doping a dopant (except hydrogen) into the amorphous silicon layer deposited at frame 320, thereby converting the amorphous silicon layer into a multi-element silicon-containing film at frame 330. Alternatively, the formation of a multi-element silicon-containing film can be carried out without depositing an amorphous silicon layer at frame 320. In this case, the multi-element silicon-containing film is conformally deposited by CVD, PECVD, ALD, PEALD or other suitable deposition techniques. In one example, the silicon-carbon containing film can be deposited on the substrate by remote plasma CVD. In another example, the multi-element silicon containing film is conformally deposited by thermal ALD or thermal CVD, and then the silicon containing film is treated with a densification gas plasma.

[0095] In the case of forming a silicon-containing film by conversion of an amorphous silicon layer, the amorphous silicon layer may be exposed to a gas plasma stream. The gas plasma stream may contain one or more gas species, including oxygen-containing reactants (e.g., oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), nitrous oxide (N2O), or nitrogen dioxide (NO2)), carbon-containing reactants (e.g., acetylene (C2H2), ethylene (C2H4), or propylene (C3H6)), hydrogen-containing reactants (e.g., hydrogen (H2) or methane (CH4)), or nitrogen-containing reactants (e.g., nitrogen (N2), ammonia (NH3), diazene (N2H2), hydrazine (N2H4)), or mixtures thereof. Thus, the gas plasma stream may include hydrogen radicals (H*), nitrogen radicals (N*), oxygen radicals (O*), carbon radicals (C*), amine radicals (NH*, NH2*), or combinations thereof. In some embodiments, the gas plasma stream is a remote gas plasma stream. In some cases where the silicon-containing film is formed by conversion of an amorphous silicon layer, the amorphous silicon layer may be exposed to an elevated temperature, which may be between about 200°C and about 650°C, with one or more gas species flowed to the substrate.

[0096] In the case of forming a silicon-containing film by CVD, PECVD, ALD, PEALD or other suitable deposition techniques without converting an amorphous silicon layer, a silicon-containing precursor may react in a gas phase to deposit a silicon-containing film. A silicon-containing precursor may react with one or more reactants in a gas phase to deposit a silicon-containing film. In some embodiments, the one or more reactants may include oxygen-containing reactants, such as oxygen, ozone, carbon monoxide, carbon dioxide, nitrous oxide, nitrogen dioxide or a mixture thereof. In some embodiments, the one or more reactants may include carbon-containing reactants, such as acetylene, methane, ethylene, propylene or a mixture thereof. In some embodiments, the one or more reactants may include nitrogen-containing reactants, such as nitrogen, ammonia, diazene, hydrazine or a mixture thereof. The silicon-containing precursor may have one or more silicon-hydrogen (Si-H) bonds and / or one or more silicon-silicon (Si-Si) bonds. In some embodiments, the silicon-containing precursor may have one or more silicon-carbon (Si—C) bonds, one or more silicon-oxygen (Si—O) bonds, and / or one or more silicon-nitrogen (Si—N) bonds.

[0097] A silicon-containing film having excellent step coverage can be formed in a recessed feature of a substrate. The step coverage can be calculated by comparing the average thickness of the deposited film on the bottom, sidewall or top of the feature with the average thickness of the deposited film on another portion of the feature. For example, the step coverage can be calculated by dividing the average thickness of the deposited film on the sidewall by the average thickness of the deposited film at the top of the feature and multiplying by 100 to obtain a percentage. In some embodiments, the step coverage of the silicon-containing film can be at least about 85%. In some embodiments, the step coverage can be at least about 90% or at least about 95%. Depositing a silicon-containing film having excellent step coverage along the sidewall of the recessed feature can establish a vertical structure.

[0098] In some cases, the silicon-containing film can be conformally deposited in the recessed features using remote plasma CVD such as remote hydrogen plasma CVD. The silicon-containing film can be formed by causing the silicon-containing precursor to flow into the processing chamber via the first gas outlet and introducing hydrogen radicals generated from the remote plasma source into the processing chamber via the second gas outlet. The first gas outlet can be located downstream of the second gas outlet. The hydrogen radicals react with the silicon-containing precursor in an environment adjacent to the substrate to deposit the silicon-containing film. Si-H bonds and / or Si-Si bonds are selectively cleaved by hydrogen radicals and used as reaction sites for forming bonds between silicon-containing precursors. The broken bonds can also serve as sites for crosslinking during or after deposition. The bonding and crosslinking at the reaction sites can form the main skeleton or matrix in the resulting silicon-containing film. In some implementations, the hydrogen radicals are in a low energy state or ground state when reacting with the silicon-containing precursor in an environment adjacent to the substrate. The process conditions can be controlled and the plasma processing device can be designed to relax the hydrogen radicals from an excited state to a low energy state or ground state when reacting with the silicon-containing precursor. As such, the hydrogen radicals may selectively cleave Si-H and Si-Si bonds, while generally preserving Si-O, Si-N, and Si-C bonds. In some implementations, the hydrogen radicals may be delivered with an inert gas such as argon (Ar), helium (He), neon (Ne), krypton (Kr), or xenon (Xe). In some implementations, one or more co-reactants may flow into the processing chamber to react with the silicon-containing precursor to increase or decrease the carbon, oxygen, or nitrogen content of the silicon-containing film. Details regarding the remote hydrogen plasma CVD process for depositing silicon-containing films can be found in U.S. Patent No. 10,325,773, filed by Varadarajan et al. on February 6, 2015, entitled “CONFORMAL DEPOSITION OF SILICON CARBIDE FILMS,” U.S. Patent Application No. 16 / 044,357, filed by Weimer et al. on July 24, 2018, entitled “CONFORMAL DEPOSITION OF SILICON CARBIDE FILMS USING HETEROGENEOUS PRECURSOR INTERACTION,” and U.S. Patent Application No. 17 / 286,407, filed by Yuan et al. on April 16, 2021, entitled “DOPED OR UNDOPED SILICON CARBIDE DEPOSITION AND REMOTE HYDROGEN PLASMA EXPOSURE FOR GAPFILL,” each of which is incorporated by reference in its entirety for all purposes.

[0099] In some cases, the silicon-containing film may be conformally deposited in the recessed features using ALD or PEALD. In some implementations, the silicon-containing film is conformally deposited in the recessed features using remote plasma ALD. ALD is a technique for depositing thin layers of material using continuous self-limiting reactions. Typically, an ALD cycle includes operations of delivering and adsorbing at least one precursor to a substrate surface and then reacting the adsorbed precursor with one or more reactants to form a partial layer of the film. As an example, a silicon nitride ALD cycle may include the following operations: (i) delivering / adsorbing a silicon-containing precursor, (ii) removing the silicon-containing precursor from the chamber, (iii) exposing the nitrogen-containing reactant to an optional plasma, and (iv) removing excess reactants from the chamber. In some implementations, the plasma may include radical species of nitrogen, ammonia, and / or hydrogen (N*, NH2*, NH*, and / or H*) that react with the adsorbed silicon-containing precursor to deposit a silicon nitride film. In some cases, the plasma may be an in-situ plasma or a remote plasma. Other types of films may be deposited using pulses of multiple precursors and co-reactants.

[0100] In some cases, the silicon-containing film may be conformally deposited in the recessed features using thermal CVD or thermal ALD, and subsequently subjected to plasma treatment using a densification gas plasma operation, thereby changing the composition or density of the silicon-containing film. The thermal CVD or thermal ALD operation may be performed at a substrate temperature of less than about 700° C. or less than about 650° C. The plasma treatment operation may be performed at a substrate temperature of less than about 700° C. or less than about 650° C. The deposition of the silicon-containing film by thermal CVD or thermal ALD may be performed using a halogen-free silicon-containing precursor.

[0101] The silicon-containing film is deposited to a thickness that partially fills the recessed feature. The silicon-containing film is continuously formed along the bottom, sidewalls, and top surfaces of the recessed feature. In some implementations, the thickness of the silicon-containing film is equal to or less than about Between about About between About between or between About between.

[0102] In block 340 of process 300, at least a portion of the silicon-containing film is etched to at least one of a desired depth and a desired profile by exposure to a remote plasma. In some implementations, the remote plasma is a remote hydrogen plasma. The remote plasma exposure is provided under conditions that achieve controlled etching of the silicon-containing film in the recessed feature. In addition to or as an alternative to densifying or treating the silicon-containing film, the remote plasma selectively removes a controlled amount of the silicon-containing film at or near the top of the recessed feature and selectively removes another controlled amount of the silicon-containing film along the sidewall of the recessed feature. As used herein, "controlled etching" or "controlled amount" does not refer to an exact amount or value, but more broadly refers to the overall shape of the silicon-containing film achieved by the remote plasma exposure. Similarly, as used herein, "desired profile" and "desired depth" do not refer to exact amounts or values, but more broadly refer to an obtained profile close to a target profile and an obtained depth close to a target depth. In some cases, the desired profile or desired depth is a profile or depth anywhere within 1 nm of a target profile or target depth and within 5 or 10 degrees of a target cone angle. The remote plasma etch preferentially removes more silicon-containing film at a certain location of the recessed feature than at other locations of the recessed feature. How much silicon-containing film is removed at various locations of the recessed feature (i.e., top, bottom, sidewalls) is affected by the remote plasma etch conditions.

[0103] In some implementations, the remote plasma includes one or more plasma-activated species including hydrogen (H*), halogens (e.g., F*, Cl*), hydrocarbons (e.g., CH*), fluorocarbons (e.g., CF*), amines (e.g., NH*), or combinations thereof. For example, the one or more plasma-activated species include hydrogen radicals. The plasma-activated species may be generated from one or more source gases. Example source gases may include, but are not limited to, hydrogen (H2), fluorine (F2), chlorine (Cl2), bromine (Br2), hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), nitrogen trifluoride (NF3), boron trichloride (BCl3), ammonia (NH3), methane (CH4), ethane (C2H6), acetylene (C2H2), ethylene (C2H4), propylene (C3H6), butene (C4H8), pentadiene (C5H8), hexene (C6H 12), propyne (C3H4), butyne (C4H6), pentyne (C5H8), toluene (C7H8), benzene (C6H6), tetrafluoromethane (CF4), octafluorocyclobutane (C4F8), hexafluorobutadiene (C4F6) and difluoromethane (CH2F2). The one or more source gases are delivered to the remote plasma source from a gas supply source. In some cases, the one or more source gases are supplied together with an inert gas (e.g., argon, helium, neon, krypton or xenon). The one or more source gases are ignited to generate a plasma including a plasma-activated species. The plasma-activated species may include ions, free radicals, charged neutral species and other reactive species of the one or more source gases. The plasma-activated species may be delivered from the remote plasma source to the processing chamber to etch at least a portion of the silicon-containing film. In some embodiments, the remote plasma source is located upstream of the processing chamber.

[0104] The remote plasma etching occurs without delivering any silicon-containing precursors. Although the deposition of the silicon-containing film may involve the delivery of silicon-containing precursors, the remote plasma exposure for etching at least a portion of the silicon-containing film terminates the flow of any silicon-containing precursors. Additionally or alternatively, the remote plasma etching occurs without delivering any oxygen-containing species, any carbon-containing species, or any nitrogen-containing species. Although some of the above-mentioned species may be used as dopants during the conversion of the amorphous silicon layer to form a multi-element silicon-containing film, such species do not flow during the remote plasma etching.

[0105] In some implementations, deposition of the silicon-containing film occurs in the same processing chamber as the remote plasma etch. Conformal deposition of the silicon-containing film can be performed in the processing chamber, and etching of at least a portion of the silicon-containing film using remote plasma can also be performed in the processing chamber. This allows deposition and etching to occur in the same tool or chamber, so that deposition and etching occur without introducing vacuum breaks (such as air breaks). Vacuum breaks can reduce yields and cause substrate oxidation, which can result in higher resistance and performance degradation. In some cases, plasma processing operations using densification gas plasma and remote plasma etching can occur in the same processing chamber.

[0106] One or both of the desired profile and the desired depth are achieved by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition of remote plasma, relative concentration of gas composition, and RF power. One or more of the aforementioned etching parameters can be controlled to produce different types of etching profiles and etching depths. Typically, conventional etching of silicon-containing films involves fluorine-based etchants, which leave undesirable residues, or conventional etching of silicon-containing films can be controlled and directional. Remote plasma etching of the present invention provides a variety of etching profiles and depths according to the conditions of the remote plasma. This allows controlled removal of the feature top and / or sidewall silicon-containing film.

[0107] In some embodiments, the depth of remote plasma etching is adjusted according to the chamber pressure. The chamber pressure may be between about 0.01 Torr and about 10 Torr, between about 0.05 Torr and about 5 Torr, or between about 0.1 Torr and about 2 Torr. In general, the chamber pressure may be adjusted to obtain more effective concentrations of the etchant. By adjusting to a lower pressure, the etching rate increases and the etching depth becomes deeper. Using high pressure, more silicon-containing films may be selectively etched at or near the top of the recessed feature than at or near the middle and bottom of the recessed feature, and using low pressure, more silicon-containing films may be etched at or near the top and middle of the recessed feature than at or near the bottom of the recessed feature.

[0108] In some embodiments, the depth of remote plasma etching is adjusted according to RF power.RF power can be between about 300W and about 15kW per station, between about 500W and about 10kW per station, or between about 1kW and about 8kW per station.RF power can be regulated to increase the generation of hydrogen radical species, amine radical species or other radical species.In some embodiments, the remote plasma source can be an inductively coupled plasma (ICP) reactor for generating radical species.By adjusting to higher RF power, the concentration of etchant increases and the etching depth becomes deeper.Using low RF power, more silicon-containing films can be selectively etched at or near the top of the recessed feature than at or near the middle and bottom of the recessed feature, and more silicon-containing films can be selectively etched at or near the top and middle of the recessed feature than at or near the bottom of the recessed feature using higher RF power.

[0109] In some embodiments, the depth of remote plasma etching is adjusted according to the substrate temperature. The substrate temperature may be between about 25°C and about 750°C, between about 50°C and about 700°C, or between about 200°C and about 650°C. The temperature may be regulated to increase the etching rate of the silicon-containing film. By adjusting to a lower temperature, the etching depth becomes deeper. Moderate temperatures may selectively remove more silicon-containing film at or near the top of the recessed feature than at or near the middle and bottom of the recessed feature, while lower temperatures may selectively remove more silicon-containing film at or near the top and middle of the recessed feature than at or near the bottom of the recessed feature.

[0110] In some embodiments, the depth of remote plasma etching is adjusted according to the exposure time. The exposure time can be between about 1 second and about 5 minutes, about 2 seconds and about 3 minutes, or about 5 seconds and about 2 minutes. It should be understood that the exposure time can vary according to the size of the recessed features. By adjusting to a longer exposure time, the etching depth becomes deeper.

[0111] In some embodiments, at least one of the depth and profile of remote plasma etching is adjusted according to the relative concentration of gas composition. The gas composition may include a source gas, such as hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or a mixture thereof. The gas composition may further include an inert gas, such as argon, helium, neon, krypton, or xenon. For example, the gas composition may include a mixture of hydrogen and helium or a mixture of hydrogen and argon. The relative concentration of hydrogen and inert gas may be adjusted to affect the etching depth and / or profile. In some implementations, the flow rate ratio of hydrogen to inert gas may be between about 1:10 and about 100:1, between about 1:2 and about 50:1, or between about 1:1 and about 20:1.

[0112] Whether increasing the concentration of the source gas increases or decreases the etch rate depends on the chemical properties of the source gas. Accordingly, an increase in the source gas concentration may or may not result in a deeper etch. In the case of utilizing hydrogen and an inert gas, adjusting to a medium to low concentration of the source gas results in a deeper etch depth. A low source gas concentration can selectively remove more silicon-containing film at or near the top of the recessed feature than at or near the middle and bottom of the recessed feature.

[0113] Increasing or decreasing the source gas concentration relative to the inert gas concentration can affect the profile of the remote plasma etching. Other etching parameters (such as chamber pressure, substrate temperature, RF power, exposure time and gas composition) can additionally or alternatively affect the profile of the remote plasma etching. By controlling the deposition thickness and etching depth in each step, a final film profile with a desired taper can be formed. In some cases, controlling the pressure or mean free path can be used to change the taper of the film in the recessed feature. For example, lower pressures can cause hydrogen radicals to diffuse deeper in the recessed feature, while higher pressures can cause more concentrated etching near the top of the recessed feature. Nevertheless, the combination of pressure, temperature, plasma power, exposure time and gas composition can tune the etching profile in the present invention. The etching profile can be described according to the shape of the silicon-containing film at various positions (i.e., top, bottom, sidewall) of the recessed feature. In some cases, the etching profile can have a taper so that the thickness of the silicon-containing film is reduced closer to the top of the recessed feature than at the bottom of the recessed feature. The taper can be measured by the slope or angle from the upper region of the silicon-containing film in the recessed feature relative to a line perpendicular to the substrate surface. The slope or angle can be between 0 and 60 degrees, between about 5 and about 50 degrees, or between about 10 and about 45 degrees. In some cases, the etch profile can have rounded or sharp corners at the upper region of the silicon-containing film in the recessed feature. In some cases, the etch profile can reflect notches, bends, undercuts, faceting, and other deviations from a vertically shaped film in the recessed feature.

[0114] Manipulating the various knobs of the remote plasma etch can modify the etch depth and etch profile of the remote plasma etch. In some implementations, the remote plasma etch removes more silicon-containing film near the recessed feature opening than along the recessed feature sidewalls and bottom. In some implementations, the remote plasma etch provides a tapered etch profile. For example, the tapered etch profile may be between about 30 degrees and about 70 degrees. In some implementations, the remote plasma etch removes at least 10%, at least 20%, at least 25%, at least 30%, at least 40%, or at least 50% of the silicon-containing film from the top of the recessed feature. For example, the remote plasma etch partially removes the silicon-containing film so that between about 10% and about 50% of the silicon-containing film is removed from the top of the recessed feature.

[0115] In some implementations, process 300 further includes repeating deposition and etching operations to fill or at least substantially fill the recessed features. As used herein, substantially filling relative to filling the recessed features may refer to a silicon-containing gap filling material that occupies at least 98% of the recessed feature volume. The recessed features may be filled without seams or gaps. Controlling the shape and depth of the remote plasma etch between deposition operations may achieve gap filling without seams or gaps. After the remote plasma etch at frame 340, an additional thickness of a silicon-containing film may be deposited as a gap filling material after process 300. The initially deposited silicon-containing film and any additional thickness of the silicon-containing film may constitute a silicon-containing gap filling material. The additional thickness of the silicon-containing film may partially fill or completely fill the one or more recessed features. Some aspects of depositing an additional thickness of a silicon-containing film may be equivalent to depositing and forming a silicon-containing film at frame 330. Thereafter, process 300 may be followed by another remote plasma etch that shapes the silicon-containing gap filling material according to at least one of a desired depth and a desired profile. Some aspects of this remote plasma etch may be identical to the remote plasma etch of block 340. However, etch parameters such as chamber pressure, substrate temperature, RF power, gas composition, and relative concentrations of gas composition may be the same or different than block 340. The deposition and etching operations may be repeated at least once, at least twice, at least three times, at least five times, at least eight times, or at least ten times to fill or at least substantially fill the recessed features before performing a final deposition of the silicon-containing gapfill material.

[0116] Figure 4A-4B A schematic cross-sectional view of an exemplary substrate feature partially etched to a shallow depth using a remote plasma according to some implementations is shown. Figure 4AAn example of a feature 401 of a substrate 400 in which a silicon-containing layer 402 is deposited is shown. The silicon-containing layer 402 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 401. In some embodiments, the silicon-containing layer 402 is an amorphous silicon layer deposited by thermal CVD using a silane-based precursor that is thermally decomposed on the exposed surface of the substrate 400. In some embodiments, the silicon-containing layer 402 is a doped silicon layer, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon oxynitride carbonitride. The doped silicon layer can be deposited using any suitable deposition technique, such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer can be deposited by remote plasma CVD. Alternatively, the doped silicon layer can be formed by converting the amorphous silicon layer, wherein the conversion occurs by exposing the amorphous silicon layer to a plasma stream comprising a gaseous substance containing carbon, nitrogen, and / or oxygen. Alternatively, the conversion may occur by exposing the amorphous silicon layer to an elevated temperature and flowing a gas species containing carbon, nitrogen, and / or oxygen, wherein the elevated temperature may be between about 200° C. and about 650° C. In some implementations, the silicon-containing layer 402 is deposited by thermal CVD or thermal ALD and is followed by a plasma treatment operation using a densification gas plasma. The plasma treatment operation may at least change the composition or density of the silicon-containing layer 402. The silicon-containing layer 402 (which may include an amorphous silicon layer or a doped silicon layer) may be deposited within the feature 401 to have a step coverage of at least 85%, at least 90%, or at least 95%. The silicon-containing layer 402 only partially fills the feature 401.

[0117] Figure 4B An example of a feature 401 of a substrate 400 in which a silicon-containing layer 402 is partially etched is shown. The substrate 400 may be exposed to a remote plasma under certain conditions to partially etch the silicon-containing layer 402 to a shallow depth. The remote plasma may remove the silicon-containing layer 402 to an etching depth of between about 1% and 50% from the top of the feature 401, between about 5% and about 45% from the top of the feature 401, or between about 10% and about 40% from the top of the feature 401. In some implementations, the partially etched silicon-containing layer 402 may have a tapered profile. The remote plasma removes the silicon-containing layer 402 from the top of the feature 401, but not from the middle or bottom of the feature 401. The remote plasma may include one or more gas species, including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma comprises hydrogen and an inert gas. In some embodiments, the remote plasma may be generated in a plasma source located upstream of a processing chamber for depositing and etching the silicon-containing layer 402. Remote plasma control of etching parameters chamber pressure, substrate temperature, RF power, exposure time, gas composition and / or relative concentrations of gas compositions to perform Figure 4BBy tuning one or more of the aforementioned etching parameters, the silicon-containing layer 402 can undergo a partial etching in the feature 401 to achieve a desired depth and / or profile. In some implementations, the remote plasma for removing at least a portion of the silicon-containing layer 402 can continue after the plasma treatment operation of the silicon-containing layer 402 using the densification gas plasma.

[0118] Figure 5A-5B A schematic cross-sectional view of an exemplary substrate feature partially etched to a deep depth using a remote plasma according to some implementations is shown. Figure 5A An example of a feature 501 of a substrate 500 in which a silicon-containing layer 502 is deposited in the feature 501 is shown. The silicon-containing layer 502 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 501. In some embodiments, the silicon-containing layer 502 is an amorphous silicon layer deposited by thermal CVD using a silane-based precursor that is thermally decomposed on the exposed surface of the substrate 500. In some embodiments, the silicon-containing layer 502 is a doped silicon layer, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbon oxynitride. The doped silicon layer can be deposited using any suitable deposition technique, such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer can be deposited by remote plasma CVD. Alternatively, the doped silicon layer can be formed by converting an amorphous silicon layer, wherein the conversion occurs by exposing the amorphous silicon layer to a plasma flow including a gas species containing carbon, nitrogen, and / or oxygen, or by exposing the amorphous silicon layer to an elevated temperature and flowing a gas species containing carbon, nitrogen, and / or oxygen to the substrate. In some implementations, the doped silicon layer can be formed by thermal CVD or thermal ALD, followed by a plasma treatment operation using a densification gas plasma. The silicon-containing layer 502 (which may include an amorphous silicon layer or a doped silicon layer) can be deposited within the feature 401 to have a step coverage of at least 85%, at least 90%, or at least 95%. The silicon-containing layer 502 only partially fills the feature 501.

[0119] Figure 5B An example of a substrate 500 feature 501 is shown with a silicon-containing layer 502 partially etched. The substrate 500 can be exposed to a remote plasma under conditions to partially etch the silicon-containing layer 502 to a deep depth. The remote plasma can remove the silicon-containing layer 502 to an etch depth of between about 40% and 95% from the top of the feature 501, between about 50% and about 90% from the top of the feature 501, or between about 60% and about 85% from the top of the feature 501. In some implementations, the partially etched silicon-containing layer 502 can have a tapered profile. Figure 5B The silicon-containing layer 502 may be etched to a depth of Figure 4BThe remote plasma may include one or more gas species, including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma includes hydrogen and an inert gas. In some embodiments, the remote plasma may be generated in a plasma source located upstream of a process chamber used to deposit and etch the silicon-containing layer 502. The remote plasma controls the etching parameters chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentrations of the gas composition to perform etching. Figure 5B By tuning one or more of the aforementioned etching parameters, silicon-containing layer 502 can undergo a partial etching in feature 501 to achieve a desired depth and / or profile.

[0120] Figure 6A-6B A schematic cross-sectional view of an exemplary substrate feature partially etched at a top surface using a remote plasma according to some implementations is shown. Fig. 6A An example of a feature 601 of a substrate 600 in which a silicon-containing layer 602 is deposited in the feature 601 is shown. The silicon-containing layer 602 is conformally deposited along the top surface, sidewalls, and bottom surface of the feature 601. In some embodiments, the silicon-containing layer 602 is an amorphous silicon layer deposited by thermal CVD using a silane-based precursor that is thermally decomposed on the exposed surface of the substrate 600. In some embodiments, the silicon-containing layer 602 is a doped silicon layer, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbonitride. The doped silicon layer can be deposited using any suitable deposition technique, such as ALD, PEALD, CVD, PECVD, or other techniques. For example, the doped silicon layer can be deposited by remote plasma CVD. Alternatively, the doped silicon layer can be formed by converting an amorphous silicon layer, wherein the conversion occurs by exposing the amorphous silicon layer to a plasma flow including a gas species containing carbon, nitrogen, and / or oxygen, or by exposing the amorphous silicon layer to an elevated temperature and flowing a gas species containing carbon, nitrogen, and / or oxygen to the substrate. In some implementations, the doped silicon layer can be formed by thermal CVD or thermal ALD, followed by a plasma treatment operation using a densification gas plasma. The silicon-containing layer 602 (which may include an amorphous silicon layer or a doped silicon layer) can be deposited within the feature 601 to have a step coverage of at least 85%, at least 90%, or at least 95%. The silicon-containing layer 602 only partially fills the feature 601.

[0121] Figure 6BAn example of a feature 601 of a substrate 600 with a silicon-containing layer 602 partially etched is shown. The substrate 600 can be exposed to a remote plasma under conditions to partially etch the silicon-containing layer 602 such that the silicon-containing layer 602 is substantially removed from the top surface of the feature 601, while the silicon-containing layer 602 along the sidewalls and bottom surface of the feature 601 substantially remains. The silicon-containing layer 602 can be shaped such that the opening at the top surface of the feature 601 is larger than the opening in the middle or bottom of the feature 601. The opening at the top surface of the feature 601 can taper as the silicon-containing layer 602 extends downward. Figure 6B The silicon-containing layer 602 may be etched to a depth of Figure 5B The silicon-containing layer 502 has different depths and profiles and is etched to a depth and profile different from that of the silicon-containing layer 502. Figure 4B The remote plasma may include one or more gas species including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some embodiments, the remote plasma comprises hydrogen and an inert gas. In some embodiments, the remote plasma may be generated in a plasma source located upstream of a process chamber used to deposit and etch the silicon-containing layer 602. The remote plasma controls the etching parameters chamber pressure, substrate temperature, RF power, exposure time, gas composition, and / or relative concentrations of the gas composition to perform etching. Figure 6B By tuning one or more of the aforementioned etching parameters, the silicon-containing layer 602 can undergo a partial etching in the feature 601 to achieve a desired depth and / or profile.

[0122] Figures 7A-7C A schematic cross-sectional view of an exemplary substrate feature performing gap filling in a deposition-etch-deposition process according to some implementations. The gap filling operation can be compared to Figures 7A-7C The gap filling operation may be performed using, for example, Fig.12 and 13 The plasma processing apparatus shown is used for processing.

[0123] exist Fig. 7A, a silicon-containing layer 702a of a first thickness is deposited in a feature 701 of a substrate 700. Although substrate 700 shows only a single feature 701, it should be understood that substrate 700 may have one or more features 701. In some embodiments, the silicon-containing layer 702a includes amorphous silicon. In some other embodiments, the silicon-containing layer 702a includes a doped silicon layer, such as silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon oxynitride, silicon carbonitride, or silicon carbon nitride. The silicon-containing layer 702a of the first thickness can be deposited using any suitable deposition technique. In the case where the silicon-containing layer 702a is amorphous silicon, for example, the silicon-containing layer 702a can be deposited by thermal CVD using a silane-based precursor that is thermally decomposed at an elevated temperature to be adsorbed on the substrate surface. In the case where the silicon-containing layer 702a is a doped silicon layer, the silicon-containing layer 702a can be deposited by ALD, PEALD, CVD, PECVD, or other techniques. Alternatively, the silicon-containing layer 702a may be formed by converting amorphous silicon, wherein the conversion occurs by exposure to a plasma flow containing carbon, nitrogen, and / or oxygen to form doped silicon, or by exposure to an elevated temperature and flowing a gas species containing carbon, nitrogen, and / or oxygen to the substrate to form doped silicon. In some implementations, the silicon-containing layer 702a may be formed by thermal CVD or thermal ALD, wherein the silicon-containing layer 702a is exposed to a plasma treatment operation using a densifying gas plasma that affects the composition and / or density of the silicon-containing layer 702a. The silicon-containing layer 702a (which may include an amorphous silicon layer or a doped silicon layer) may be deposited within the feature 701 to have a step coverage of at least 85%, at least 90%, or at least 95%.

[0124] exist Figure 7B In the embodiment of the present invention, a silicon-containing layer 702a of a first thickness is exposed to a remote plasma to partially etch the silicon-containing layer 702a. Etching is performed under conditions that increase the size of the opening at the top surface of the feature 701. The remote plasma may etch the silicon-containing layer 702a to a shallow depth so that the opening is free of gap filling material near the top of the feature 701. The remote plasma may etch the silicon-containing layer 702a into a tapered profile that narrows as the silicon-containing layer 702a extends downward in the feature 701. The remote plasma may include one or more gaseous substances, including hydrogen, ammonia, one or more hydrocarbons, one or more fluorocarbons, one or more halides, or mixtures thereof. In some implementations, the remote plasma includes hydrogen and an inert gas. In some implementations, the remote plasma may be generated in a plasma source located upstream of a processing chamber for depositing and etching the silicon-containing layer 702a. This allows alternating deposition and remote plasma etching cycles in the same tool or chamber. Therefore, deposition and etching may occur without introducing a vacuum interruption (e.g., an air interruption) during gap filling. Remote plasma control of etching parameters chamber pressure, substrate temperature, RF power, exposure time, gas composition and / or relative concentrations of gas compositions to perform Figure 7B By tuning one or more of the aforementioned etching parameters, the silicon-containing layer 702a can undergo a partial etching in the feature 701 to achieve a desired depth and / or profile.

[0125] exist Figure 7C , a second thickness of silicon-containing layer 702b is deposited in feature 701 of substrate 700. The second thickness of silicon-containing layer 702b is deposited on the first thickness of silicon-containing layer 702a. Some aspects of depositing the second thickness may be equivalent to or at least similar to the aspects of depositing the first thickness. The second thickness of silicon-containing layer 702b may be compositionally identical to the first thickness of silicon-containing layer 702a, wherein the silicon-containing layers 702a, 702b serve as gap fill materials. The deposition of the first thickness, the etching, and the deposition of the second thickness may occur in the same tool or the same processing chamber. The deposition of the first thickness may be a thermal CVD process, the etching of the first thickness may be a remote plasma etch, and the deposition of the second thickness may also be a thermal CVD process, all of which may be performed in the same tool or the same processing chamber. The deposition of the first thickness may be a thermal CVD or thermal ALD process, the processing may be a plasma process, the etching of the first thickness may be a remote plasma etch, the deposition of the second thickness may also be a thermal CVD or thermal ALD process, and the processing may be a plasma process, all of which may be performed in the same tool or the same processing chamber. The second thickness can have a step coverage of at least 85%, at least 90%, or at least 95%. In some cases, the silicon-containing layers 702a, 702b can fill or at least substantially fill the feature 701. Interrupting the deposition operation using remote plasma etching as described herein can avoid seams and / or voids during gap filling or at least minimize the size of seams and / or voids. The gap filling material deposition and remote plasma etching operations of the present invention can be repeated until at least 100% of the gap fill material is removed. Figure 7C Complete the gap filling.

[0126] As discussed above, aspects of the present invention may involve depositing a silicon-containing layer in a feature followed by a controlled etching process using a remote plasma. However, regardless of whether an etching process is performed after depositing the silicon-containing layer in the feature, aspects of the present invention may involve depositing the silicon-containing layer by thermal ALD and / or thermal CVD. Such deposition may be performed using halogen-free deposition precursors. The silicon-containing layer may have an adjustable film composition and deposition. In some implementations, the silicon-containing layer deposited by thermal ALD and / or thermal CVD is treated by exposure to a densification gas plasma. The deposition of the silicon-containing layer may be performed at a temperature below about 700°C (e.g., below about 650°C), between about 250°C and about 350°C (e.g., about 275°C).

[0127] Fig. 8AA process flow diagram is provided that depicts operations that may be performed according to certain disclosed embodiments. In operation 802, a patterned substrate may be provided in a process chamber that may be set to a chamber pressure of about 0 Torr to about 30 Torr. The pressure may vary from operation to operation, or may be Fig. 8A remains the same in all operations in , or can be Fig. 8A The following references Fig.12 and 13 An example processing chamber is further described. As described above, the substrate may be a silicon wafer on which one or more dielectric, conductive or semiconductor materials are deposited. The substrate may be patterned to have features with an aspect ratio between about 1:1 and about 60:1, or greater than about 1.5:1, or greater than about 4:1, or between about 1.5:1 and 60:1, or between about 1.5:1 and 40:1, or between about 1.5:1 and 20:1 (e.g., about 5:1). When the patterned substrate is provided to the processing chamber, the substrate may be subjected to a "temperature soak", whereby the substrate is heated to a process temperature at which the substrate will be subjected to the operations described herein. For example, in some embodiments, the substrate may be heated to a temperature below about 700°C, such as below about 650°C, between about 650°C and about 400°C, or about 275°C.

[0128] In operation 804, the substrate is exposed to a silicon-containing deposition precursor and a reactant to form a conformal silicon-containing film in a thermal manner. In various embodiments, "halogen-free" means that the silicon-containing precursor molecule does not contain any halogen substituents. In various embodiments, the silicon-containing precursor is halogen-free. The silicon-containing deposition precursor can be any suitable silicon-containing precursor, such as those listed in the definition and precursor section herein. In some embodiments, the halogen-free silicon-containing precursor has a decomposition temperature of less than about 700° C., or less than about 650° C. In some embodiments, the halogen-free silicon-containing deposition precursor is an aminosilane, or an alkylsilane, or a silazane. In some embodiments, the silicon-containing precursor is trimethylsilane. In some embodiments, the silicon-containing precursor is dimethylsilane. In some embodiments, the silicon-containing precursor is tetramethylsilane.

[0129] The selected deposition reactant depends on the film to be deposited. In various embodiments, the reactant may be an oxygen-containing gas, a carbon-containing gas and / or a nitrogen-containing gas. Exemplary oxygen-containing gases include oxygen (O2), ozone (O3), peroxides (e.g., hydrogen peroxide (H2O2)), carbon monoxide (CO), carbon dioxide (CO2), nitrous oxide (N2O), nitric oxide (NO2) or a combination thereof. Oxygen-containing reactants may contribute to an increase in oxygen content in the deposited film. Exemplary carbon-containing gases include CO, CO2 and a combination thereof. Carbon-containing reactants may contribute to an increase in carbon content in the deposited film. Exemplary nitrogen-containing gases include nitrogen (N2), ammonia (NH3), nitrous oxide (N2O), nitric oxide (NO2), hydrazine (e.g., hydrazine (N2H4)) or a combination thereof. Nitrogen-containing reactants may contribute to an increase in nitrogen content in the deposited film.

[0130] In some implementations, operation 804 can be performed by thermal CVD. In thermal CVD implementations, both deposition precursors and reactants can be flowed continuously to a processing chamber housing a substrate.

[0131] In some embodiments, operation 804 may be performed by thermal ALD. In thermal ALD embodiments, the deposition precursor and the reactant flow may be separated in time; that is, when the deposition precursor flows, the reactant does not flow, and when the reactant flows, the deposition precursor does not flow. Each exposure of the deposition precursor and the reactant may be referred to as a "pulse". In some embodiments, a "pulse" of a deposition precursor may be referred to as "dosing". A "pulse" of a reactant may be referred to as a "conversion", which may refer to the conversion of adsorbed precursor molecules into film materials. However, it should be understood that although "conversion" assumes that the precursor has been adsorbed, in some embodiments, even if the deposition precursor has not been pulsed or the substrate does not have adsorbed deposition precursor molecules, a pulse of the reactant may still be performed. The pulses separated in time may be pulsed cyclically so that each cycle includes one pulse of the deposition precursor and one pulse of the reactant.

[0132] Figure 8B shows that thermal ALD can be performed as a Fig. 8A 804-a, the substrate is exposed to a halogen-free silicon-containing deposition precursor that can be adsorbed onto the substrate surface. In some embodiments, the adsorption onto the substrate surface can form a thin layer of the silicon-containing precursor on the substrate surface. The thin layer can be less than a monolayer and can have a thickness between about 0. About During operation 804-a, a carrier gas may flow. In some embodiments, a carrier gas may be used to co-flow with the silicon-containing precursor. The carrier gas may be an inert gas, such as helium, argon, neon, and combinations thereof. The carrier gas may be diverted so that the carrier gas is used to deliver the deposition precursor gas to the processing chamber. In some embodiments, a carrier gas may be provided to assist in pressure and / or temperature control of the processing chamber. In some embodiments, a carrier gas is used to ensure that the gas is delivered to the processing chamber more rapidly. A carrier gas may be provided to assist in pressure and / or temperature control of the processing chamber, evaporation of liquid reactants, more rapid delivery of reactants, and / or as a purge gas for removing process gases from the processing chamber and / or the processing chamber piping.

[0133] In operation 804-b, the process chamber is optionally purged. Before purging, the flow of the halogen-free silicon-containing precursor may be stopped or transferred from the process chamber. Purging may remove silicon-containing precursors that are not adsorbed onto the substrate surface. Purging the chamber may involve flowing a purge gas or purge gas, which may be a carrier gas used in other operations or may be a different gas. In some embodiments, purging may involve evacuating the chamber. Exemplary purge gases include argon, nitrogen, hydrogen, and helium. In some embodiments, operation 804-b may include one or more evacuation substages of evacuating the process chamber. Alternatively, it should be understood that operation 804-b may be omitted in some embodiments. Operation 804-b may have any suitable duration, such as between about 0 seconds and about 60 seconds, such as about 0.01 seconds. In some embodiments, increasing the flow rate of one or more purge gases may reduce the duration of operation 804-b. For example, the sweep gas flow rate can be adjusted based on various reactant thermodynamic properties and / or geometric properties of the process chamber and / or process chamber piping to modify the duration of operation 804-b. In a non-limiting example, the duration of the sweep phase can be adjusted by adjusting the sweep gas flow rate. This can reduce the deposition cycle time, thereby improving substrate throughput. After sweeping, the silicon-containing precursor molecules are still adsorbed on the substrate surface. In some embodiments, the sweep gas flows to the chamber containing the substrate at a flow rate between about 100 sccm and about 5000 sccm.

[0134] In operation 804-c, the substrate is exposed to a reactant in the absence of plasma to form a silicon-containing film on the substrate surface. In some embodiments, this operation allows the reactant to react with the adsorbed silicon-containing precursor molecules to convert the silicon-containing precursor molecules into molecules of the silicon-containing film. It should be understood that although Figure 8B The example in involves adsorption prior to exposure to the reactant, but in some embodiments, the substrate may be exposed to the reactant and then to the silicon-containing precursor. Operation 804-c is performed without plasma so that the reaction between the silicon-containing precursor and the reactant is a thermal reaction.

[0135] In some embodiments, the reactants as described above may be oxygen-containing reactants or oxidants. In some embodiments, the silicon-containing precursor is an aminosilane and the reactant is an oxidant; in this case, the reaction between the aminosilane and the oxidant is a thermal reaction, so that no plasma is required to drive the reaction. In some embodiments, the reactants flow into the chamber containing the substrate at a flow rate between about 1 sccm and about 5000 sccm.

[0136] In operation 804-d, the chamber is optionally purged to remove any remaining byproducts. Operation 804-d may be performed using any of the conditions described above with respect to operation 804-b.

[0137] A determination is made as to whether a film of the desired thickness has been deposited. If not, operations 804-a through 804-d are repeated for sufficient cycles to deposit a silicon-containing film of the desired thickness. Any suitable number of deposition cycles may be included in the ALD process to deposit a silicon-containing film of the desired film thickness. For example, about fifty deposition cycles may be performed using the disclosed embodiments to deposit a silicon-containing film on the substrate. In some embodiments, the silicon-containing film is formed to about to about Thickness.

[0138] return Fig. 8A In operation 806, the process chamber may be optionally purged. Operation 806 may utilize the above-mentioned Figure 8B The sweep may be used to remove deposition precursors and / or reactants from the chamber and / or from the processing region above the substrate surface.

[0139] In operation 808, after depositing at least a portion of the silicon-containing film, the silicon-containing film is exposed to a densification plasma (1) without precursors or reactants or (2) with a densification gas. For example, the densification plasma may be generated by igniting a densification gas, which may include, but is not limited to, hydrogen (H2) gas, oxygen-containing gases, nitrogen-containing gases, and combinations thereof. The gas may be selected based on the type of film to be deposited and the reactants used during the deposition process. A general list of possible gases includes nitrogen only, ammonia only, nitrogen / ammonia mixtures, argon only, helium only, argon / helium mixtures, oxygen only, oxygen / nitrogen mixtures, hydrogen / oxygen mixtures, hydrogen only, hydrogen / nitrogen mixtures, and combinations thereof. Other noble gases may also be used.

[0140] Exposure to the densification plasma may change the composition or density of at least the portion of the silicon-containing film.The composition of the silicon-containing film refers to the relative amounts of silicon and oxygen, carbon, nitrogen, and hydrogen.

[0141] In some embodiments, even if nitrogen is used to form silicon nitride in operation 808, operation 808 may involve exposure to a nitrogen plasma during post-processing to reduce hydrogen content and densify the film.

[0142] In various embodiments, an oxygen-free plasma is used; that is, no oxygen (O 2 ) gas or oxygen-containing gas is used to generate the plasma.

[0143] Operation 808 is performed for a specific duration sufficient to densify or treat the silicon-containing film. In some embodiments, operation 808 is performed for a duration of about 10 seconds to about 60 seconds.

[0144] The plasma may be ignited at a plasma frequency of 13.56 MHz. In some embodiments, the plasma is generated using a dual frequency RF generator. In some embodiments, the plasma power during operation 808 is about 0 to about 6500 W or about 100 W to about 6500 W per station. In some embodiments, the plasma is generated using a single frequency RF generator. In various embodiments, the plasma power of the high frequency plasma is about 400 W (0.1 W / cm 2 ) to about 5000W(1.5W / cm 2 In various embodiments, the plasma power of the low frequency plasma is about 400 W (0.1 W / cm 2 ) to about 3000W(1W / cm 2). In some embodiments, exposure to the plasma is performed in pulses. For example, in some embodiments, rather than turning on the plasma during operation 808 and keeping it on, operation 808 involves pulsing the plasma between on and off phases or between high and low phases. The plasma can be pulsed at a pulse frequency of about 2 Hz to about 100 kHz, with a duty cycle ranging from about 1% to about 95%. The duty cycle is defined as the duration that the plasma is on during a period of duration T. The duration T includes the duration of the pulse on (ON) time (the duration that the plasma is in the ON state) and the duration of the plasma off (OFF) time (the duration that the plasma is in the OFF state) during a given period. The pulse frequency will be understood to be 1 / T. For example, for a plasma pulse period T=100 μs, the frequency is 1 / T=1 / 100 μs, or 10 kHz. The duty cycle or duty ratio is the fraction or percentage of the period T that the plasma is in the on state, such that the duty cycle or duty ratio is the pulse on time divided by T. For example, for a plasma pulse period T=100 μs, if the pulse on time is 70 μs (so that the duration of the plasma in the on state during one period is 70 μs), and the pulse off time is 30 μs (so that the duration of the plasma in the off state during one period is 30 μs), the duty cycle is 70%. In some embodiments, the shortest RF on time during the pulse step can be as low as about 5 microseconds. In some embodiments, the shortest RF off time can be about 5 microseconds. Depending on the duty cycle and frequency, various combinations of RF on / RF off pulses can be performed. For example, in some embodiments, the operation can be performed for a duration of about 0.01 ms to about 60 seconds, or about 1 second to about 60 seconds, or about 0.01 ms to about 5 ms, or about 0.02 ms to about 5 ms, or about 0.05 ms to about 5 ms, or about 0.05 ms to about 1.9 ms, or about 0.5 ms to about 1.9 ms. During operation 808, the plasma can be pulsed hundreds to thousands of times depending on the total plasma duration.

[0145] During operation 808, the silicon-containing precursor and reactants are not flowed.

[0146] The plasma may be generated in situ or in the chamber. In some embodiments, the plasma may be generated in a remote plasma generator to form plasma species, which is then delivered to the processing chamber via a showerhead. The plasma may be an inductively coupled plasma, or a capacitively coupled plasma, or a microwave plasma.

[0147] When the plasma is ignited, a densifying gas or combination of densifying gases flows to the processing chamber during operation 808, thereby generating plasma species that may be capable of modifying and densifying the deposited film.

[0148] Operation 808 can be performed using the same substrate temperature as during operation 804. In some embodiments, operations 808 and 804 can be performed without breaking vacuum. In some embodiments, operations 808 and 804 are performed in the same chamber.

[0149] In some embodiments, operations 808 and 804 are performed at different temperatures. In some embodiments, operations 808 and 804 are performed with an air break between operations or in separate chambers.

[0150] Process conditions for densification may depend on the chemistry used to deposit the silicon-containing film, the thickness of the silicon-containing film, the topography of the substrate, the composition of the layers underlying the silicon-containing film, and other factors.

[0151] In operation 812, operations 804-810 may optionally be repeated for a number of cycles. In some embodiments, for each approximately to about or about to about Operation 808 is performed. That is, at least about to about or about to about After forming the silicon-containing film, operation 808 is performed.

[0152] The chemical selection, process conditions, and reaction mechanisms used during deposition in operation 804 and densification in operation 808 tune the composition and properties of the silicon-containing film. For example, in some embodiments, using a silicon-containing precursor with more Si-C bonds can result in more Si-C bonds in the resulting film. In some embodiments, when certain silicon-containing precursors are used, lower temperatures can be used, thereby forming the film using lower deposition rates that may affect the quality of the film. In some embodiments, switching gas flows and / or plasma conditions can incorporate more or less oxygen atoms or more or less hydrogen atoms. In some embodiments, multiple gases are used as additive gases during deposition. For example, multiple gases can be used during reactant exposure in an ALD process or during deposition of a silicon-containing film by CVD, which can switch the film composition by incorporating more or certain molecules.

[0153] In some embodiments, a gradient film composition may be desired. A gradient film may be obtained by changing the gas composition during deposition and / or during processing and / or during different deposition cycles. A gradient film composition is defined as a film having a composition that varies over different regions of the film, such as along the depth of the film, or over the surface of the substrate, or otherwise. In a limiting example, a gradient film composition may include a film having SiCON and SiCO that is deposited using at least about 20 deposition cycles, which is deposited at least about 100% of the film composition. to about SiCO with little to no nitrogen content and 20% carbon content, with at least about to about Alternating between SiCON having about 15% nitrogen content but only about 5% carbon content.

[0154] Fig. 9 is a timing diagram of exemplary pulses according to the disclosed embodiment. Fig. 9 The stages of the example process 900 are shown for a variety of process parameters, such as reactant gas flow, densification gas flow, silicon-containing precursor flow, and plasma state. These lines indicate when to turn on and off the flow and when to turn on and off the plasma. Although this example shows on / off flow and on / off plasma state, it should be understood that in some embodiments, the flow and / or plasma can be switched between low and high positions, rather than between off and on positions. It should also be understood that "closing" may not refer to completely closing the valve, but may also include embodiments in which the gas is transferred. Various disclosed embodiments depend on process parameters, including but not limited to the flow rate of densification and reactant materials, the flow rate of silicon-containing precursor gas, plasma conditions during processing, substrate temperature, and chamber pressure. Fig. 9 The example in refers to a CVD-based process, where the silicon-containing film is thermally deposited by CVD and then plasma treated.

[0155] Process 900 includes two cycles—one cycle includes a deposition phase 902A and a periodic plasma post-treatment phase 915A. The other cycle includes a deposition phase 902B and a periodic plasma post-treatment phase 915B. During the deposition phase 902A, the flow of the densification gas (which may be H2) is turned off, the flow of the silicon-containing precursor gas is turned on, the flow of the reactant is turned on, and the plasma is turned off. This may refer to Fig. 8A During the periodic plasma post-treatment phase 915A, the densification gas flow is turned on, the silicon-containing precursor flow is turned off, the reactant flow is turned off, and the plasma is turned on. This may refer to Fig. 8A 808 implementation example. The cycle is then repeated. In deposition phase 902B, the silicon-containing precursor gas flow is turned on, the reactant gas flow is turned on, and the plasma is turned off, and the densification gas flow is turned off. In periodic plasma post-treatment phase 915B, the densification gas flow is turned on, the silicon-containing precursor gas flow is turned off, the reactant flow is turned off, and the plasma is turned on. This can be repeated for multiple cycles. Although Fig. 9 Not specified, but in some embodiments, in addition to Fig. 9 In addition to or in lieu of the hydrogen densification gas flow shown Fig. 9With the hydrogen densification gas flow shown, the plasma post-treatment stage may involve flowing an oxygen-containing gas (e.g., oxygen) or a nitrogen-containing gas (e.g., nitrogen) or a mixture of the two (e.g., a mixture of oxygen and nitrogen). While the densification gas is flowing, a plasma may be ignited.

[0156] Certain disclosed embodiments may utilize densification to achieve a specific film density. For example, for a film having a density of at least about 2.0 g / cm 3 To about 2.6g / cm 3 For films having a density of about 2.3 g / cc or about 2.3 g / cc, the film may be densified using a plasma power of at least about 100 W to about 6500 W for about 1 second to about 60 seconds.

[0157] Wafers or substrates used in the semiconductor equipment industry typically have a diameter of 200 mm, or 300 mm, or 450 mm. Unless otherwise specified, the processing details (e.g., flow rates, power levels, etc.) set forth herein are related to processing a 300 mm diameter substrate or a processing chamber configured to process a 300 mm diameter substrate, and may be appropriately scaled for substrates or chambers of other sizes. Experimental

[0158] Experiment 1:

[0159] Silicon oxycarbonitride films were deposited using silicon-containing precursors, and the films were treated and untreated. Using a particular precursor, the FTIR spectra of the two films are shown in Fig.10 In the present invention, BTBAS was used to deposit silicon oxycarbonitride films with oxygen co-flow, and the films were treated or not treated. The FTIR spectra of the two films are shown in Fig.11 These results indicate that the film is densified by H2 plasma treatment. The typical Si-O-Si stretching peak is located at (1040 cm -1 ), Si-O bending peak is located at (820cm -1 ), SiN peak is located at 840cm -1 The Si-C peak is located at 810 cm -1 The peak of Si-C overlaps with the peaks of Si-O and Si-N, resulting in a peak at 600 cm -1 Up to 1200cm -1 The denser the membrane, the stronger the main peak; for example, the NH peak (3350cm -1 ) is indeed reduced after densification.

[0160] Experiment 2:

[0161] Silicon oxycarbonitride films were deposited using silicon-containing precursors with or without co-flowing oxygen, with and without treating the films. The silicon, carbon, oxygen, and nitrogen contents and densities in g / cc are shown in Table 1 below. These results show that the gas chemistry used with the precursors and the use of treatments can affect film composition and density. For example, plasma treatment can be used to significantly densify the film.

[0162] Table 1. Silicon, carbon, oxygen and nitrogen content & film density Device

[0163] One aspect of the present invention is a device configured to implement the methods described herein. In some implementations, the device is configured to complete the film deposition method described herein. In some implementations, the device is configured to complete the film deposition method and etching method described herein. Suitable devices include hardware for completing process operations and a system controller with instructions for controlling process operations according to the present invention. In some embodiments, the device for performing the aforementioned process operations may include a remote plasma source. Compared to direct plasma, a remote plasma source can provide mild reaction conditions. An example of a suitable remote plasma device is described in U.S. Patent Application No. 14 / 062,648 filed on October 24, 2013, the entire contents of which are incorporated herein by reference for all purposes. In some embodiments, the device for performing the aforementioned process operations may include a pedestal for heating the substrate to an elevated temperature.

[0164] Fig.12 FIG. 1 is a schematic diagram of an exemplary plasma processing apparatus having a remote plasma source according to some implementation schemes. It should be understood that according to some embodiments, Fig.12 The plasma processing apparatus in the embodiment of the present invention can be used to deposit a silicon-containing layer, and / or etch a silicon-containing layer formed in a reaction chamber. In some embodiments, a silicon-containing layer can be formed in a reaction chamber and then etched in the same reaction chamber using a remote plasma source without exposing the silicon-containing layer to the ambient atmosphere. In some embodiments, a silicon-containing layer can be formed in a reaction chamber and then a plasma processing operation using a densification gas plasma can be performed using a remote plasma source.

[0165] The plasma processing device 1200 includes a reaction chamber 1210 having a showerhead 1220. Inside the reaction chamber 1210, a substrate 1230 is retained on a platform or pedestal 1235. In some embodiments, the pedestal 1235 may be equipped with a heating / cooling element. The controller 1240 may be connected to the components of the plasma processing device 1200 to control the operation of the plasma processing device 1200. For example, the controller 1240 may include instructions for controlling the process conditions of the operation of the plasma processing device 1200, such as temperature process conditions and / or pressure process conditions. In some embodiments, the controller 1240 may include instructions for controlling the flow rate of the precursor gas, the reactant gas, the source gas and / or the carrier gas. The controller 1240 may include instructions for changing the flow rate of the reactant gas, the source gas and / or the carrier gas over time. The controller 1240 may include instructions for controlling the chamber pressure, substrate temperature, RF power, exposure time, gas composition and relative concentration of the gas composition. A more detailed description of the controller 1240 is provided below.

[0166] During operation, a gas or gas mixture is introduced into the reaction chamber 1210 via one or more gas inlets coupled to the reaction chamber 1210. In some embodiments, two or more gas inlets are coupled to the reaction chamber 1210. A first gas inlet 1255 can be coupled to the reaction chamber 1210 and connected to the container 1250, while a second gas inlet 1265 can be coupled to the reaction chamber 1210 and connected to the remote plasma source 1260. In some embodiments, the second gas inlet 1265 can provide a carrier gas to the reaction chamber 1210. In embodiments including a remote plasma source, the delivery lines for the precursor and the radical species generated in the remote plasma source are separate. Thus, the precursor and the radical species do not substantially interact before reaching the substrate 1230. It should be understood that in some embodiments, the gas lines can be reversed so that the container 1250 can provide a precursor gas flow through the second gas inlet 1265, while the remote plasma source 1260 can provide ions and radicals through the first gas inlet 1255.

[0167] One or more free radical species may be generated in a remote plasma source 1260 and configured to enter the reaction chamber 1210 via a second gas inlet 1265. Any type of plasma source may be used in the remote plasma source 1260 to generate the free radical species. This includes, but is not limited to, an inductively coupled plasma (ICP) source, a capacitively coupled plasma (CCP) source, a microwave plasma source, a DC plasma source, and a laser generated plasma source. An example of a capacitively coupled plasma may be a radio frequency (RF) plasma. A high frequency plasma may be configured to operate at 13.56 MHz or higher. An example of such a remote plasma source 1260 may be a 1200 plasma source manufactured by Lam Research Corporation (Fremont, California). Another example of such a remote plasma source 1260 is the MKS 1260 manufactured by MKS Instruments (Wilmington, Massachusetts). It can operate at 440 kHz and can be provided as a subunit screwed onto a larger device for processing one or more substrates in parallel. In some embodiments, a microwave plasma can be used as a remote plasma source 1260, such as the MKS 1260, also manufactured by MKS Instruments. The microwave plasma may be configured to operate at a frequency of 2.45 GHz. The gas species provided to the remote plasma source 1260 may include hydrogen, nitrogen, oxygen, carbon, or other gases as mentioned elsewhere herein. In certain embodiments, hydrogen is provided in a carrier gas (e.g., helium). As an example, hydrogen may be provided in a helium carrier gas at a concentration of about 1-50% hydrogen by volume.

[0168] The precursor may be provided in a container 1250 and may be supplied to the showerhead 1220 via a first gas inlet 1255. The showerhead 1220 distributes the precursor into the reaction chamber 1210 and toward the substrate 1230. The substrate 1230 may be located below the showerhead 1220. It should be understood that the showerhead 1220 may have any suitable shape and may have any number and arrangement of ports for distributing gas to the substrate 1230. The precursor may be supplied to the showerhead 1220 and ultimately to the substrate 1230 at a controlled flow rate.

[0169] The one or more radical species formed in the remote plasma source 1260 can be carried in the gas phase toward the substrate 1230. The one or more radical species can flow through the second gas inlet 1265 and into the reaction chamber 1210. It should be understood that the second gas inlet 1265 need not be as Fig.121230. In some embodiments, the second gas inlet 1265 can be located directly above the substrate 1230 or at other locations. The distance between the remote plasma source 1260 and the reaction chamber 1210 can be configured to provide mild reaction conditions so that the free species generated in the remote plasma source 1260 are substantially neutralized, but at least some free radical species in a low energy state or ground state remain in the environment adjacent to the substrate 1230. Such low energy state free radical species will not recombine to form stable compounds. The distance between the remote plasma source 1260 and the reaction chamber 1210 can depend on the aggressiveness of the plasma (e.g., determined in part by the source RF power level), the density of the gas in the plasma (e.g., if there is a high concentration of hydrogen atoms, a large portion of them may recombine to form H2 before reaching the reaction chamber 1210), and other factors. In some embodiments, the distance between the remote plasma source 1260 and the reaction chamber 1210 can be between about 1 cm and 30 cm, such as about 5 cm or about 15 cm.

[0170] In some embodiments, a co-reactant or reactant that is not a primary silicon-containing precursor or hydrogen radical may be introduced. In some embodiments, a co-reactant or reactant may be introduced during the deposition of a silicon-containing layer by thermal ALD or thermal CVD. In some embodiments, a co-reactant or reactant may be introduced during a plasma treatment operation to tune the composition and / or density of the silicon-containing layer. In some embodiments, a co-reactant or reactant may be introduced during remote plasma etching. In some embodiments, the plasma treatment apparatus 1200 is configured to introduce a co-reactant or reactant through a second gas inlet 1265. In some cases, the co-reactant or reactant is at least partially converted into plasma. In some embodiments, the plasma treatment apparatus 1200 is configured to introduce a co-reactant or reactant through a showerhead 1220 via a first gas inlet 1255. Examples of co-reactants or reactants include oxygen, nitrogen, ammonia, carbon dioxide, carbon monoxide, and the like. The flow rate of the co-reactant or reactant may vary over time to produce a composition gradient in the gradient film.

[0171] In some embodiments, a gas plasma stream can be generated from a remote plasma source 1260. The gas plasma stream from the remote plasma source 1260 can include ions, free radicals, charged neutral species, and other reactive species of the reactive gas. For example, the reactive species can include free radical species of hydrogen, nitrogen, oxygen, carbon, or amines, which can be supplied to the surface of the substrate 1230 for remote plasma etching.

[0172] Fig.13 Schematic diagram of an exemplary plasma processing apparatus with a remote plasma source according to some implementations is shown. It should be understood that Fig.13The reaction chamber in the reactor chamber can be used to deposit a silicon-containing layer, process a silicon-containing layer, and / or etch a silicon-containing layer formed in the reactor chamber according to some embodiments. In some embodiments, a silicon-containing layer can be formed in the reactor chamber and subsequently etched in the same reactor chamber using a remote plasma source without exposing the silicon-containing layer to ambient atmosphere. In some embodiments, a silicon-containing layer can be formed in the reactor chamber and subsequently processed in the same reactor chamber using a remote plasma without exposing the silicon-containing layer to ambient atmosphere.

[0173] The plasma processing apparatus 1300 includes a remote plasma source 1302 separated from a reaction chamber 1304. The remote plasma source 1302 is fluidly connected to the reaction chamber 1304 through a gas distributor or showerhead 1306. In some embodiments, the showerhead 1306 includes an ion filter for filtering ions to limit ion bombardment damage to the substrate 1312. Radical species and / or ions are generated in the remote plasma source 1302, where the radical species can be supplied to the reaction chamber 1304. Precursors (e.g., one or more silicon-containing precursors) are supplied to the reaction chamber 1304 through a gas outlet 1308 disposed downstream of the remote plasma source 1302 and the showerhead 1306.

[0174] The substrate 1312 is supported on a substrate support structure or wafer pedestal 1314. The wafer pedestal 1314 may be configured with lift pins or other movable support members to position the substrate 1312 within the deposition / etching zone 1310. The substrate 1312 may be moved closer to or further away from the showerhead 1306. The wafer pedestal 1314 may be configured with lift pins or other movable support members to position the substrate 1312 within the deposition / etching zone 1310. Fig.13 In FIG. 1 , the substrate 1312 is shown to have been raised into the deposition / etching zone 1310 .

[0175] In some embodiments, the wafer pedestal 1314 includes an electrostatic chuck 1316. The electrostatic chuck 1316 includes one or more electrostatic clamping electrodes 1318 embedded in the body of the electrostatic chuck 1316. In some embodiments, the one or more electrostatic clamping electrodes 1318 can be coplanar or substantially coplanar. The electrostatic clamping electrodes 1318 can be powered by a direct current (DC) power source or a DC clamping voltage (e.g., between about 200V and about 2000V) so that the substrate 1312 can be held on the electrostatic chuck 1316 by electrostatic attraction. The electrostatic clamping electrodes 1318 can be powered by a first wire 1320. The electrostatic chuck 1316 can further include one or more heating elements 1322 embedded in the body of the electrostatic chuck 1316. The one or more heating elements 1322 can include a resistive heater. In some embodiments, the one or more heating elements 1322 are disposed below the one or more electrostatic clamping electrodes 1318. The one or more heating elements 1322 may be configured to heat the substrate 1312 to a temperature greater than about 450° C., greater than about 500° C., greater than about 550° C., greater than about 600° C., or greater than about 650° C. The one or more heating elements 1322 provide selective temperature control of the substrate 1312. The one or more heating elements 1322 may be powered by a second electrical wire 1324.

[0176] The coil 1328 is arranged around the remote plasma source 1302, wherein the remote plasma source 1302 includes an outer wall (e.g., a quartz dome). The coil 1328 is electrically coupled to a plasma generator controller 1332, which can be used to form and maintain a plasma in the plasma region 334 through inductively coupled plasma generation. In some embodiments, the plasma generator controller 1332 may include a power supply source for supplying power to the coil 1328, wherein the power may be in a range between about 300 W and about 15 kW per station during plasma generation, or in a range between about 1 kW and about 10 kW per station. In some embodiments, an electrode or antenna used for parallel plate or capacitively coupled plasma generation may be used to generate a continuous supply of free radicals through plasma excitation rather than inductively coupled plasma generation. Regardless of the mechanism used to ignite and maintain the plasma in the plasma region 1334, plasma excitation may be used to continuously generate free radical species during layer formation (e.g., film deposition) and / or remote plasma processing.

[0177] In some embodiments, hydrogen radicals (H*), nitrogen radicals (N*), oxygen radicals (O*), carbon radicals (C*), amine radicals (NH*, NH2*), or combinations thereof are generated in the plasma region 1334 under approximately steady-state conditions during steady-state film deposition or remote plasma processing controlled by the plasma generator controller 1332, but transients may occur at the beginning and end of film deposition and / or remote plasma etching. For example, hydrogen radicals may be generated in the plasma region 1334. In another example, two or more different types of radicals may be generated in the plasma region 1334, such as nitrogen-containing radicals and hydrogen radicals. Although Fig.13 Nitrogen (N*), amine radicals (NH*, NH2*) and hydrogen radicals (H*) are shown, but it should be understood that the aforementioned radicals are only illustrative. Fig.13 Other free radicals may additionally or alternatively be present to the free radicals depicted.

[0178] While the source gas is being supplied to the remote plasma source 1302, a supply of ions and radicals may be continuously generated within the plasma region 1334. The ions generated in the plasma region 1334 may be filtered out by an ion filter of the showerhead 1306. In this way, the radicals generated in the plasma region 1334 may be supplied to the substrate 1312 in the reaction chamber 1304 and ion bombardment may be limited. Filtering ions and / or photons may reduce substrate damage, undesired re-excitation of molecules, and / or selective cracking or decomposition of hydrocarbon precursors within the reaction chamber 1304.

[0179] Conditions in the remote plasma source 1302, including the composition of the source gas provided to the remote plasma source 1302 and the RF power supplied to the coil 1328, can be controlled to optimize the generation of desired radical species in the plasma region 1334. In some embodiments, the source gas can include an oxygen-containing reactant (e.g., oxygen (O2), ozone (O3), carbon monoxide (CO), carbon dioxide (CO2), nitrogen dioxide (NO2), nitrous oxide (N2O)), a carbon-containing reactant (e.g., acetylene (C2H2), ethylene (C2H4), or propylene (C3H6)), a hydrogen-containing reactant (e.g., hydrogen (H2) or methane (CH4)), or a nitrogen-containing reactant (e.g., nitrogen (N2), ammonia (NH3), diazene (N2H2), or hydrazine (N2H4)), or a mixture thereof. In some embodiments, the source gas can include hydrogen. For example, hydrogen radicals may be generated in the plasma region 1334 , wherein a source gas of hydrogen may be provided to the remote plasma source 1302 to provide a gas plasma flow including hydrogen radicals to the substrate 1312 in the reaction chamber 1304 .

[0180] In some embodiments, the source gas may be mixed with one or more additional gases. These one or more additional gases may be supplied to the remote plasma source 1302. In some embodiments, the source gas is mixed with one or more additional gases to form a gas mixture, wherein the one or more additional gases may include a carrier gas. Non-limiting examples of additional gases may include helium, neon, argon, krypton, and xenon. The one or more additional gases may support or stabilize steady-state plasma conditions within the remote plasma source 1302 or assist in transient plasma ignition or extinguishing processes. Fig.13 In the embodiment, source gas supply source 1336 is fluidly connected to remote plasma source 1302 to supply source gas. For some embodiments, about 5 sccm to about 10,000 sccm, or about 10 sccm to about 200 sccm of source gas can be supplied from source gas supply source 1336. In addition, additional gas supply source 1338 is fluidly connected to remote plasma source 1302 to supply the one or more additional gases. Fig.13 The embodiments in 1300 depict the gas mixture of the source gas and the one or more additional gases as being introduced through separate gas outlets, but it should be understood that the gas mixture can be introduced directly into the remote plasma source 1302. That is, the premixed dilution gas mixture can be supplied to the remote plasma source 1302 through a single gas outlet.

[0181] Plasma activated species 1342 (e.g., excited nitrogen, hydrogen, carbon, oxygen, and / or amine radicals) flow out of the remote plasma source 1302 and enter the reaction chamber 1304 through the showerhead 1306. The plasma activated species 1342 within the showerhead 1306 and the reaction chamber 1304 generally do not undergo sustained plasma excitation therein. The showerhead 1306 may have a plurality of gas ports to diffuse the flow of plasma activated species 1342 into the reaction chamber 1304. In some embodiments, the plurality of gas ports may be spaced apart from one another. In some embodiments, the plurality of gas ports may be arranged in an array of regularly spaced channels or through holes extending through a plate separating the remote plasma source 1302 from the reaction chamber 1304. The plurality of gas ports may allow the radicals (including the plasma activated species 1342) exiting the remote plasma source 1302 to be dispersed and diffused smoothly into the deposition / etching region 1310 of the reaction chamber 1304 and filter out ions.

[0182] Typical remote plasma sources are far from the reaction vessel. Therefore, free radical quenching and recombination (e.g., through wall collision events) may greatly reduce active species. On the contrary, in some implementations, the size of multiple gas ports may be configured to facilitate free passage of free radicals into the reaction chamber 1304 in consideration of the mean free path or gas flow residence time under typical processing conditions. In some embodiments, the openings of the multiple gas ports may occupy between about 5% and about 20% of the exposed surface area of ​​the showerhead 1306. In some implementations, the multiple gas ports may each have an axial length to diameter ratio between about 3:1 and 10:1 or between about 6:1 and about 8:1. This aspect ratio can reduce the wall collision frequency of free radical species passing through the multiple gas ports, and provide sufficient time for most excited radical species to relax to the ground state free radical species. In some implementations, the size of the multiple gas ports may be configured so that the residence time of the gas passing through the showerhead 1306 is greater than the typical energy relaxation time of the excited radical species.

[0183] Under the plasma activated material 1342 delivered from the showerhead 1306 to the reaction chamber 1304, a precursor 1344 (or other process gas) can be introduced into the reaction chamber 1304. The precursor 1344 can include a silicon-containing precursor, such as silane. The precursor 1344 can be introduced through a gas outlet 1308, wherein the gas outlet 1308 can be fluidly connected to the precursor supply source 1340. The gas outlet 1308 can include openings spaced apart from each other so that the stream of the precursor 1344 can be introduced in a direction parallel to the flow of the plasma activated material 1342 out of the showerhead 1306. In some embodiments, the gas outlet 1308 can be located downstream of the showerhead 1306. In some embodiments, the gas outlet 1308 is part of the showerhead 1306, such as in a dual plenum showerhead. The dual plenum showerhead can provide separate outlets / channels for the plasma activated material 1342 and the precursor 1344 to avoid mixing in the showerhead 1306. In this way, the precursor 1344 can flow into the reaction chamber 1304 through the showerhead 1306 without being exposed to the plasma in the remote plasma source 1302. The gas outlet 1308 can be located upstream of the deposition / etching zone 1310 and the substrate 1312. The deposition / etching zone 1310 is located inside the reaction chamber 1304 between the gas outlet 1308 and the substrate 1312.

[0184] During the film deposition process, most of the precursor 1344 can be prevented from mixing with the plasma activated species 1342 in or near the showerhead 1306. In some embodiments, the precursor 1344 can be delivered to the substrate 1312 during the dosing phase of the ALD cycle, separate from the plasma activated species 1342 delivered to the substrate 1312 during the plasma exposure phase of the ALD cycle. The adsorbed precursor 1344 can react with radicals of the plasma activated species 1342 during the plasma exposure phase of the ALD cycle to deposit a film. In some embodiments, the precursor 1344 can be delivered to the substrate 1312 in a continuous manner to interact with the plasma activated species 1342 in the deposition / etching zone 1310 to deposit a film by CVD. In some embodiments, the plasma activated species 1342 can be delivered to the substrate 1312 without delivering the precursor 1344 to etch the film.

[0185] Gas can be removed from reaction chamber 1304 through outlet 1348, which is fluidly connected to a pump (not shown). Thus, free radical species or purge gas can be removed from reaction chamber 1304.

[0186] In some embodiments, a heat shield (not shown) may be disposed below the wafer pedestal 1314. The heat shield acts as a thermal insulator below the wafer pedestal 1314 to slow down heat loss through thermal radiation, thereby reducing the amount of power required to maintain the wafer pedestal 1314 at a certain high temperature and also preventing other components within the reaction chamber 1304 from overheating due to excessive heat radiated from the wafer pedestal 1314. For example, the heat shield may be radially offset from the rod 1326 and may have a thin annular body with a high view factor relative to the underside of the electrostatic chuck 1316. Thus, the annular heat shield may reduce radiative heat loss from the wafer pedestal 1314.

[0187] Electrostatic chuck 1316 of wafer pedestal 1314 can adsorb / desorb substrate 1312 in plasma processing apparatus 1300 configured to operate at high temperatures. Such high temperatures can be greater than about 350°C, greater than about 400°C, greater than about 450°C, greater than about 500°C, or greater than about 550°C.

[0188] In some embodiments, a controller 1350 (e.g., a system controller) is in operative communication with the plasma processing apparatus 1300. In some embodiments, the controller 1350 includes a processor system 1352 (e.g., a microprocessor) configured to execute instructions stored in a data system 1354 (e.g., a memory). In some embodiments, the controller 1350 can communicate with the plasma generator controller 1332 to control plasma parameters and / or conditions in the remote plasma source 1302. In some embodiments, the controller 1350 can communicate with the wafer pedestal 1314 to control pedestal elevation, electrostatic adsorption and desorption, and temperature. In some embodiments, the controller 1350 can control other processing conditions, such as RF power settings, frequency settings, duty cycle, pulse time, pressure within the reaction chamber 1304, pressure within the remote plasma source 1302, gas flow rates from the source gas supply 1336, gas flow rates from the additional gas supply 1338 and other sources, temperature of the wafer pedestal 1314, and temperature of the reaction chamber 1304, as well as other processing conditions.

[0189] The controller 1350 may include instructions for controlling the process conditions for operating the plasma processing apparatus 1300. The controller 1350 will typically include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, etc. Instructions for implementing appropriate control operations are executed on the processor. These instructions may be stored on a memory device associated with the controller 1350 or they may be provided via a network.

[0190] In certain embodiments, the controller 1350 controls all or most of the activities of the plasma processing apparatus 1300 described herein. For example, the controller 1350 may control all or most of the activities of the plasma processing apparatus 1300 associated with film deposition, film processing, and / or remote plasma etching. The controller 1350 may execute system control software, including instruction sets for controlling timing, gas composition, gas flow rate, chamber pressure, chamber temperature, RF power level, substrate position, substrate temperature, and / or other parameters. Other computer programs, scripts, or routines stored on a memory device associated with the controller 1350 may be employed in some embodiments. In a multi-station reactor, the controller 1350 may include different or identical instructions for different equipment stations, thereby allowing the equipment stations to operate independently or synchronously.

[0191] In some embodiments, the controller 1350 may include instructions configured to perform operations such as conformally depositing a silicon-containing film in a recessed feature of the substrate 1312, and exposing the substrate 1312 to plasma-activated species 1342 generated in the remote plasma source 1302 to etch the silicon-containing film to at least one of a desired depth and a desired profile. In some embodiments, exposing the substrate 1312 to the plasma-activated species 1342 to etch the silicon-containing film to the desired depth and / or the desired profile occurs by adjusting one or more of the following parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentrations of the gas composition, and RF power.

[0192] In some embodiments, the controller 1350 may include instructions configured to perform operations such as causing a silicon-containing film to be formed over the substrate 1312 at a substrate temperature below about 700° C. without igniting a plasma, and causing the silicon-containing film to be treated with a densifying gas plasma. The silicon-containing film may be deposited using thermal ALD and / or thermal CVD. The controller 1350 may include instructions further configured to adjust at least one of a silicon-containing precursor, reactant, or process condition during plasma treatment to at least change a composition or density of the silicon-containing film.

[0193] In some embodiments, plasma processing apparatus 1300 may include a user interface associated with controller 1350. The user interface may include a display screen, a graphical software display of plasma processing apparatus 1300 and / or process conditions, and a user input device (e.g., a pointing device, a keyboard, a touch screen, a microphone, etc.).

[0194] The computer program code for controlling the above operations may be written in any conventional computer readable programming language: such as assembly language, C, C++, Pascal, Fortran, etc. The compiled object code or script is executed by the processor to perform the tasks specified in the program.

[0195] Signals for monitoring the process may be provided through analog and / or digital input connections of the controller 1350. Signals for controlling the process are output on analog and digital output connections of the system.

[0196] Broadly speaking, the controller 1350 can be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuit can include a chip in the form of firmware that stores program instructions, a digital signal processor (DSP), a chip defined as an application specific integrated circuit (ASIC), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). The program instructions can be instructions sent to the controller in the form of various individual settings (or program files) that define operating parameters for performing a specific process on or for a semiconductor wafer or system. In some embodiments, the operating parameters can be part of a recipe defined by a process engineer to complete one or more processing steps during the manufacture of one or more layers, materials (e.g., amorphous silicon), surfaces, circuits, and / or dies of a wafer.

[0197] In some embodiments, the controller 1350 can be a part of or coupled to a computer that is integrated with the system, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller 1350 can be in the "cloud" or all or part of a wafer factory (fab) host system, which can allow remote access to wafer processing. The computer can implement remote access to the system to monitor the current progress of manufacturing operations, check the history of past manufacturing operations, check the trends or performance standards of multiple manufacturing operations, change the parameters of the current processing, set the processing steps to follow the current processing, or start a new process. In some examples, a remote computer (e.g., a server) can provide a process recipe to the system through a network (which can include a local network or the Internet). The remote computer can include a user interface that enables input or programming of parameters and / or settings, and then sends the parameters and / or settings from the remote computer to the system. In some examples, the controller receives instructions in the form of data that specify the parameters of each processing step to be performed during one or more operations. It should be understood that the parameters can be specific to the type of process to be performed and the type of tool, and the controller 1350 is configured to interface with or control the tool. Thus, as described above, the controller 1350 can be distributed, for example, by including one or more discrete controllers networked together and working toward a common purpose (e.g., the processes and controls described herein). An example of a distributed controller for such a purpose is one or more integrated circuits on a chamber that communicate with one or more integrated circuits remotely (e.g., at a platform level or as part of a remote computer), which combine to control the process on the chamber. Definition and Precursors

[0198] The terms "acyl" or "alkanoyl" used interchangeably herein refer to a group of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms or hydrogen in straight chain, branched, cyclic configuration, saturated, unsaturated and aromatic and combinations thereof, attached to the parent molecular group through a carbonyl group as defined herein. Examples of such groups are formyl (-C(O)H), acetyl (Ac or -C(O)Me), propionyl, isobutyryl, butyryl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, wherein R is hydrogen, an aliphatic group or an aromatic group, as defined herein.

[0199] "Alkanoyloxy" refers to an alkanoyl group, as defined herein, attached to a parent molecular group through an oxy group, as defined herein. Such a group is exemplified by acetoxy (-OAc or -OC(O)Me). In some embodiments, alkanoyloxy is -OC(O)-R, wherein R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0200] "Aliphatic" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), and hydrocarbon groups including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic forms thereof, and also including straight chain and branched arrangements, as well as all stereo and positional isomers. Aliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aliphatic groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0201] "Aliphatic-carbonyl" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0202] "Aliphatic-carbonyloxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, aliphatic-carbonyloxy is -OC(O)-R, wherein R is an optionally substituted aliphatic group, as defined herein.

[0203] "Aliphatic-oxy" refers to an aliphatic group that is or can be coupled to a compound disclosed herein, wherein the aliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, aliphatic-oxy ​​is -OR, wherein R is an optionally substituted aliphatic group as defined herein.

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

[0205] "Alkyl-aryl", "alkenyl-aryl" and "alkynyl-aryl" mean an alkyl, alkenyl or alkynyl, respectively, as defined herein, coupled (or linked) or capable of being coupled (or linked) to a parent molecular group through an aryl, as defined herein. Alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl and / or alkynyl-aryl groups can be substituted with one or more substituents, as described herein for alkyl and / or aryl groups. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon (C 2+) atoms. 7-16 alkyl-aryl), and those having an alkyl group containing 1 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 1-6 Alkyl-C 4-18 Exemplary unsubstituted alkenyl-aryl groups have 7 to 16 carbon atoms (C 7-16 alkenyl-aryl), and those having an alkenyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkenyl-C 4-18 Exemplary unsubstituted alkynyl-aryl groups have 7 to 16 carbon (C 7-16 alkynyl-aryl), and those having an alkynyl group containing 2 to 6 carbons and an aryl group containing 4 to 18 carbons (i.e., C 2-6 Alkynyl-C 4-18 In some embodiments, alkyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkyl as defined herein. In some embodiments, alkenyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkenyl as defined herein. In some embodiments, alkynyl-aryl is -LR, wherein L is aryl or arylene as defined herein, and R is alkynyl as defined herein.

[0206] "Alkenyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50), for example, 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent olefin. The alkenyl group can be branched, straight chain, cyclic (e.g., cycloalkenyl), cis or trans (e.g., E or Z). Exemplary alkenyl groups include optionally substituted C 2-24 Alkyl. Alkenyl can be monovalent or multivalent (e.g., divalent) by removing one or more hydrogens to form a suitable connection with the parent molecular group or a suitable connection between the parent molecular group and another substituent. Alkenyl can also be substituted or unsubstituted. For example, alkenyl can be substituted with one or more substituents, as described herein for alkyl. Non-limiting alkenyl includes allyl (All), vinyl (Vi), 1-butenyl, 2-butenyl, etc.

[0207] "Alkoxy" refers to -OR, where R is an optionally substituted aliphatic group, as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy such as trifluoromethoxy, and the like. Alkoxy groups can be substituted or unsubstituted. For example, alkoxy groups can be substituted with one or more substituents, as described herein for alkyl groups. Exemplary unsubstituted alkoxy groups include C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 Alkoxy.

[0208] "Alkoxyalkyl" refers to an alkyl group, as defined herein, substituted with an alkoxy group, as defined herein. Exemplary unsubstituted alkoxyalkyl groups contain 2 to 12 carbon (C 2-12 alkoxyalkyl), and those having an alkyl group containing 1 to 6 carbons and an alkoxy group containing 1 to 6 carbons (i.e., C 1-6 Alkoxy-C 1-6 In some embodiments, the alkoxyalkyl is -LOR, wherein L and R are each independently alkyl as defined herein.

[0209] "Alkoxycarbonyl" refers to -C(O)-OR, where R is an optionally substituted aliphatic group as described herein. In specific embodiments, the alkoxycarbonyl group is -C(O)-OAk, where Ak is an alkyl group as defined herein. The alkoxycarbonyl group may be substituted or unsubstituted. For example, the alkoxycarbonyl group may be substituted with one or more substituents, as described herein for alkyl. Exemplary unsubstituted alkoxycarbonyl groups include C 2-3 , C 2-6 , C 2-7 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 Alkoxycarbonyl.

[0210] "Alkyl" refers to a group having at least one carbon atom and up to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 ), wherein the saturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent compound (e.g., an alkane). The alkyl group can be branched, straight or cyclic (e.g., a cycloalkyl group). Exemplary alkyl groups include branched or unbranched saturated hydrocarbon groups of 1 to 24 carbon atoms, such as methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), isobutyl (iBu), sec-butyl (sBu), tert-butyl (tBu), pentyl (Pe), n-pentyl (nPe), isopentyl (iPe), sec-pentyl (sPe), neopentyl (neoPe), tert-pentyl (tPe), hexyl (Hx), heptyl (Hp), octyl (Oc), nonyl (Nn), decyl (De), dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can also be substituted or unsubstituted. The alkyl group may be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate linkage to the parent molecular group or between the parent molecular group and another substituent. For example, the alkyl group may be substituted with one, two, three, or in the case of an alkyl group of two or more carbons, four substituents independently selected from the group consisting of: (1) C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (2) C 1-6 Alkylsulfinyl (e.g., C 1-6 , wherein R is a C1-6 alkyl group); (3) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 (4) amino (e.g., -NR 1 R2 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein, or R 1 and R 2 (e.g., -C(O)-R, wherein R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C(O)-R; (12) C(O)-R; (13) C(O)-R; (14) C(O)-R; (15) C(O)-R; (16) C(O)-R; (17) C(O)-R; (18) C(O)-R; (19) C(O)-R; (20) C(O)-R; (21) C(O)-R; (22) C(O)-R; (23) C(O)-R; (24) C(O)-R; (25) C(O)-R; (26) C(O)-R; (27) C(O) 3-8 Cycloalkyl; (12) halo; (13) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (14) heterocyclyloxy (e.g., -OR, wherein R is heterocyclyl, as defined herein); (15) heterocyclylacyl (e.g., -C(O)-R, wherein R is heterocyclyl, as defined herein); (16) hydroxy (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =O); (20) C 1-6 Thioalkyl (e.g., -SR, where R is alkyl); (21) thiol (e.g., -SH); (22) -CO2R 1 , where R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (23)-C(O)NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (24)-SO2R 1 , where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (25)-SO2NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); and (26)-NR 1 R 2 , where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 or C 1-24 alkyl.

[0211] "Alkylene", "alkenylene" or "alkynylene" refers to a polyvalent (e.g., divalent) form of an alkyl, alkenyl or alkynyl group, respectively, as described herein. Exemplary alkylene groups include methylene, ethylene, propylene, butylene, and the like. In some embodiments, alkylene is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , C 1-24 , C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 In other embodiments, the alkylene group is C 2-3 , C 2-6 , C 2-12 , C 2-16 , C 2-18 , C 2-20 or C 2-24 The alkylene, alkenylene or alkynylene groups may be branched or unbranched. The alkylene, alkenylene or alkynylene groups may also be substituted or unsubstituted. For example, the alkylene, alkenylene or alkynylene groups may be substituted with one or more substituents, as described herein for alkyl groups.

[0212] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -S(O)- group. In some embodiments, unsubstituted alkylsulfinyl is C 1-6 or C 1-12 In other embodiments, alkylsulfinyl is -S(O)-R, wherein R is alkyl as defined herein.

[0213] "Alkylsulfinylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfinyl group. In some embodiments, unsubstituted alkylsulfinylalkyl is C 2-12 or C 2-24 Alkylsulfinylalkyl (e.g., C 1-6 Alkylsulfinyl-C 1-6 Alkyl or C 1-12 Alkylsulfinyl-C 1-12 In other embodiments, alkylsulfinylalkyl is -LS(O)-R, wherein L and R are each independently alkyl as defined herein.

[0214] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO2- group. In some embodiments, unsubstituted alkylsulfonyl is C1-6 or C 1-12 In other embodiments, alkylsulfonyl is -SO2-R, wherein R is optionally substituted alkyl (e.g., as described herein, comprising optionally substituted C 1-12 alkyl, haloalkyl or perfluoroalkyl).

[0215] "Alkylsulfonylalkyl" refers to an alkyl group, as defined herein, substituted with an alkylsulfonyl group. In some embodiments, unsubstituted alkylsulfonylalkyl is C 2-12 or C 2-24 Alkylsulfonylalkyl (e.g., C 1-6 Alkylsulfonyl-C 1-6 Alkyl or C 1-12 Alkylsulfonyl-C 1-12 In other embodiments, alkylsulfonylalkyl is -L-SO2-R, wherein L and R are each independently alkyl as defined herein.

[0216] "Alkynyl" refers to a group having at least 2 carbon atoms and up to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ), or 2 to 10 carbon atoms (C 2-10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be obtained by removing a hydrogen atom from a carbon atom of a parent alkyne. The alkynyl group can be branched, straight chain or cyclic (e.g., cycloalkynyl). Exemplary alkynyl groups include optionally substituted C 2-24 Alkyl. Alkyl groups can be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or an appropriate bond between the parent molecular group and another substituent. Alkyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more substituents, as described herein for alkyl.

[0217] By "ambient temperature" is meant a temperature in the range of 16°C to 26°C, for example 19°C to 25°C or 20°C to 25°C.

[0218] "Amide" refers to -C(O)NR 1 R 2 or-NHCOR 1 , where R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, an aromatic group as defined herein, or any combination thereof, or wherein R 1 and R 2Together with the respective nitrogen atom to which they are attached they may form a heterocyclyl group as defined herein.

[0219] "Amino" refers to -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl, or optionally substituted siloxy. In specific embodiments, R 1 and R 2 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0220] "Aminoalkyl" refers to an alkyl group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminoalkyl is -L-NR 1 R 2 , wherein L is alkyl as defined herein, and R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. In other embodiments, aminoalkyl is -LC(NR 1 R 2 )(R 3 )-R 4 , wherein L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, heteroaliphatic or aromatic group as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each is independently H or alkyl as defined herein.

[0221] "Aminooxy" refers to an oxy group, as defined herein, substituted with an amino group, as defined herein. In some embodiments, aminooxy is -O-NR 1 R 2 , where R 1 and R 2 R is each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein. 1 and R 2 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, optionally substituted silyl or optionally substituted siloxy.

[0222] Unless otherwise indicated, "aromatic group" refers to a cyclic conjugated group or moiety having 5 to 15 ring atoms of a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring and optionally multiple fused rings have a continuous delocalized π electron system. Typically, the number of out-of-plane π electrons corresponds to the Huckel rule (4n+2). The point of connection to the parent structure is typically through the aromatic portion of the fused ring system. Aromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, aromatic groups may be substituted with one or more substituents, as described herein for alkyl and / or aryl groups.

[0223] "Aromatic-carbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the aromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0224] "Aromatic-carbonyloxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the aromatic carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted aromatic group as defined herein.

[0225] "Aromatic-oxy" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, aromatic-oxy ​​is -OR, wherein R is an optionally substituted aromatic group as defined herein.

[0226] "Aromatic-oxycarbonyl" refers to an aromatic group that is or can be coupled to a compound disclosed herein, wherein the aromatic group is coupled or becomes coupled through an oxycarbonyl (-C(O)O-). In some embodiments, the aromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted aromatic group as defined herein.

[0227] "Aryl" refers to a group comprising at least 5 carbon atoms and up to 15 carbon atoms (C 5-15 ), such as 5 to 10 carbon atoms (C 5-10 ), an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic groups, heteroaliphatic groups, aromatic groups, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl groups, which are defined as groups containing aromatic groups having at least one heteroatom bound to the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl is also included in the term aryl, which defines groups containing aromatic groups without heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (e.g., -C(O)-R, where R is C 1-6 Alkyl); (2) C 1-6 Alkyl; (3)C 1-6 Alkoxy (e.g., -OR, where R is C 1-6 Alkyl); (4) C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LOR, wherein L and R are each independently C 1-6 Alkyl); (5) C 1-6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1-6 Alkyl); (6) C 1-6 Alkylsulfinyl-C 1-6 Alkyl (e.g., -LS(O)-R, wherein L and R are each independently C 1-6Alkyl); (7) C 1-6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1-6 Alkyl); (8) C 1-6 Alkylsulfonyl-C 1-6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1-6 alkyl); (9) aryl; (10) amino (e.g., -NR 1 R 2 , where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, halogenated aliphatic, halogenated heteroaliphatic, aromatic, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein); (11) C 1-6 Aminoalkyl (e.g., -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 Alkyl; R 1 and R 2 are each independently selected from hydrogen, an aliphatic, a heteroaliphatic, a halogenated aliphatic, a halogenated heteroaliphatic, an aromatic group, or any combination thereof as defined herein; or R 1 and R 2 Together with the nitrogen atom to which they are attached, they may form a heterocyclic group as defined herein; and R 3 and R 4 Each independently is H or C 1-6 alkyl); (12) heteroaryl; (13) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 aryl); (14) aroyl (e.g., C(O)-R, wherein R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (e.g., -L-N3, where L is C 1-6 alkyl); (18) aldehydes (e.g., -C(O)H); (19) aldehydes-C 1-6Alkyl (e.g., -LC(O)H, where L is C 1-6 Alkyl); (20)C 3-8 Cycloalkyl; (21)C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 Cycloalkyl); (22) halo; (23) C 1-6 Haloalkyl (e.g., -L 1 -X or -L 2 -C(X)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 Is a covalent bond or C 1-6 alkyl; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each independently is H or C 1-6 alkyl); (24) heterocyclyl (e.g., as defined herein, such as a 5-, 6-, or 7-membered ring containing one, two, three, or four non-carbon heteroatoms); (25) heterocyclyloxy (e.g., -OR, wherein R is a heterocyclyl, as defined herein); (26) heterocyclylacyl (e.g., -C(O)-R, wherein R is a heterocyclyl, as defined herein); (27) hydroxyl (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (29) nitro; (30) C 1-6 Nitroalkyl (e.g., -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 , where L 1 It is C 1-6 Alkyl; L 2 is a covalent bond or an alkyl group; and R 1 and R 2 Each independently is H or C 1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-C 1-6Alkyl; (33) Oxo (eg, =O); (34) C 1-6 Thioalkyl (e.g., -SR, where R is C 1-6 (35) thio-C 1-6 Alkoxy-C 1-6 Alkyl (e.g., -LSR, where L and R are each independently C 1-6 Alkyl); (36)-(CH2) r CO2R 1 , where r is an integer from 0 to 4, and R 1 Selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (37)-(CH2) r CONR 1 R 2 , wherein r is an integer from 0 to 4 and wherein R 1 and R 2 are each independently selected from: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (38)-(CH2) r S02R 1 , where r is an integer from 0 to 4, and where R 1 Selected from the group consisting of: (a) C 1-6 Alkyl, (b) C 4-18 Aryl, and (c) C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d) C 4-18 Aryl-C1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4, and where R 1 and R 2 are each independently selected from the group consisting of: (a) hydrogen, (b) an N-protecting group, (c) a C 1-6 Alkyl, (d)C 2-6 Alkenyl, (e)C 2-6 Alkynyl, (f)C 4-18 Aryl, (g)C 4-18 Aryl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 4-18 Aryl), (h)C 3-8 Cycloalkyl, and (i) C 3-8 Cycloalkyl-C 1-6 Alkyl (e.g., -LR, where L is C 1-6 Alkyl and R is C 3-8 (41) thiols (e.g., -SH); (42) perfluoroalkyls (e.g., -(CF2) n CF3, wherein n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2) n CF3, wherein n is an integer from 0 to 10); (44) aryloxy (e.g., -OR, wherein R is aryl); (45) cycloalkoxy (e.g., -OR, wherein R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, wherein L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -OLR, wherein L is alkyl and R is aryl). In specific embodiments, the unsubstituted aryl is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Aryl.

[0228] "Aryl-alkyl", "aryl-alkenyl" and "aryl-alkynyl" refer to an aryl group, as defined herein, coupled (or linked) to a parent molecular group through an alkyl, alkenyl or alkynyl group, respectively, as defined herein. Aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted or unsubstituted. For example, aryl-alkyl, aryl-alkenyl and / or aryl-alkynyl groups can be substituted with one or more substituents, as described herein for aryl and / or alkyl groups. Exemplary unsubstituted aryl-alkyl groups have 7 to 16 carbon atoms (C 7-16 aryl-alkyl), and those having an aryl group of 4 to 18 carbons and an alkyl group of 1 to 6 carbons (i.e., C 4-18 Aryl-C 1-6 Exemplary unsubstituted aryl-alkenyl groups have 7 to 16 carbon (C 7-16 aryl-alkenyl), and those having an aryl group containing 4 to 18 carbons and an alkenyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 Exemplary unsubstituted aryl-alkynyl groups have 7 to 16 carbon (C 7-16 aryl-alkynyl), and those having an aryl group containing 4 to 18 carbons and an alkynyl group containing 2 to 6 carbons (i.e., C 4-18 Aryl-C 2-6 In some embodiments, the aryl-alkyl group is -LR, wherein L is alkyl or alkylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkenyl group is -LR, wherein L is alkenyl or alkenylene as defined herein, and R is aryl as defined herein. In some embodiments, the aryl-alkynyl group is -LR, wherein L is alkynyl or alkynylene as defined herein, and R is aryl as defined herein.

[0229] "Arylene" refers to a polyvalent (e.g., divalent) form of an aryl group as described herein. Exemplary arylene groups include phenylene, naphthylene, biphenylene, triphenylene, diphenyl ether, acenaphthene, anthracene, or phenanthrenyl. In some embodiments, the arylene group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 or C 6-10 Arylene. Arylene can be branched or unbranched. Arylene can also be substituted or unsubstituted. For example, arylene can be substituted with one or more substituents, as described herein for aryl.

[0230] "Arylalkoxy" refers to an aryl-alkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, arylalkoxy is -OLR, wherein L is alkyl, as defined herein, and R is aryl, as defined herein.

[0231] "Aryloxy" refers to -OR, where R is an optionally substituted aryl as described herein. In some embodiments, unsubstituted aryloxy is C 4-18 or C 6-18 In other embodiments, R is aryl optionally substituted with alkyl, alkanoyl, amino, hydroxyl, and the like.

[0232] "Aryloxycarbonyl" refers to an aryloxy group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aryloxycarbonyl is C 5-19 Aryloxycarbonyl. In other embodiments, aryloxycarbonyl is -C(O)OR, wherein R is aryl as defined herein.

[0233] "Aroyl" refers to an aryl group attached to the parent molecular group through a carbonyl group. In some embodiments, unsubstituted aroyl is C 7-11 Aroyl or C 5-19 In other embodiments, aroyl is -C(O)-R, wherein R is aryl as defined herein.

[0234] "Aroyloxy" refers to an aroyl group, as defined herein, attached to the parent molecular group through an oxy group. In some embodiments, unsubstituted aroyloxy is C 5-19 In other embodiments, aroyloxy is -OC(O)-R, wherein R is aryl as defined herein.

[0235] "Azide" refers to a -N3 group.

[0236] "Azidoalkyl" refers to an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, azidoalkyl is -L-N3, wherein L is an alkyl group as defined herein.

[0237] "Azo" refers to the group -N=N-.

[0238] "Carbamoyl" refers to an amino group attached to the parent molecular group through a carbonyl group, as defined herein. In some embodiments, carbamoyl is -C(O)NR 1 R 2 Group, where R 1 and R 2are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0239] "Carbamoyloxy" refers to a carbamoyl group, as defined herein, appended to the parent molecular group through n oxy groups, as defined herein. In some embodiments, the carbamoyl group is -OC(O)NR 1 R 2 Group, where R 1 and R 2 are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 Together with the respective nitrogen atom to which it is attached, they may form a heterocyclyl group as defined herein.

[0240] "Carboimidoyl" refers to a -C(NR)- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof.

[0241] "Carbonyl" refers to a -C(O)- group, which may also be represented as >C=O.

[0242] "Carboxyl" refers to a -CO2H group or its anion.

[0243] "Catalyst" refers to a compound capable of catalyzing a synthesis reaction, typically present in a small amount relative to the reactants, as readily understood by one of ordinary skill in the art. In some embodiments, the catalyst may include a transition metal coordination complex.

[0244] "Cyanato" refers to an -OCN group.

[0245] "Cyano" refers to a -CN group.

[0246] "Cycloaliphatic" means a cyclic aliphatic radical as defined herein.

[0247] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, cycloalkoxy is -OR, wherein R is a cycloalkyl group, as defined herein.

[0248] "Cycloalkylalkoxy" means a -OLR group where L is alkyl or alkylene as defined herein and R is cycloalkyl as defined herein.

[0249] Unless otherwise indicated, "cycloalkyl" refers to a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical of 3 to 8 carbons, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl], and the like. Cycloalkyls may also be substituted or unsubstituted. For example, cycloalkyls may be substituted with one or more groups, including those described herein for alkyls. In addition, cycloalkyls may include one or more double bonds and / or triple bonds.

[0250] "Cycloheteroaliphatic" refers to a heteroaliphatic group as defined herein that is cyclic.

[0251] "Disilyl" refers to a group containing a Si-Si bond. In some embodiments, the disilyl group is -SiR S1 R S2 -SiR S3 R S4 R S5 Or-SiR S1 R S2 -SiR S3 R S4 - group, where R S1 , R S2 , R S3 , R S4 and R S5 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino.

[0252] "Disulfide" means -SSR, wherein R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof as defined herein.

[0253] An "electron donating group" refers to a functional group that is capable of donating at least a portion of its electron density to the ring to which it is directly attached, such as by resonance.

[0254] "Electron withdrawing group" refers to a functional group capable of accepting electron density from the ring to which it is directly attached, such as by inductive electron withdrawal.

[0255] "Halo" refers to F, Cl, Br or I.

[0256] "Haloaliphatic" means an aliphatic group as defined herein wherein one or more hydrogen atoms (eg, 1 to 10 hydrogen atoms) are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0257] "Haloalkyl" refers to an alkyl group as defined herein in which one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently replaced by halogen atoms, e.g., fluorine, bromine, chlorine, or iodine. In independent embodiments, haloalkyl can be a -C4 group, in which each X can be independently selected from fluorine, bromine, chlorine, or iodine. In some embodiments, haloalkyl is -LX, in which L is an alkyl group as defined herein, and X is fluorine, bromine, chlorine, or iodine. In other embodiments, haloalkyl is -LC(X)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein; X is fluorine, bromine, chlorine or iodine; and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0258] "Haloheteroaliphatic" refers to a heteroaliphatic group as defined herein wherein one or more hydrogen atoms, eg, 1 to 10 hydrogen atoms, are independently replaced by a halogen atom (eg, fluorine, bromine, chlorine, or iodine).

[0259] "Heteroaliphatic" refers to an aliphatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaliphatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaliphatic groups may be substituted with one or more substituents, such as described herein for alkyl groups.

[0260] "Heteroaliphatic-carbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaliphatic-carbonyl group is -C(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0261] "Heteroaliphatic-carbonyloxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaliphatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0262] "Heteroaliphatic-oxy" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is or becomes coupled via an oxy group (-C(O)-). In some embodiments, the heteroaliphatic-oxy ​​group is -OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0263] "Heteroaliphatic-oxycarbonyl" refers to a heteroaliphatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaliphatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, heteroaliphatic-oxycarbonyl is -C(O)OR, wherein R is an optionally substituted heteroaliphatic group as defined herein.

[0264] "Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" refer to an alkyl, alkenyl or alkynyl group (which may be branched, straight chain or cyclic) as defined herein, respectively, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms, which heteroatoms may be selected from but are not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus and oxidized forms thereof.

[0265] "Heteroalkylene," "heteroalkenylene," and "heteroalkynylene" refer to polyvalent (eg, divalent) forms of heteroalkyl, heteroalkenyl, or heteroalkynyl groups, respectively, as described herein.

[0266] "Heteroaromatic" refers to an aromatic group as defined herein, which contains at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms or one to 5 heteroatoms within the group, the heteroatoms being selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Heteroaromatic groups are unsubstituted or substituted, for example, with functional groups as described herein. For example, heteroaromatic groups may be substituted with one or more substituents, such as described herein for alkyl and / or aryl groups.

[0267] By "heteroaromatic-carbonyl" is meant a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyl group (-C(O)-). In some embodiments, the heteroaromatic-carbonyl is -C(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0268] "Heteroaromatic-carbonyloxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through a carbonyloxy group (-OC(O)-). In some embodiments, the heteroaromatic-carbonyloxy group is -OC(O)-R, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0269] "Heteroaromatic-oxy" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxy group (-O-). In some embodiments, the heteroaromatic-oxy ​​is -OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0270] "Heteroaromatic-oxycarbonyl" refers to a heteroaromatic group that is or can be coupled to a compound disclosed herein, wherein the heteroaromatic group is coupled or becomes coupled through an oxycarbonyl group (-C(O)O-). In some embodiments, the heteroaromatic-carbonyl is -C(O)OR, wherein R is an optionally substituted heteroaromatic group as defined herein.

[0271] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms (e.g., one to four heteroatoms) in the ring, wherein the heteroatoms are selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups may have a monocyclic or multiple condensed rings, wherein the condensed rings may or may not be aromatic and / or contain heteroatoms, provided that the point of attachment is through an atom of an aromatic heteroaryl group. Heteroaryl groups may be substituted by one or more groups that are not hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary heteroaryl groups include a subset of heterocyclic groups as defined herein, which are aromatic, i.e., they contain 4n+2 π electrons in a monocyclic or polycyclic ring system.

[0272] "Heteroarylene" refers to a polyvalent (eg, divalent) form of a heteroaryl group as described herein.

[0273] "Heteroatom" refers to an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In particular disclosed embodiments, heteroatoms do not include halogen atoms, such as when valence restrictions do not permit.

[0274] Unless otherwise indicated, "heterocyclyl" refers to a 5, 6 or 7-membered ring containing one, two, three or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur or halide). The 5-membered ring has 0 to 2 double bonds, and the 6-membered and 7-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic and tetracyclic groups, wherein any of the above heterocyclic rings is fused with one, two or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuranyl, benzothienyl, etc. The heterocyclic group includes thiirane, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridinyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidinone, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isoxazolidinyl, thiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furanyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxathiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0275] "Heterocyclyloxy" refers to a heterocyclyl, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, heterocyclyloxy is -OR, wherein R is heterocyclyl, as defined herein.

[0276] "Heterocycloacyl" means a heterocyclyl, as defined herein, attached to the parent molecular moiety through a carbonyl group. In some embodiments, heterocycloacyl is -C(O)-R, wherein R is a heterocyclyl, as defined herein.

[0277] "Hydrazino" refers to -NR 1 -NR 2 R 3 , where R 1 , R 2 and R 3are each independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl or optionally substituted siloxy as defined herein, or any combination thereof; or wherein R 1 and R 2 A combination of or 2 and R 3 The combination of together with the nitrogen atom to which they are attached may form a heterocyclic group as defined herein. 1 , R 2 or R 3 Each is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl. In specific embodiments, R 2 and R 3 Together with the respective nitrogen atom to which they are attached, they may form an optionally substituted heterocyclic group.

[0278] "Hydroxyl" refers to -OH.

[0279] "Hydroxyalkyl" refers to an alkyl group as defined herein substituted with 1 to 3 hydroxy groups, provided that no more than one hydroxy group may be attached to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, hydroxyalkyl is -L-OH, wherein L is an alkyl group as defined herein. In other embodiments, hydroxyalkyl is -LC(OH)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0280] "Imino" refers to a moiety comprising a carbon imino group. In some embodiments, the imino group is C(NR 1 )R 2 , where R 1 and R 2 Each is independently selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, optionally substituted siloxy, or any combination thereof. In other embodiments, the imino group is -C(NR 1 )H、-C(NR 1 )R Ak or -C(NR N1 )R Ar , where R1 R is hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, optionally substituted silyl, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl or optionally substituted aryl-alkyl, or optionally substituted siloxy; R Ak is optionally substituted alkyl or optionally substituted aliphatic; and R Ar is an optionally substituted aryl group or an optionally substituted aromatic group.

[0281] "Imino" refers to a -NR- group. In some embodiments, R is selected from hydrogen, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic. In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0282] "Isocyanato" refers to a -NCO group.

[0283] "Isocyano" refers to a -NC group.

[0284] "Ketone" refers to -C(O)R or a compound containing this group, wherein R is selected from aliphatic, heteroaliphatic, aromatic or any combination thereof as defined herein. Examples of ketones may include R 1 C(O)R, where R and R 1 Each is independently selected from aliphatic, halogenated aliphatic, halogenated heteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof as defined herein.

[0285] "Nitro" refers to a -NO2 group.

[0286] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with 1 to 3 nitro groups. In some embodiments, nitroalkyl is -L-NO, wherein L is an alkyl group, as defined herein. In other embodiments, nitroalkyl is -LC(NO)(R 1 )-R 2 , wherein L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each is independently H or alkyl as defined herein.

[0287] "Oxo" refers to a =0 group.

[0288] "Oxy" refers to -O-.

[0289] "Perfluoroalkyl" refers to an alkyl group as defined herein in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, wherein n is an integer from 0 to 10.

[0290] "Perfluoroalkoxy" refers to an alkoxy group as defined herein wherein each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, wherein R is a perfluoroalkyl group as defined herein.

[0291] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound, or composition described herein) that contains a cation or anion compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge SM et al., "Pharmaceutical salts," J. Pharm. Sci. 1977 January; 66 (1): 1-19; and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. PHStahl and CGWermuth). Salts can be prepared in situ during the final isolation and purification of the compounds of the invention, or prepared separately by reacting a free base group with a suitable organic acid (thereby producing anionic salts) or by reacting an acid group with a suitable metal or organic salt (thereby producing cationic salts). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, ethylenediaminetetraacetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptanoate, hexanoate, hydrobromide, hydrochloride, hydroiodide, isethionate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, malate, The invention also includes but is not limited to iodine, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, subacetate, succinate, sulfate, tannate, tartrate, theophyllinate, thiocyanate, triethyl iodide, toluenesulfonate, undecanoate, valerate, and the like. Representative cationic salts include metal salts, such as alkali metal or alkaline earth metal salts, for example, barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; and non-toxic ammonium, quaternary ammonium, and amino cations, including but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like.Other cationic salts include organic salts such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine and procaine. Other salts include ammonium, sulfonium, sulfoxonium, phosphorus, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepi nium), optionally substituted indolium, optionally substituted isoindolinium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0292] "Silyl" refers to -SiR 1 R 2 R 3 Or-SiR 1 R 2 - group. In some embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyl is -Si(R) a (OR)b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0293] "Silyloxy" refers to -OR, where R is an optionally substituted silyl group as described herein. In some embodiments, silyloxy is -O-SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 Each is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, optionally substituted heteroaromatic, or optionally substituted amino. In specific embodiments, R 1 , R 2 and R 3 Each is independently H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted alkyl-aryl, optionally substituted aryl-alkyl, or optionally substituted amino. In other embodiments, silyloxy is —O—Si(R) a (OR) b (NR2) c , wherein each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic, or optionally substituted heteroaromatic; a, b, and c are each ≥ 0; and a+b+c=3. In specific embodiments, each R is independently H, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkyl-aryl, or optionally substituted aryl-alkyl.

[0294] "Sulfinyl" refers to a -S(O)- group.

[0295] "Sulfo" refers to a -S(O)2OH group.

[0296] "Sulfonyl" or "sulfonate" refers to a -S(O)2- group or -SO2R, where R is selected from hydrogen, an aliphatic, a heteroaliphatic, a haloaliphatic, a haloheteroaliphatic, an aromatic group as defined herein, or any combination thereof.

[0297] "Thioalkyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkyl groups include C 1-6 In some embodiments, the thioalkyl group is -SR, wherein R is alkyl as defined herein.

[0298] "Thiol" refers to a -SH group.

[0299] One of ordinary skill in the art will recognize that the definitions provided above are not intended to encompass impermissible substitution patterns (e.g., a methyl group substituted with 5 different groups, etc.). Such impermissible substitution patterns are readily recognized by one of ordinary skill in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted, unless otherwise specified therein.

[0300] As used herein, the term "about" refers to a difference of ±10% from any stated value. When used, the term modifies any stated value, range of values, or endpoints of one or more ranges.

[0301] As used herein, the terms "top", "bottom", "lower", "above", and "below" are used to provide relative relationships between multiple structures. The use of these terms does not indicate or require that a particular structure must be located at a particular position in the device.

[0302] Other features and advantages of the invention will be apparent from the following description and claims.

[0303] In various embodiments, the silicon-containing precursor is a silane. Silanes include, but are not limited to, substituted and unsubstituted silanes, halosilanes, aminosilanes, organosilanes, alkylsilanes, alkylaminosilanes, and alkylhalosilanes. In specific embodiments, the silicon-containing precursor comprises a halosilane precursor. In specific embodiments, the silicon-containing precursor comprises an aminosilane precursor.

[0304] Aminosilanes include at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogen, oxygen, halogens, and carbon. Examples of aminosilanes are mono-, di-, tri-, and tetra-aminosilanes (H3Si(NH2), H2Si(NH2)2, HSi(NH2)3, and Si(NH2)4, respectively), and substituted mono-, di-, tri-, and tetra-aminosilanes, such as tert-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tert-butylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butyl silylcarbamate (tert-butyl silylcarbamate), and tert-butyl silylcarbamate (tert-butyl silylcarbamate). silylcarbamate), SiH(CH3)-(N(CH3)2)2, SiHCl-(N(CH3)2)2, (Si(CH3)2NH)3, di(sec-butylamino)silane (DSBAS), di(isopropylamino)silane (DIPAS), bis(diethylamino)silane (BDEAS), and the like. A further example of aminosilane is trisilylamine (N(SiH3)3). In one example, the silicon-containing precursor is DI PAS. In another example, the silicon-containing precursor is BTBAS. In some embodiments, the silane precursor is a siloxane precursor. In some embodiments, the aminosilane is a siloxane. The siloxane precursor may be a disiloxane, or a trisiloxane, or a cyclic siloxane, or a tetrasiloxane. The cyclic siloxane may include a cyclic tetrasiloxane, such as 2,4,6,8-tetramethylcyclotetrasiloxane (TMCTS), octamethylcyclotetrasiloxane (OMCTS), and heptamethylcyclotetrasiloxane (HMCTS). Other cyclic siloxanes may also include, but are not limited to, cyclotrisiloxane and cyclopentasiloxane. In some embodiments, the silicon-containing deposition precursor is 1-dimethylamino-1,1,5,5,5,-pentamethyldisiloxane. In some embodiments, siloxane may have a three-dimensional or cage-shaped structure. Cage-shaped siloxanes have silicon atoms bridged to each other by oxygen atoms to form a polyhedron or any 3-D structure. An example of a cage-shaped siloxane precursor molecule is silsesquioxane. Cage-shaped siloxane structures are further described in detail in Cleemput et al., co-owned U.S. Patent No. 6,576,345, the entire contents of which are incorporated herein by reference for all purposes. In some embodiments, siloxanes may be linear. Linear siloxanes may include, but are not limited to, disiloxanes, such as pentamethyldisiloxane (PMDSO), tetramethyldisiloxane (TMDSO) and hexamethyltrisiloxane. PMDSO and TMDSO can be used to form SiOC films.

[0305] The silicon-containing precursor may contain one or more optionally substituted amino groups, thereby providing non-limiting aminosilanes. In one embodiment, the precursor has the formula (R') 4-x Si(NR"2) x ,in: x is 1, 2, 3, or 4; each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazino, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano, or isocyano, any of which may be optionally substituted; and Each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0306] In another embodiment, the precursor has the formula (R"2N) x (R') 3-x Si-L-Si(R') 3-x (NR"2) x ,in: Each x is independently 0, 1, 2, or 3; L is a linking group such as a covalent bond, an optionally substituted aliphatic group, an optionally substituted heteroaliphatic group, an optionally substituted aromatic group, an optionally substituted heteroaromatic group, an oxy group (—O—), an imino group or a silyl group; Each R' is independently H, aliphatic, aliphatic-carbonyl, aliphatic-carbonyloxy, aliphatic-oxy, aliphatic-oxycarbonyl, heteroaliphatic, heteroaliphatic-carbonyl, heteroaliphatic-carbonyloxy, heteroaliphatic-oxy, heteroaliphatic-oxycarbonyl, aromatic, aromatic-carbonyl, aromatic-carbonyloxy, aromatic-oxy, aromatic-oxycarbonyl, heteroaromatic, heteroaromatic-oxy, amino, hydrazine, azido, hydroxy, silyl, siloxy, cyanato, isocyanato, cyano or isocyano, any of which may be optionally substituted; and each R" is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic or amino, any of which may be optionally substituted; or optionally, wherein two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclyl.

[0307] In specific embodiments, L is an optionally substituted imino group, such as -NR-, wherein R is H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group. In other embodiments, L is an optionally substituted silyl group, such as -SiR2-, wherein each R is independently H, an optionally substituted aliphatic group, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, or an optionally substituted aromatic group.

[0308] In one case, at least one x is not 0. In another embodiment, x can be 0 (e.g., if L comprises a carbon atom or a heteroatom). In yet another embodiment, x is 0; and / or L comprises an optionally substituted aliphatic, an optionally substituted alkylene, an optionally substituted alkenylene, an optionally substituted alkynylene, an optionally substituted heteroaliphatic, an optionally substituted heteroalkylene, an optionally substituted heteroalkenylene, an optionally substituted heteroalkynylene, an optionally substituted aromatic, an optionally substituted arylene, an optionally substituted heteroaromatic, an optionally substituted heteroarylene, an oxy (—O—), an imino, or a silyl group.

[0309] In specific embodiments, at least one R' or R" is not H. The precursor can have any useful combination of R' groups and amino groups (NR"2) attached to one or more silicon atoms.

[0310] In some embodiments, R' is H, optionally substituted amino (e.g., -NR2), aliphatic-oxy ​​(e.g., alkoxy or -OR), aliphatic-carbonyl (e.g., alkanoyl or -C(O)R), aliphatic-carbonyloxy (e.g., alkanoyloxy or -OC(O)R), aliphatic-oxycarbonyl (e.g., alkoxycarbonyl or -C(O)OR), silyl (e.g., -SiR3), aliphatic-oxy-silyl (e.g., alkoxysilyl or -Si(R) a (OR) b ), aminosilyl (e.g., -Si(R) a (NR2) b ), silyloxy (e.g., -O-SiR3), aliphatic-oxy-silyloxy (e.g., alkoxysilyloxy or -O-Si(R) a (OR) b ), aminosilyloxy (e.g., -O-Si(R) a (NR2) b), aromatic groups (e.g., aryl), aromatic-oxy ​​groups (e.g., aryloxy or -OR), hydroxyl (-OH), formyl (-C(O)H), etc. In specific embodiments, each R is independently H, optionally substituted aliphatic groups, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, optionally substituted heteroaliphatic groups, optionally substituted aromatic groups, optionally substituted aryl groups, and optionally substituted heteroaromatic groups; a≥0; b≥1; and a+b=3. In some embodiments, two R groups may form an optionally substituted heterocyclic group together with the nitrogen atom to which they are attached. In other embodiments, each R is independently H, optionally substituted alkyl groups, optionally substituted alkenyl groups, optionally substituted alkynyl groups, or optionally substituted aryl groups.

[0311] In other embodiments, R" is H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted silyl, or optionally substituted siloxy. In some embodiments, R" is optionally substituted alkyl (e.g., Me, Et, nPr, iPr, sBu, or tBu). In other embodiments, R" is -SiR'3, -SiR3, -Si(R') a (OR) b 、-Si(R) a (OR) b 、-Si(R') a (NR2) b 、-Si(R) a (NR2) b 、-Si(R') a (OR) b (NR2) c 、-Si(R) a (OR) b (NR2) c , -O-SiR'3, -O-SiR3, -O-Si(R') a (OR) b 、-O-Si(R) a (OR) b 、-O-Si(R') a (NR2) b 、-O-Si(R) a (NR2) b 、-O-Si(R') a (OR) b (NR2) c or -O-Si(R) a (OR) b (NR2) c, wherein each R' is independently H, aliphatic, heteroaliphatic, aromatic, heteroaromatic, amino, hydrazine, azido, hydroxyl, silyl, siloxy, cyanato, isocyanato, cyano or isocyano, any of which may be optionally substituted; each R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted aromatic or optionally substituted heteroaromatic; a, b and c are each ≥ 0; and a+b+c=3 or a+b=3 (if c is absent). In specific embodiments, R is H, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl.

[0312] The silicon-containing precursor may include at least one R' group attached to a silicon atom. In one embodiment, the precursor has the formula (R')(H) 3-x Si(NR"2) x , wherein R' and R" can be any of those described herein, and wherein x is 1, 2 or 3. In another embodiment, the precursor has the formula (R')(H)2Si(NR"2), wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')(H)Si(NR"2)2, wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R')2(H)Si(NR"2), wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R')2Si(NR"2)2, wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R')3Si(NR"2), wherein R' and R" can be any of those described herein.

[0313] The precursor may have no R' groups attached to the silicon atom. In one embodiment, the precursor has the formula (H) 4- x Si(NR"2) x , wherein each R" can independently be any of those described herein, and wherein x is 1, 2, 3 or 4. In another embodiment, the precursor has the formula Si(NR"2) x , wherein each R" can independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, or heteroaromatic.

[0314] The precursor may contain one or more hydrogen atoms attached to a silicon atom. In one embodiment, the precursor has the formula (H)3Si(NR"2) or (H)2Si(NR"2)2 or (H)Si(NR"2)3, wherein each R" may independently be any of those described herein. In specific embodiments, each R" is independently aliphatic, heteroaliphatic, aromatic, heteroaromatic, or amino, wherein any of these groups may be optionally substituted.

[0315] The precursor may contain a heterocyclic group having a nitrogen atom. In one embodiment, the formula has the formula H3Si-Het, wherein Het is an optionally substituted heterocyclic group containing at least one nitrogen atom. In a specific embodiment, the precursor has the formula wherein the heterocyclyl group may be optionally substituted (e.g., substituted with any substituent described herein as substituted with an alkyl group), and wherein n is 1, 2, 3, 4, or 5. In one embodiment, the formula is of the formula R'3Si-Het, wherein Het is an optionally substituted heterocyclyl group comprising at least one nitrogen atom, and each R' may independently be any of those described herein. In a specific embodiment, the precursor is of the formula wherein the heterocyclyl group can be optionally substituted (eg, with any substituent described herein as substituted with alkyl); each R′ can independently be any of those described herein; and wherein n is 1, 2, 3, 4, or 5.

[0316] In some cases, the precursor may have two or more silicon atoms, wherein the precursor may contain Si-Si bonds. In a specific embodiment, the precursor has the formula (R"2N): x (R') 3-x Si-Si(R') 3-x (NR"2) x , wherein R' and R" can be any of those described herein. In one embodiment, the precursor has the formula (R"2N)(R')2Si-Si(R')2(NR"2), wherein R' and R" can be any of those described herein. In another embodiment, the precursor has the formula (R"2N)2(R')Si-Si(R')(NR"2)2, wherein R' and R" can be any of those described herein. In yet another embodiment, the precursor has the formula (R"2N)3Si-Si(NR"2)3, wherein each R" can independently be any of those described herein.

[0317] The precursor may include different groups attached to the silicon atom. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-SiH3, wherein R' and R" can be any of those described herein.

[0318] The linking group may be present between two silicon atoms. In one case, the precursor has the formula (R"2N): x (R') 3-x Si-NR-Si(R') 3-x (NR"2) x , wherein R' and R" can be any of those described herein, and wherein is H, an optionally substituted aliphatic, an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, or an optionally substituted aromatic. In another embodiment, the precursor has the formula (R"2N) x (H) 3-x Si-NR-Si(H) 3-x (NR"2) x , wherein R, R' and R" can be any of those described herein.

[0319] The precursor may comprise a combination of an R' group and a linker having a heteroatom. In one instance, the precursor has the formula (R')3Si-NR-Si(R')3, wherein R and R' may be any of those described herein. In another instance, the precursor has the formula (R')3Si-L-Si(R')3, wherein L and R' may be any of those described herein. In a specific embodiment, L is an oxy group (-O-), an optionally substituted imino group (e.g., -NR-), or an optionally substituted silyl group (e.g., -SiR2-).

[0320] The precursor may include any useful combination of R' and NR"2 groups in combination with two silicon atoms. In one instance, the precursor has the formula (R"2N)(R')2Si-L-Si(R')2(NR"2) x , wherein L, R' and R" can be any of those described herein.

[0321] The precursor may contain a heterocyclic group containing silicon and nitrogen atoms. In one embodiment, the precursor has the formula wherein R' and R" can be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0322] In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein each R" can independently be any of those described herein; and wherein n is 1, 2, 3 or 4. In another embodiment, the precursor has the formula wherein R' and R" may be any of those described herein, and wherein n is 1, 2, 3 or 4. In yet another embodiment, the precursor has the formula wherein R" can independently be any of those described herein, and wherein n is 1, 2, 3 or 4.

[0323] In any of the precursors described herein, two R" may be taken together with the nitrogen atom to which they are attached to form an optionally substituted heterocyclic group.

[0324] 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、(R')3Si(NHR Ak In some embodiments, R' and R" can each independently be any of those described herein (e.g., H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl). In other embodiments, each R Ak R is independently H, optionally substituted aliphatic, optionally substituted heteroaliphatic, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted alkynyl. Ak It is methyl (Me), ethyl (Et), n-propyl (nPr), isopropyl (iPr), n-butyl (nBu), sec-butyl (sBu), isobutyl (iBu), tert-butyl (tBu) and the like.

[0325] Non-limiting examples of the precursor 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 (Si H2Et[NEt2]); ethylaminotrimethylsilane (SiMe3[NHEt]); diethylaminodimethylsilane (SiHMe2[NEt2]); diethylaminodiethylsilane (SiHEt2[NEt2]); diethylaminotrimethylsilane (SiMe3[NEt2]); diethylaminotriethylsilane (SiEt3[NEt2]); isopropylaminodimethylsilane (SiHMe2[NHiPr]); isopropylaminotrimethylsilane (SiMe3[NHiPr]); isopropylaminodiethylsilane (SiHEt2[NHiPr]); isopropylaminotriethylsilane (SiEt3[NHiPr]); diisopropylaminotrimethylsilane (SiMe3[NiPr2]); diisopropylaminosilane (SiH3[NiPr2], C6H 17NSi or DIPAS); diisopropylaminomethylsilane (SiH2Me[NiPr2]); diisopropylaminodimethylsilane (SiHMe2[NiPr2]); diisopropylaminodiethylsilane (SiHEt2[NiPr2]); diisopropylaminotriethylsilane (SiEt3[NiPr2]); n-propylaminotrimethylsilane (SiMe3[NHnPr]); di-sec-butylaminosilane (SiH3[NsBu2]); di-sec-butylaminomethylsilane (SiH2Me[NsBu2]); isobutylaminotrimethylsilane (SiMe3[NHiBu]); n-butylaminotrimethylsilane (SiMe3[NHnBu]); tert-butylamino tert-Butylaminotrimethylsilane (SiMe3[NHtBu]); tert-Butylaminodiethylsilane (SiHEt2[NHtBu]); tert-Butylaminotriethylsilane (SiEt3[NHtBu]); dicyclohexylaminosilane (SiH3[NCy2], where Cy is cyclohexyl); N-propylisopropylaminosilane (SiH3[NiPrnPr]); N-methylcyclohexylaminosilane (SiH3[NMeCy]); N-ethylcyclohexylaminosilane (SiH3[NEtCy]); allylphenylaminosilane (SiH3[NAllPh]); N-isopropylcyclohexylaminosilane (SiH3[NCy2]); N-isopropylcyclohexyl ... H3[NiPrCy]); allylcyclopentylaminosilane (SiH3[NAllCp]); phenylcyclohexylaminosilane (SiH3[NPhCy]); cyclohexylaminotrimethylsilane (SiMe3[NHCy], wherein Cy is cyclohexyl); pyrrolyltrimethylsilane (SiMe3[NHPy], wherein Py is pyrrolyl); pyrrolidinyltrimethylsilane (SiMe3[NHPyr], wherein Pyr is pyrrolidinyl); piperidinyltrimethylsilane (SiMe3[NHPip], wherein Pip is piperidinyl); piperazinyltrimethylsilane (SiMe3[NHPz], wherein Pz is piperazinyl); imidazolyltrimethylsilane (SiMe3[NHIm], wherein wherein Im is an imidazolyl group); bis(dimethylamino)silane (SiH2[NMe2]2 or BDMAS); bis(dimethylamino)methylsilane (SiMeH[NMe2]2); bis(dimethylamino)dimethylsilane (SiMe2[NMe2]2 or BDMADMS); bis(dimethylamino)diethylsilane (SiEt2[NMe2]2); bis(dimethylamino)methylvinylsilane (SiMeVi[NMe2]2); bis(ethylamino)dimethylsilane (SiMe2[NHEt]2); bis(ethylmethylamino)silane (SiH2[NMeEt]2); bis(ethylmethylamino)dimethylsilane (SiMe2[NMeEt]2);Bis(ethylmethylamino)diethylsilane (SiEt2[NMeEt]2); Bis(ethylmethylamino)methylvinylsilane (SiMeVi[NMeEt]2); Bis(diethylamino)silane (SiH2[NEt2]2, C8H; 22 N2Si or BDEAS); bis(diethylamino)dimethylsilane (SiMe2[NEt2]2); bis(diethylamino)methylvinylsilane (SiMeVi[NEt2]2); bis(diethylamino)diethylsilane (SiEt2[NEt2]2); bis(isopropylamino)dimethylsilane (SiMe2[NHiPr]2); bis(isopropylamino)diethylsilane (SiEt2[NHiPr]2); bis(isopropylamino)methylvinylsilane (SiMeVi[NHiPr]2 ); bis(diisopropylamino)silane (SiH2[NiPr2]2); bis(diisopropylamino)dimethylsilane (SiMe2[NiPr2]2); bis(diisopropylamino)diethylsilane (SiEt2[NiPr2]2); bis(diisopropylamino)methylvinylsilane (SiMeVi[NiPr2]2); bis(methylamino)silane (SiH2[NHMe]2); bis(sec-butylamino)silane (SiH2[NHsBu]2); bis(sec-butylamino)methylsilane (SiHMe [NHsBu]2); bis(sec-butylamino)ethylsilane (SiHEt[NHsBu]2); bis(tert-butylamino)silane (SiH2[NHtBu]2 or BTBAS); bis(tert-butylamino)dimethylsilane (SiMe2[NHtBu]2); bis(tert-butylamino)methylvinylsilane (SiMeVi[NHtBu]2); bis(tert-butylamino)diethylsilane (SiEt2[NHtBu]2); bis(1-imidazolyl)dimethylsilane (SiMe2[Im]2, where I m is imidazolyl); tris(dimethylamino)silane (SiH[NMe2]3 or 3DMAS); tris(dimethylamino)phenylsilane (SiPh[NMe2]3); tris(dimethylamino)methylsilane (SiMe[NMe2]3); tris(dimethylamino)ethylsilane (SiEt[NMe2]3); tris(ethylmethylamino)silane (SiH[NEtMe]3); tris(diethylamino)silane (SiH[NEt2]3); tris(isopropylamino)silane (SiH[NHiPr]3, C9H 25N3Si or TIPAS); tris(dimethylamino)silylamide (Si[NMe2]3[NH2]); tetrakis(dimethylamino)silane (Si[NMe2]4); tetrakis(ethylmethylamino)silane (Si[NEtMe]4); tetrakis(diethylamino)silane (Si[NEt2]4); 1,2-diethyl-tetrakis(diethylamino)disilane ([Et2N]2EtSi-SiEt[NEt2]2); 1,2-dimethyl-tetrakis(dimethylamino)disilane ([ Hexa(methylamino)disilane ([MeHN]3Si-Si[NHMe]3); Hexa(ethylamino)disilane ([EtHN]3Si-Si[NHEt]3); Hexa(dimethylamino)disilazane (Me2N-Si[NMe2]2-Si[NMe2]2-NMe2), etc. in conclusion

[0326] In the foregoing description, numerous specific details are set forth to provide a thorough understanding of the embodiments presented. The disclosed embodiments may be practiced without some or all of these specific details. In other cases, well-known process operations are not described in detail so as not to unnecessarily obscure the disclosed embodiments. Although the disclosed embodiments are described in conjunction with specific embodiments, it should be understood that this is not intended to limit the disclosed embodiments.

[0327] Although the foregoing embodiments have been described in detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems and devices of the present embodiments. Therefore, the present embodiments should be considered illustrative rather than restrictive, and the embodiments are not limited to the details given herein.

Claims

1. A method for processing a substrate, the method comprising: conformally depositing a silicon-containing film in one or more recessed features of the substrate; as well as At least a portion of the silicon-containing film is etched to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma. The method of claim 1 , wherein the silicon-containing film comprises an amorphous silicon layer. 3 . The method of claim 1 , wherein the silicon-containing film comprises silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbon oxynitride.

4. The method of claim 3, wherein conformally depositing the silicon-containing film comprises: flowing a silicon-containing precursor to adsorb onto the surface of the substrate; thermally decomposing the silicon-containing precursor to form an amorphous silicon layer; as well as The amorphous silicon layer is exposed to plasma to convert the amorphous silicon layer into silicon oxide, silicon nitride, silicon carbide, silicon oxycarbide, silicon carbonitride, silicon oxynitride, or silicon carbon oxynitride.

5. The method of claim 1 , wherein conformally depositing the silicon-containing film comprises: depositing the silicon-containing film by thermal ALD or thermal CVD; as well as The silicon-containing film is treated with a densification gas plasma.

6. The method of claim 1 , wherein at least one of the desired depth and the desired profile of the etch is based on one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition, relative concentrations of the gas composition, and RF power.

7. A method for processing a substrate, the method comprising: flowing a silane-based precursor into a reaction chamber to adsorb into one or more recessed features of the substrate, wherein the substrate is at an elevated temperature to thermally decompose the silane-based precursor and conformally deposit an amorphous silicon layer in the one or more recessed features of the substrate; generating a remote plasma in a remote plasma chamber upstream of the reaction chamber, the remote plasma comprising radicals of hydrogen, halides, hydrocarbons, fluorocarbons, or combinations thereof; as well as The substrate is exposed to the remote plasma in the reaction chamber to etch at least a portion of the silicon-containing layer in the one or more recessed features to at least one of a desired depth and a desired profile by adjusting one or more of the following etching parameters: chamber pressure, substrate temperature, exposure time, gas composition of the remote plasma, relative concentrations of the gas composition, and RF power.

8. A method of processing a substrate contained in a processing chamber, the method comprising: introducing a silicon-containing precursor and a reactant into the process chamber to form a silicon-containing film over the substrate without igniting a plasma when the substrate temperature is below about 700° C.; After forming the silicon-containing film, a plasma treatment operation is performed, the plasma treatment operation comprising: stopping the flow of the silicon-containing precursor and the flow of the reactant; introducing a densification gas into the process chamber; and igniting a plasma to treat the silicon-containing film; and At least one of the silicon-containing precursor, the reactants, or process conditions is adjusted during the plasma treatment operation to change at least a composition or density of the silicon-containing film to form a treated silicon-containing film.

9. The method according to claim 8, further comprising: At least a portion of the treated silicon-containing film is etched to at least one of a desired depth and a desired profile by exposing the substrate to a remote plasma.

10. An apparatus for processing a substrate, the apparatus comprising: one or more processing chambers, each processing chamber including a chuck; one or more gas inlets leading into the process chamber and associated flow control hardware; as well as A controller having at least one processor and a memory, wherein the at least one processor is communicatively connected to the memory, the at least one processor is at least operably connected to the flow control hardware, and the memory stores computer executable instructions for controlling the at least one processor to at least control the flow control hardware to: causing a silicon-containing film to form over the substrate at a substrate temperature below about 700° C. without igniting a plasma; and The silicon-containing film is caused to be treated with a densification gas plasma.

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