Passivation for selective etching semiconductor materials

Abstract

Methods and apparatuses for selectively etching dielectric material having variable germanium content are provided herein. The method comprises providing a substrate having a first material and a second material, wherein germanium content of the first material is less than the germanium content of the second material, introducing flow of a gas mixture to a process chamber housing the substrate, and after introducing the flow of the gas mixture, introducing flow of a halogen source to the process chamber in a plasma-free environment to thermally etch the first material selectively relative to the second material.

Description

PASSIVATION FOR SELECTIVE ETCHING SEMICONDUCTOR MATERIALSCROSS-REFERENCES

[0001] A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in their entireties and for all purposes.BACKGROUND

[0002] Fabrication of semiconductors involves many kinds of processing. One type of processing involves depositing materials on the surface of a substrate. Another type of processing involves etching materials from the surface of the substrate. In some cases, such etching is done selectively to target one or more material on the substrate for removal. The background description provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.SUMMARY

[0003] One aspect involves a method for processing substrates, the method including: providing a substrate having a first material and a second material, such that germanium content of the first material is less than the germanium content of the second material; introducing flow of a gas mixture to a process chamber housing the substrate; and after introducing the flow of the gas mixture, introducing flow of a halogen source to the process chamber in a plasma-free environment to thermally etch the first material selectively relative to the second material.

[0004] In various embodiments, the first material includes silicon, and the germanium content of the first material is less than 1%.

[0005] In various embodiments, the second material includes silicon, and the germanium content of the second material is at least about 2%.

[0006] In various embodiments, the method also includes, after introducing the flow of the gas mixture and prior introducing the flow of the halogen source, stopping the flow of the gas mixture. In various embodiments, the method also includes repeating introducing the flow of the gas mixture, then stopping the flow of the gas mixture, then introducing the flow of the halogen source, and stopping the flow of the halogen source in cycles. In some embodiments, during each cycle, flow of the halogen source is performed for a duration shorter than a duration of the flow of the gas mixture. In some embodiments, during each cycle, flow of the halogen source is performed for a duration of about 10 seconds to about 40 seconds. In some embodiments, during each cycle,flow of the gas mixture is performed for a duration of about 40 seconds to about 80 seconds. In some embodiments, about 10 to about 20 cycles are performed.

[0007] In various embodiments, the halogen source and gas mixture are co-flowed.

[0008] In various embodiments, the method also includes modulating flow rate of at least one of the flow of the halogen source or the flow of the gas mixture.

[0009] In various embodiments, the halogen source includes a mixture of two halogencontaining gases, where a ratio of a first halogen-containing gas to a second halogen-containing gas is about 0.05 to about 0.6. In various embodiments, the halogen source includes fluorine (F2) and hydrogen fluoride (HF).

[0010] In various embodiments, the gas mixture is vapor phase and includes: an organic solvent and / or water, an additive, and a carrier gas. In various embodiments, the organic solvent includes an alcohol. In some embodiments the additive is a nitrogen-containing compound. In some embodiments the nitrogen-containing compound is an amine. For example, in some embodiments, the amine is a primary amine. In some embodiments, the nitrogen-containing compound includes pyridine. In some embodiments, the nitrogen-containing compound includes trimethylamine.

[0011] In various embodiments, the halogen source is flowed with an inert gas. For example, in some embodiments, the inert gas includes hydrogen gas. For example, in some embodiments, the inert gas includes argon.

[0012] In various embodiments, the substrate further includes a third material having a germanium content of at least about 30%, wherein germanium content of the second material is different from the germanium content of the third material.

[0013] In various embodiments, the method is performed at a temperature of about 60°C to about 80°C.

[0014] In various embodiments, a ratio of flow rate of the halogen source to flow rate of the gas mixture is about 0.1 : 1.1 to about 0.5:1.5.

[0015] In various embodiments, the first material includes epitaxially deposited silicon.

[0016] In various embodiments, the second material includes silicon germanium.

[0017] In various embodiments, the third material includes silicon germanium.

[0018] In various embodiments, the halogen source includes fluorine. For example, the halogen source includes fluorine gas. In some embodiments, the halogen source further includes hydrogen fluoride vapor. In some embodiments, the halogen source includes nitrogen trifluoride.

[0019] In various embodiments, the halogen source includes chlorine.

[0020] In various embodiments, the gas mixture is introduced for a duration of about 5 seconds to about 20 seconds.

[0021] Another aspect involves an apparatus for processing substrates, the apparatus including:one or more process chambers, each process chamber including a chuck or substrate holder; one or more halogen sources; one or more gas sources for generating a gas mixture; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, whereby the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with 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: cause introduction of a halogen source to the one or more process chambers; and after introduction of the halogen source, cause introduction of a gas mixture to the one or more process chambers.

[0022] In various embodiments, the one or more gas sources includes a nitrogen-containing gas source.

[0023] In various embodiments, the one or more gas sources includes an organic solvent vapor.

[0024] In various embodiments, the one or more gas sources includes an additive.

[0025] These and other aspects are described further below with reference to the drawings.BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG. 1 is a flow chart describing a method of etching a semiconductor substrate according to certain embodiments.

[0027] FIG. 2 is a flow chart describing a method of etching a semiconductor substrate.

[0028] FIG. 3 depicts a cross-sectional side view of an example apparatus in accordance with disclosed embodiments.

[0029] FIG. 4-7 are graphs depicting experimental results performed in accordance with various disclosed embodiments.DETAILED DESCRIPTION

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

[0031] Semiconductor device fabrication involves depositing and etching various materials including but not limited to semiconductor materials. Certain disclosed embodiments are suitable for etching a variety of semiconductor materials. One example is silicon. Another example is silicon germanium. Silicon germanium may have different relative silicon and germanium content. Other examples include Si, SiGe, SiP, SiOC and other semiconductor materials.

[0032] In some semiconductor device patterns, multiple silicon-containing surfaces may be exposed but it may be desirable to etching one silicon-containing material selective to another. A first material being etched “selectively” to a second material as used herein means the first material etches at a rate faster than the second material. In some cases, “selectively etching” the first material etches the first material much faster than the second material such that the etch rate of the second material is small, negligible, or zero.

[0033] It is challenging to etch certain silicon-containing materials relative to another silicon- containing material. One possible reason is because of the similarity in molecular structure and properties of the materials. It is also challenging to etch silicon materials relative to, for example, silicon germanium. It is also challenging to etch silicon materials relative to two silicon germanium materials having different germanium content. Generally, achieving etch selectivity between any two or more of the following materials may be challenging: silicon, silicon germanium, silicon oxide, and silicon nitride. Often, etching selectively may not necessarily be achieved by using plasma, which can be used to etch silicon. Plasma generates high energy ions and radicals (such as halogen radicals) which may sometimes reduce etch selectivity. However, etch selectivity may be used to achieve particular semiconductor processing structures for various applications, such as, but not limited to, 3D-NAND, 3D DRAM, advancing packaging, gate all around, CFET, and others. While plasma is not the only etching technology, other processes such as thermal etching with fluorine gas, or wet processes involving alcoholic solvents, are unable to achieve high selectivity and are associated with high cost.

[0034] Provided herein are methods and apparatuses for etching silicon materials with high etch selectivity using a combination of halogen-based thermal etching with a vapor-based gas mixture that is capable of passivating certain materials and achieving tunable selectivity for silicon, silicon germanium, thermal silicon oxide, silicon nitride, hafnium oxide, low-k films, and other materials. The vapor-based gas mixture include (1) an organic solvent and / or water, (2) an additive, and (3) a carrier gas. The terms “vapor phase” and “gas phase” are used interchangeably in this disclosure. The additive may have particular properties or a particular composition, as described further below. The substrate may be etched at low pressure using thermal energy, for example in a vacuum reaction chamber. In such cases, the substrate is not exposed to plasma during the etching reaction. The substrate may be etched in a selective manner, such that one or more materials are targeted for removal while other materials are etched to a lesser degree. One advantage of the disclosed techniques is that they achieve a high degree of selectivity during etching. Another advantage of the disclosed techniques is that they provide extremely precise control of the etching rate and etch removal amount, especially compared to other thermally-driven etch processes.

[0035] As mentioned above, the substrate is etched using a particular set of chemistry. Thischemistry includes a halogen source such as hydrogen fluoride (HF), fluorine (F2), or a mixture thereof. It may also include one or more organic solvent and / or water, one or more additive, and one or more carrier gas. The reactants are provided to the reaction chamber and exposed to the substrate while they are in vapor phase. Appropriate hardware may be provided to ensure that the reactants are adequately vaporized before and during delivery to the reaction chamber, as described further below. Two or more of the reactants may be mixed before delivery to the reaction chamber. In other embodiments, each of the reactants may be delivered to the reaction chamber individually, for example in separate lines or at separate times.

[0036] The techniques described herein may be used to etch a variety of substrate materials in a number of different contexts. In many cases, the substrate includes two or more different materials that are exposed on a surface of the substrate. One of these materials may be targeted for removal over another of these materials in a selective etching process. In some implementations, the substrate includes a first material and a second material, the first material being selectively etched compared to the second material. In other cases, the substrate may include only a single material that is exposed, such that the etching does not need to be selective. In still other cases, the substrate may include multiple different materials that are all removed without any need for selectivity. The first and / or second materials on the substrate may each be selected from the group consisting of: oxides (e.g., silicon oxide, tin oxide, etc.), nitrides (e.g., silicon nitride, tantalum nitride, titanium nitride, etc.), carbides (e.g., silicon carbide, etc.), carbonitrides (e.g., silicon carbonitride, etc.), carboxides (e.g., silicon carboxide, etc.), etc. In some cases, at least one of the first and second materials may be a dielectric material such as a high-k dielectric material or a low-k dielectric material. Generally, high-k dielectric materials are dielectric materials that have a high dielectric constant relative to silicon dioxide, and low-k dielectric materials are dielectric materials that have a low dielectric constant relative to silicon oxide. Silicon oxide has a dielectric constant of about 3.7-3.9. As such, high-k dielectric materials typically have a dielectric constant greater than about 3.9, while low-k dielectric materials typically have a dielectric constant lower than about 3.7. Examples of low-k dielectric materials include carbon-doped silicon oxides, fluorine-doped silicon oxides, as well as spin-on organic polymeric dielectric materials such as polyimides, polynorbenes, and benzocyclobutenes. Examples of high-k dielectric materials include hafnium silicate, zirconium silicate, hafnium dioxide, and zirconium dioxide. In some cases, at least one of the first and second materials is an epitaxial material such as silicon (Si), or silicon germanium (SiGe). The materials exposed on the substrate may be selected in various combinations and provided in various structures, as desired for a particular application. The techniques described herein are widely applicable to many different applications. Further description of etch selectivity on a first material (e.g., silicon dioxide) with a second material (e.g., silicon nitride) is given below.

[0037] FIG. 1 presents a flow chart for a method of etching a substrate according to various embodiments herein. The method begins with operation 101, where a substrate is provided in a reaction chamber. The substrate includes one or more materials thereon that are to be removed. Example materials are listed above. At operation 103, the substrate is exposed to a gas mixture (which may include an organic solvent and / or water, an additive, and a carrier gas). The gas mixture may act as a passivation gas and aids in achieving selectivity when the substrate is etched in operation 105. At operation 105, a halogen source is flowed into the reaction chamber. The halogen source may be one or more halogen-containing gases or halogen-containing compounds in vapor phase, such as fluorine or chlorine or bromine or iodine or HF. In some embodiments, the gas mixture is a mixture of HF vapor and F2. The gas mixture may have a composition and other properties as described herein. Similarly, one or more processing variables such as pressure, temperature, absolute and relative flow rates, etc. may be controlled as described herein. During this operation one or more of the materials on the substrate are etched as a result of such exposure. These operations may overlap in time. In some embodiments, operations 103 and 105 are performed in temporally separated pulses. In some embodiments, operations 103 and 105 are performed for at least an amount of time that overlaps. In some embodiments, operation 103 is performed prior to operation 105. In some embodiments, operation 105 is performed prior to operation 103. In some embodiments, operations 103 and 105 are performed in cycles.

[0038] In some examples, the gas mixture is prepared by first creating a mixture of (1) the additive and (2) the organic solvent and / or water. The mixture of the additive and the organic solvent and / or water may be added to the carrier gas, and then the hydrogen fluoride gas or other halogen source may be added. In other examples, the hydrogen fluoride or other halogen source gas, the carrier gas and the alcohol may be mixed together to form a gas flow, and then the additive may be added to the gas flow. Various mixing schemes are possible, and all are considered to be within the scope of the disclosed embodiments.

[0039] In some implementations, one or more processing variable may be controlled during etching. For instance, a pressure within the reaction chamber may be controlled at about 10 Torr or less, for example between about 0.2-10 Torr in some embodiments. A temperature within the reaction chamber may be controlled, for example by controlling the temperature of a substrate support on which the substrate is positioned during etching, and / or by controlling the temperature of the gas mixture and / or the temperature of showerhead used to deliver the gas mixture into the reaction chamber. In some embodiments, the temperature of one or more of the reaction chamber, the substrate support, and the showerhead may be controlled during etching, for example at temperatures between about 20-500°C. In some embodiments, the temperature of one or more of these elements may cycle between two or more different temperatures. In some embodiments, theduration over which the substrate is exposed to the gas mixture may be controlled. For instance, this duration may be between about 0-10 minutes. In some cases, the duration of exposure to the gas mixture may control the degree to which the materials on the substrate are etched. In other cases, the etching process may be self-limiting, such that additional exposure duration does not lead to additional etching of a targeted material.

[0040] FIG. 2 is a flow chart describing a cyclic etching method that may be used in some embodiments. In various embodiments, a temperature of about 60°C to about 80°C may be used for performing certain disclosed embodiments.

[0041] The method of FIG. 2 begins with operation 201, where a substrate is provided to a reaction chamber. The substrate may have one or more materials thereon, as described above. One or more of these materials may be targeted for removal compared to other materials present on the substrate. In one example, the substrate may include two or more silicon-containing materials, such as a first material having silicon with a first germanium content, a second material having silicon with a second germanium content, and a third material having silicon with a third germanium content. The first germanium content may be less than about 1% atomic, or about 0% atomic, or 0% atomic. The second germanium content may be at least about 2% atomic. The third germanium content may be at least about 2% atomic. In some embodiments, the third germanium content may be at least about 30% atomic.

[0042] Next, at operation 299, a halogen gas is flowed into the reaction chamber. During this operation, the flow of the halogen gas may be modulated. For example, the flow rate, or flow duration, or both flow rate and flow duration may be modulated.

[0043] The halogen gas may be one or more of the following gases: chlorine (Ch), fluorine (F2), bromine (Br2), or iodine (I2). In some embodiments, a halogen-containing gas may be used, such as a gas that includes at least one atom that is a halogen, such as chlorine, fluorine, bromine or iodine. In various embodiments, the halogen gas may be introduced with one or more inert gases, which may be used to dilute the gas or may be used to deliver or carry the gas, or both. Example inert gases include but are not limited to argon, hydrogen, neon, and krypton. In various embodiments, this halogen gas is an etching gas, or an etchant gas.

[0044] Next, at operation 203, a gas mixture is flowed into the reaction chamber. The gas mixture includes one or more species that will act to modify or passivate one or more materials present on the surface of the substrate. In some cases, the modification involves formation of an oxide material. In these or other cases, the modification involves fluorination of an exposed material, organic molecule adsorption on an exposed material, etc. Various surface modifications are available. In many embodiments, the first reactant or first gas mixture may selectively modify one or more of the materials on the substrate compared to other materials on the substrate. Thegas mixture may include any of the gases described herein in the section titled Etching.

[0045] At operation 205, the substrate is exposed to the gas mixture, and material is selectively etched away. In cases where the substrate includes more than one material exposed, the modified material formed in operation 205 may be selectively etched away compared to other materials such as spacer materials, etc. At this point, some portion of the material targeted for removal has been modified and then removed from the substrate. The gas mixture may have the composition and properties described herein. For example, it may include (1) HF or other halogen source(s), (2) one or more organic solvents and / or water, (3) one or more additives as described above, and (4) a carrier gas. In some embodiments, exposure to the gas mixture is performed for a duration of about 5 seconds to about 20 seconds.

[0046] In various embodiments, HF is flowed at a flow rate of at least about 800 seem. Etching using a variety of combinations of the halogen gas and the gas mixture allows tunability of etch selectivity. A ratio of flow of the halogen gas to flow of the gas mixture may be about 0.1:1 to about 0.5: 1.5. In one example, co-flowing fluorine gas with the gas mixture can be used to etch a silicon material relative to a silicon germanium material with high etch selectivity (such as etch selectivity greater than about 15:1 or greater than about 20: 1 ). In one example, cycling between a mixture of fluorine / argon and the gas mixture can be used to etch silicon oxide material selectively relative to silicon material.

[0047] In various embodiments, during each of operation 299 and 205, the pressure of the process chamber and the temperature may also be modulated to achieve various effects. For example, the temperature may be modulated so as not to be too high which will cause the gas mixture to lose its effectiveness in passivating and preventing etching of a particular material, while a temperature is also not set too low so as to avoid losing effectiveness of etching silicon material. Higher pressure may be used to achieve better passivation, but pressure may not be set too low (otherwise the gas mixture may lose its ability to passivate). The relative flows may also be used to modulate the amount of etching and etch selectivity achieved. For example, too much gas mixture flow may reducing the etching ability of the halogen gas, whereas too little of the gas mixture results in low to no passivation. In some embodiments, HF vapor is added to the gas mixture to boost silicon etching, but if an insufficient amount of HF is used, the halogen gas may become the dominant etchant which results in reduced etch selectivity. If HF vapor gas flow is too high, it may also inadvertently etch oxide, in operations where it may be desirable to etch other material without etching oxide. Each of these factors as well as other factors during etching can affect the etching and etch selectivity differently depending on the material to be etched. Table 1 is an example of various trends that may be observed and thus may be used to toggle various etching capabilities using certain disclosed embodiments. Table 1 provides such trends forembodiments where halogen gas and gas mixture are co-flowed.Table 1. Co-Flow Trends

[0048] Table 2 shows example combinations of process conditions that have different effects onSiGe loss, silicon etch, thermal oxide loss, and passivation. Table 2. Process Conditions*Carbon refers to significant passivation that leads to etch stop,

[0049] In various embodiments, a high silicon to silicon-germanium etch selectivity with low thermal oxide loss can be achieved by using a fluorine gas to gas mixture ratio of about 0.1 to about 0.3 by flow rate. It is believed that using a ratio lower than 0.1 results in higher thermal oxide loss, due to the gas mixture being a dominant etchant. It is believed that using a ratio greater than 0.3 results in higher silicon-germanium loss, due to the fluorine gas becoming a dominant etchant.

[0050] In various embodiments, a temperature of about 60°C to about 80°C may be used to achieve high etch selectivity of silicon to silicon-germanium. It is believed that temperatures too low, such as about 40°C results in lower silicon-germanium etch rate and low silicon etch rate as well. However, temperatures that are too high, such as greater than 80°C, may result in etch rate of both silicon-germanium and silicon being too high.

[0051] In various embodiments, a pressure of about 1 Torr may result in higher silicon-germanium etching but lower adsorption of the gas mixture for passivation, whereas a pressure of about 2.4 Torr may result in lower silicon-germanium etching but higher adsorption of the gas mixture for passivation.

[0052] In various embodiments, relative flow of the gas mixture may be about 1g to about 2 g per minute, to achieve moderate protection for passivation while maintaining silicon-germanium etching.

[0053] In some embodiments, operation 299 and 207 are performed together. For example, the halogen gas and gas mixture may be co-flowed, or flowed together, or both introduced to the process chamber where introduction to the process chamber is at least overlapped in time for a particular duration of time. In some embodiments, the relative amounts of the halogen gas and the gas mixture may be modulated. The relative amounts may be measured by the relative flow rates of each of the halogen gas and gas mixture. For example, a ratio of flow rate of the halogen gas to flow rate of the gas mixture may be about 0.01 to about 1, or about 0.01 or about 0.7, or about 0.05 to about O.6..

[0054] Next, at operation 211, it is determined whether the etching process is sufficiently complete (e.g., whether a sufficient amount of material has been removed from the substrate 301). This determination may be made based on a number of factors including time, etch rate, thickness of material to be removed, when underlying material is exposed, etc. If it is determined that a sufficient amount of material has been removed from the substrate, then the method is complete. Otherwise, the method repeats, starting at operation 203. The surface modification and etching steps are cycled with one another until it is determined that a sufficient amount of material has been removed from the substrate.

[0055] Operations in FIG. 2 may be performed in any order. In some embodiments, operation 299 is performed prior to operation 207. In some embodiments, operation 299 is performed, flow of the halogen gas is stopped, and operations 207 and 209 are performed, and flow of the gas mixture is stopped, and this is repeated in one or more cycles, such as about 10 cycles to about 20 cycles. In some embodiments, during each cycle, flow of the halogen gas may be performed for a duration shorter than flow of the gas mixture. In some embodiments, flow of the halogen gas may be performed for a duration of about 10 seconds to about 40 seconds. In some embodiments, flow of the gas mixture is performed for a duration of about 40 seconds to about 80 seconds. In one example of cycling, the following cycle may be repeated: gas mixture exposure, followed by HF with F2 exposure, followed by purge. Example durations for each may be about 5 seconds for gas mixture exposure, about 5 seconds for HF / F2 exposure, and 20 seconds for purge.

[0056] In some embodiments, a 1:2 exposure duration ratio of gas mixture to HF / F2 flow may achieve an Si:SiGe etch ratio of less than 1 where the cycle is performed once. In someembodiments, a 1 : 1 exposure duration ratio of gas mixture to HF / F2 flow may achieve an etch ratio of Si:SiGe of greater than 1 where the cycle is repeated ten times. As you increase the number of cycles performed, silicon etching increases much faster than SiGe etching (see, as a non-limiting example, the description herein referring to FIG. 7).

[0057] Etch selectivity of silicon to silicon-germanium and silicon to thermal oxide may be toggled by modulating cycling.ETCHING

[0058] The halogen source(s) used herein may include HF. For example, hydrogen fluoride or other halogen source may be provided in the mixture at a concentration between about 20-100% (by volume), or between about 20-99% (by volume). In these or other cases, hydrogen fluoride or other halogen source may be provided in the mixture at a concentration between about 0.5-20% (by volume). The halogen source(s) may be mixed; for example, a mixture of HF vapor and F2 may be used. In such mixtures, hydrogen fluoride may be provided at a concentration between about 20-100% (by volume), or between about 20-99% (by volume). In some embodiments, hydrogen fluoride may be provided at a concentration between about 0.5-20% (by volume).

[0059] Certain disclosed embodiments involve introducing a gas mixture. The gas mixture includes vapor phase species. The vapor phase species delivered to the reaction chamber may be collectively referred to as a gas mixture. The non-inert species delivered to the reaction chamber (e.g., the reactants other than the carrier gas) may be collectively referred to as a reactant mixture. The gas mixture includes the reactant mixture and the carrier gas. In some cases, the reactant mixture and / or the gas mixture may have a particular composition. The organic solvent and / or water may be provided in the reactant mixture at a concentration between about 10-100% (by volume), or between about 10-99% (by volume). In these or other cases, the organic solvent and / or water may be provided in the gas mixture at a concentration between about 0-10% (by volume). The additive may be provided in the reactant mixture at a concentration between about 0.2-5% (by volume). In these or other cases, the additive may be provided in the gas mixture at a concentration between about 0-0.2%, or between about 0.0001-0.2% (by volume). The carrier gas may be provided in the gas mixture at a concentration between about 0-99% (by volume).

[0060] In some embodiments, the additive and organic solvent and / or water are mixed such that the additive is between about 0.1-5% (by weight) of the additive / organic solvent and / or water mixture. A reactant mixture regardless of the order of mixing may be characterized by the additive being about 0.1-5% (by weight) of the total of the amounts of additive and organic solvent and / or water.

[0061] In the same or alternate embodiments, the etching may be characterized by halogen source: additive ratio (by volume). As described further below, in some embodiments, theselectivity can be tuned by the halogen source: additive vol. ratio, with selectivity increasing with an increasing amount of additive (and thus a decreasing ratio). In some embodiments, the halogen source: additive ratio is less than or equal to 10. In some embodiments, the halogen source: additive ratio is greater than 10.

[0062] According to various embodiments, the reactant mixture may include a halogen source (such as HF), an alcohol, and an amine, where the amine is between 0. 1-5% wt of the total alcohol and amine amounts. In some embodiments, the halogen source:amine volumetric ratio is no more than 10. In other embodiments, the halogen source:amine volumetric ratio is 10 or higher. In some embodiments, the amine is pyridine. In some embodiments, the alcohol is isopropyl alcohol. In some embodiment the halogen source is HF.

[0063] As described above, according to various implementations, the etch may be selective to one material on a substrate with respect to another material. In other implementations, the etch may be non-selective with respect to multiple materials on a substrate.

[0064] In some embodiments, oxides are selectively etched with respect to one or more of nitrides and epitaxial materials such as Si and SiGe. The etch selectivity of the reactant mixture to silicon oxide can be tuned by the amount of additive in the mixture. For example, very high (at least 50: 1) etch selectivity of silicon oxide with respect to silicon nitride is achieved with a reactant mixture having a halogen source: additive (e.g., HF:pyridine) of no more than 10. The etch selectivity decreases with increasing ratio such that no selectivity is observed in the case where there is no additive. Similar effects may be observed for etch selectivity of silicon oxide with respect to Si and SiGe.APPARATUS

[0065] The methods described herein can be performed on any appropriate apparatus. The following description provides one example of an appropriate apparatus. The apparatus described herein allows for rapidly and precisely controlling a substrate’ s temperature during semiconductor processing, including performing etching using thermal energy, rather than or in addition to plasma energy, to drive the modification and removal operations. In certain embodiments, etching that relies upon chemical reactions in conjunction with primarily thermal energy, not a plasma, to drive the chemical reactions in the modification and removal operations may be considered “thermal etching”. This etching is not limited to ALE (atomic layer etching); it is applicable to any etching technique.

[0066] In certain embodiments, thermal etching processes, such as those employing one or more thermal cycles have relatively fast heating and cooling and relatively precise temperature control. In some cases, these features may be leveraged to provide good throughput and / or to reduce nonuniformity and wafer defects.

[0067] In various embodiments, apparatuses described herein are designed or configured to rapidly heat and cool a wafer, and precisely control a wafer’s temperature. In some embodiments, the wafer is heated or cooled using an electrostatic chuck, or by using a heated pedestal. In some embodiments, the wafer is rapidly heated and its temperature is precisely controlled using, in part, visible light emitted from light emitting diodes (LEDs) positioned in a pedestal under the wafer. The visible light may have wavelengths that include and range between 400 nanometers (nm) and 800 nm. The pedestal may include various features for enabling wafer temperature control, such as a transparent window that may have lensing for advantageously directing or focusing the emitted light, reflective material also for advantageously directing or focusing the emitted light, and temperature control elements that assist with temperature control of the LEDs, the pedestal, and the chamber.

[0068] The apparatuses may also thermally isolate, or thermally “float,” the wafer within the processing chamber so that only the smallest thermal mass is heated, the ideal smallest thermal mass being just the substrate itself, which enables faster heating and cooling. The wafer may be rapidly cooled using a cooling gas and radiative heat transfer to a heat sink, such as a top plate (or other gas distribution element) above the wafer, or both. In some instances, the apparatus also includes temperature control elements within the processing chamber walls, pedestal, and top plate (or other gas distribution element), to enable further temperature control of the wafer and processing conditions within the chamber, such the prevention of unwanted condensation of processing gases and vapors.

[0069] The apparatuses may also be configured to implement various control loops to precisely control the wafer and the chamber temperatures (e.g., with a controller configured to execute instructions that cause the apparatus to perform these loops). This may include the use of various sensors that determine wafer and chamber temperatures as part of open loops and feedback control loops. These sensors may include temperature sensors in the wafer supports which contact the wafer and measure its temperature, and non-contact sensors such as photodetectors to measure light output of the LEDs and a pyrometer configured to measure the temperature of different types of wafers. As described in more detail below, traditional pyrometers determine an item’s temperature by emitting infrared or other optical signals at the item and measuring the signals reflected or emitted by the item. However, many silicon wafers cannot be measured by traditional pyrometers because the silicon can be optically transparent at various temperatures and with various treatments, e.g., doped or low doped silicon. For example, a low doped silicon wafer at a temperature less than 200°C is transparent to infrared signals. The novel pyrometers provided herein are able to measure multiple types of silicon wafers at various temperatures.

[0070] FIG. 3 depicts a cross-sectional side view of an example apparatus in accordance withdisclosed embodiments. This apparatus may be used to perform any of the methods described herein, for example using the chemistry described herein. As detailed below, this apparatus 100 is capable of rapidly and precisely controlling the temperature of a substrate, including performing thermal etching operations. The apparatus 100 includes a processing chamber 102, a pedestal 104 having a substrate heater 106 and a plurality of substrates supports 108 configured to support a substrate 118, and a gas distribution unit 110.

[0071] The processing chamber 102 includes sides walls 112A, a top 112B, and a bottom 112C, that at least partially define the chamber interior 114, which may be considered a plenum volume. As stated herein, it may be desirable in some embodiments to actively control the temperature of the processing chamber walls 112A, top 112B, and bottom 112C in order to prevent unwanted condensation on their surfaces. Some emerging semiconductor processing operations flow vapors, such as water and / or alcohol vapor, onto the substrate which adsorb onto the substrate, but they may also undesirably adsorb onto the chamber’s interior surfaces. This can lead to unwanted deposition and etching on the chamber interior surfaces which can damage the chamber surfaces and cause particulates to flake off onto the substrate thereby causing substrate defects. In order to reduce and prevent unwanted condensation on the chamber’s interior surfaces, the temperature of chamber’s walls, top, and bottom may be maintained at a temperature at which condensation of chemistries used in the processing operations does not occur.

[0072] This active temperature control of the chamber’s surfaces may be achieved by using heaters to heat the chamber walls 112A, the top 112B, and the bottom 112C. As illustrated in FIG. 3, chamber heaters 116A are positioned on and configured to heat the chamber walls 112 A, chamber heaters 116B are positioned on and configured to heat the top 112B, and chamber heaters 116C are positioned on and configured to heat the bottom 112C. The chamber heaters 116A-116C may be resistive heaters that are configured to generate heat when an electrical current is flowed through a resistive element. Chamber heaters 116A-116C may also be fluid conduits through which a heat transfer fluid may be flowed, such as a heating fluid which may include heated water. In some instances, the chamber heaters 116A-116C may be a combination of both heating fluid and resistive heaters. The chamber heaters 116A-116C are configured to generate heat in order to cause the interior surfaces of each of the chamber walls 112A, the top 112B, and the bottom 112C to the desired temperature, which may range between about 40°C and about 150°C, including between about 80°C and about 130°C, or about 90°C, or about 120°C, for instance. It has been discovered that under some conditions, water and alcohol vapors do not condense on surfaces kept at about 90°C or higher.

[0073] The chamber walls 112A, top 112B, and bottom 112C, may also be comprised of various materials that can withstand the chemistries used in the processing techniques. These chambermaterials may include, for example, an aluminum, anodized aluminum, aluminum with a polymer, such as a plastic, a metal or metal alloy with a yttria coating, a metal or metal alloy with a zirconia coating, and a metal or metal alloy with aluminum oxide coating; in some instances the materials of the coatings may be blended or layers of differing material combinations, such as alternating layers of aluminum oxide and yttria, or aluminum oxide and zirconia. These materials are configured to withstand the chemistries used in the processing techniques, such as anhydrous HF, water vapor, methanol, isopropyl alcohol, chlorine, fluorine gases, nitrogen gas, hydrogen gas, helium gas, and the mixtures thereof.

[0074] The apparatus 100 may also be configured to perform processing operations at or near a vacuum, such as at a pressure of about 0.1 Torr to about 100 Torr, or about 20 Torr to about 200 Torr, or about 0.1 Torr to about 10 Torr. This may include a vacuum pump 184 configured to pump the chamber interior 114 to low pressures, such as a vacuum having a pressure of about 0.1 Torr to about 100 Torr, or another pressure range described herein.

[0075] Various features of the pedestal 104 will now be discussed. The pedestal 104 includes a heater 122 (encompassed by the dashed rectangle in FIG. 3) that has a plurality of LEDs 124 that are configured to emit visible light having wavelengths including and between 400 nm to 800 nm, including 450 nm. The heater LEDs emit this visible light onto the backside of the substrate, which heats the substrate. Visible light having wavelengths from about 400 nm to 800 nm is able to quickly and efficiently heat silicon wafers from ambient temperature, e.g., about 20°C, to about 600°C because silicon absorbs light within this range. In contrast, radiant, including infrared radiant, heating may ineffectively heat silicon at temperatures up to about 400°C because silicon tends to be transparent to infrared at temperatures lower than about 400°C. Additionally, radiant heaters that directly heat the topside of a wafer, as in many conventional semiconductor processes, can cause damage or other adverse effects to the topside films. Traditional “hot plate” heaters that rely on solid-to-solid thermal transference between the substrate and a heating platen, such as a pedestal with a heating coil, have relatively slow to heating and cooling rates, and provide non- uniform heating which may be caused by substrate warping and inconsistent contact with the heating platen. For example, it may take multiple minutes to heat a traditional pedestal to a desired temperature, and from a first to a second higher temperature, as well as to cool the pedestal to a lower temperature.

[0076] In FIG. 3, in some embodiments, the pedestal is also configured to move vertically. This may include moving the pedestal such that a gap 186 between a faceplate 176 of the gas distribution unit 110 and the substrate 118 is capable of being in a range of 2 mm and 70 mm. As provided in more detail below, moving the pedestal vertically may enable active cooling of the substrate as well as rapid cycling time of processing operations, including flowing gas and purging,due to a low volume created between the gas distribution unit 110 and the substrate 118. This movement may also enable the creation of a small process volume between the substrate and the gas distribution unit which can result in a smaller purge and process volume and thus reduce purge and gas movement times and increase throughput.

[0077] The gas distribution unit 110 is configured to flow process gases, which may include liquids and / or gases, such as a reactant, modifying molecules, converting molecules, or removal molecules, onto the substrate 118 in the chamber interior 114. As seen in FIG. 3, the gas distribution unit 110 includes one or more fluid inlets 170 that are fluidically connected to one or more gas sources 172 and / or one or more vapor sources 174. In some embodiments, the gas lines and mixing chamber may be heated to prevent unwanted condensation of the vapors and gases flowing within. These lines may be heated to at least about 40 °C, at least about 80°C, at least about 90°C, or at least about 120°C, at least about 130°C, or at least about 150°C. The one or more vapor sources may include one or more sources of gas and / or liquid which is vaporized. The vaporizing may be a direct inject vaporizer, a flow over vaporizer, or both. The gas distribution unit 110 also includes the faceplate 176 that includes a plurality of through-holes 178 that fluidically connect the gas distribution unit 110 with the chamber interior 114. These through- holes 178 are fluidically connected to the one or more fluid inlets 170 and also extend through a front surface 177 of the faceplate 176, with the front surface 177 configured to face the substrate 118. In some embodiments, the gas distribution unit 110 may be considered a top plate and in some other embodiments, it may be considered a showerhead.

[0078] The through-holes 178 may be configured in various ways in order to deliver uniform gas flow onto the substrate. In some embodiments, these through-holes may all have the same outer diameter, such as between about 0.3 inches and 0.5 inches, including about 0.4 inches (1.16 mm). These faceplate through-holes may also be arranged throughout the faceplate in order to create uniform flow out of the faceplate.

[0079] Referring back to FIG. 3, the gas distribution unit 110 may also include a unit heater 180 that is thermally connected to the faceplate 176 such that heat can be transferred between the faceplate 176 and the unit heater 180. The unit heater 180 may include fluid conduits in which a heat transfer fluid may be flowed. Similar to above, the heat transfer fluid may be heated to a temperature range of about 20°C and 120°C, for example. In some instances, the unit heater 180 may be used to heat the gas distribution unit 110 to prevent unwanted condensation of vapors and gases; in some such instances, this temperature may be at least about 90°C or 120°C.

[0080] In some embodiments, the gas distribution unit 1 10 may include a second unit heater 182 that is configured to heat the faceplate 176. This second unit heater 182 may include one or more resistive heating elements, fluid conduits for flowing a heating fluid, or both. Using two heaters180 and 182 in the gas distribution unit 110 may enable various heat transfers within the gas distribution unit 110. This may include using the first and / or second unit heaters 180 and 182 to heat the faceplate 176 in order to provide a temperature-controlled chamber, as described above, in order to reduce or prevent unwanted condensation on elements of the gas distribution unit 110.

[0081] The apparatus 100 may also be configured to cool the substrate. This cooling may include flowing a cooling gas onto the substrate, moving the substrate close to the faceplate to allow heat transfer between the substrate and the faceplate, or both. Actively cooling the substrate enables more precise temperature control and faster transitions between temperatures which reduces processing time and improves throughput. In some embodiments, the first unit heater 180 that flows the heat transfer fluid through fluid conduits may be used to cool the substrate 118 by transferring heat away from the faceplate 176 that is transferred from the substrate 119. A substrate 118 may therefore be cooled by positioning it in close proximity to the faceplate 176, such as by a gap 186 of less than or equal to 5 mm or 2 mm, such that the heat in the substrate 118 is radiatively transferred to the faceplate 176, and transferred away from the faceplate 176 by the heat transfer fluid in the first unit heater 180. The faceplate 176 may therefore be considered a heat sink for the substrate 118 in order to cool the substrate 118.

[0082] In some embodiments, the apparatus 100 may further include a cooling fluid source 173 which may contain a cooling fluid (a gas or a liquid), and a cooler (not pictured) configured to cool the cooling fluid to a desired temperature, such as less than or equal to at least about 90°C, at least about 70°C, at least about 50°C, at least about 20°C, at least about 10°C, at least about 0°C, at least about -50°C, at least about -100°C, at least about -150°C, at least about -190°C, at least about -200°C, or at least about -250°C, for instance. The apparatus 100 includes piping to deliver the cooling fluid to the one or more fluid inlets 170, and the gas distribution unit 110 which is configured to flow the cooling fluid onto the substrate. In some embodiments, the fluid may be in liquid state when it is flowed to the chamber 102 and may turn to a vapor state when it reaches the chamber interior 114, for example if the chamber interior 114 is at a low pressure state, such as described above, e.g., between about 0.1 Torr and 100 Torr, or between about 20 Torr and 200 Torr, or between about 0.1 Torr and 10 Torr, for instance. The cooling fluid may be an inert element, such as nitrogen, argon, or helium. In some instances, the cooling fluid may include, or may only have, a non-inert element or mixture, such as hydrogen gas. In some embodiments, the flow rate of the cooling fluid into the chamber interior 114 may be at least about 0.25 liters per minute, at least about 0.5 liters per minute, at least about 1 liters per minute, at least about 5 liters per minute, at least about 10 liters per minute, at least about 50 liters per minute, or at least about 100 liters per minute, for example. In certain embodiments, the apparatus may be configured to cool a substrate at one or more cooling rates, such as at least about 5°C / second, at least about10°C / second, at least about 15°C / second, at least about 20°C / second, at least about 30°C / second, or at least about 40°C / second.

[0083] In some embodiments, the apparatus 100 may actively cool the substrate by both moving the substrate close to the faceplate and flowing cooling gas onto the substrate. In some instances, the active cooling may be more effective by flowing the cooling gas while the substrate is in close proximity to the faceplate. The effectiveness of the cooling gas may also be dependent on the type of gas used.

[0084] The apparatuses provided herein can therefore rapidly heat and cool a substrate.

[0085] In some embodiments, the apparatus 100 may include a mixing plenum for blending and / or conditioning process gases for delivery before reaching the fluid inlets 170. One or more mixing plenum inlet valves may control introduction of passivation vapor and / or process gases to the mixing plenum. In some other embodiments, the gas distribution unit 110 may include one or more mixing plenums within the gas distribution unit 110. The gas distribution unit 110 may also include one or more annular flow paths fluidically connected to the through-holes 178 which may equally distribute the received fluid to the through-holes 178 in order to provide uniform flow onto the substrate.

[0086] The apparatus 100 may also include one or more additional non-contact sensors for detecting the temperature of the substrate. One such sensor may be a new pyrometer that is capable of detecting numerous temperature ranges of a silicon substrate. It is desirable to detect the temperature of substrates having different treatments, e.g., whether the silicon is doped or not doped, at different temperatures ranges at which processing operations may occur, such as under about 200°C, greater than about 200°C and less than about 600°C, or above 600°C. However, traditional pyrometers are not able to detect different substrates within these ranges. Traditional pyrometers measure the optical signals reflected or emitted by an object’s surface to determine the object’s temperature according to some calibration. However, many silicon wafers cannot be measured by these pyrometers because the silicon is optically transparent at various temperatures and with various treatments.

[0087] Lightly doped, or undoped, silicon substrates have an emission signal from approximately 0.95 to 1.1 microns when the substrates are at or below about 300°C, that doped silicon substrates have an emission signal between about 1 and 4 microns when the substrates are below about 200°C, that silicon substrates have an emission signal at approximately 1 micron when around room temperature, such as under about 100°C including, for instance 20°C, and that silicon substrates have an emission signal of about 8 to 15 microns when at temperatures over about 600°C. The new pyrometer is therefore configured to detect multiple emission ranges in order to detect multiple substrates, e.g., doped, low doped, or not doped, at various temperatureranges. This includes the configuration to detect emission ranges of about 0.95 microns to about 1.1 microns, about 1 micron, about 1 to about 4 microns, and / or about 8 to 15 microns. The new pyrometer is also configured to detect the temperature of a substrate at a shorter wavelength in order to differentiate the signal from the thermal noise of the chamber.

[0088] The new pyrometer may include an emitter configured to emit infrared signals and a detector configured to receive emissions. Referring to FIG. 3, the apparatus includes the new pyrometer 188 having an emitter within the pyrometer 188 and a detector 190. The new pyrometer may be configured to emit signals on one side of the substrate, either the top or the bottom, and configured to receive signals on the other side of the substrate. For instance, the emitter may emit signals on the top of the substrate and the detector is under the substrate and receives signals emitted through and under the substrate. The apparatus may therefore have at least a first port 192A on the top of the chamber 102, such as the port 192A through the center of the gas distribution unit 110, and a second port 192B through the pedestal 104 and substrate heater 122. The emitter in the pyrometer 188 may be connected to one of the ports 192 A or 192B via a fiberoptic connection, such as the first port 192 A as shown in FIG. 3, and the detector is optically connected to the other port, such as the second port 192B in FIG. 3. The first port 192 A may include a port window 194 to seal the first port 192A from the chemistries within the chamber interior 114. The second port 192B is seen in FIG. 3 extending through the pedestal 104 and the substrate heater such that the emitter’s emissions can pass through the substrate, through the window 150, into the second port 192B and to the detector 190 that may be positioned in the second port or optically connected to the second port through another fiberoptic connection (not shown). In some other embodiments, the emitter and the detector are flipped, such that the emitter emits through the second port 192B and the detector detects through the first port 192A.

[0089] The apparatus 100 may also include one or more optical sensors 198 to detect one or more metrics of the visible light emitted by the LEDs. In some embodiments, these optical sensors may be one or more photodetectors configured to detect the light intensity and / or thermal radiation of the visible light emitted by the LEDs of the substrate heater. In FIG. 3, a single optical sensor 198 is shown as connected to the chamber interior 114 via fiberoptic connection such that the optical sensor 198 is able to detect light emitted by the substrate heater 122. The optical sensor 198, and additional optical sensors, can be positioned in various locations in the top and sides, for instance, of the chamber 102 in order to detect the emitted light at various locations within the chamber 102. As discussed below, this may enable the measurement and adjustment of the substrate heater, such as the adjustment of one or more independently controllable zones of the LEDs. In some embodiments, there may be a plurality of optical sensors 198 arranged along a circle or multiple concentric circles in order to measure various regions of the LEDs throughoutthe chamber 102. In some embodiments, the optical sensors may be positioned inside the chamber interior 1 14.

[0090] In some embodiments, the apparatus may further be configured to generate a plasma and use the plasma for some processing in various embodiments. This may include having a plasma source configured to generate a plasma within the chamber interior, such as a capacitively coupled plasma (CCP), an inductively coupled plasma (ICP), an upper remote plasma, and a lower remote plasma.

[0091] The apparatuses described herein are not limited to ALE etching operations. These apparatuses may be used with any etching technique.

[0092] In some embodiments, the apparatuses described herein may include a controller that is configured to control various aspects of the apparatus in order to perform the techniques described herein. For example, referring back to FIG. 3, apparatus 100 includes a controller 131 (which may include one or more physical or logical controllers) that is communicatively connected with and that controls some or all of the operations of a processing chamber. The system controller 131 may include one or more memory devices 133 and one or more processors 135. In some embodiments, the apparatus includes a switching system for controlling flow rates and durations, the substrate heating unit, the substrate cooling unit, the loading and unloading of a substrate in the chamber, the thermal floating of the substrate, and the process gas unit, for instance, when disclosed embodiments are performed. In some embodiments, the apparatus may have a switching time of up to about 500 ms, or up to about 750 ms. Switching time may depend on the flow chemistry, recipe chosen, reactor architecture, and other factors.

[0093] In some implementations, the controller 131 is part of an apparatus or a system, which may be part of the above-described examples. Such systems or apparatuses can include semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and / or specific processing components (a gas flow system, a substrate heating unit, a substrate cooling unit, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller 131, depending on the processing parameters and / or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and / or load locks connected to or interfaced with a specific system.

[0094] Broadly speaking, the controller 131 may be defined as electronics having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some embodiments, be part of a recipe defined by process engineers to accomplish one or more processing operations during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or dies of a wafer.

[0095] The controller 131, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing operations to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated to the system from the remote computer. In some examples, the controller 131 receives instructions in the form of data, which specify parameters for each of the processing operations to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller 131 may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.

[0096] As noted above, depending on the process operation or operations to be performed by the apparatus, the controller 131 might communicate with one or more of other apparatus circuits ormodules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and / or load ports in a semiconductor manufacturing factory.

[0097] As also stated above, the controller is configured to perform any technique described above. This may include causing a substrate transfer robot to position the substrate in the chamber on the plurality of substrate supports causing power to be delivered to the LEDs so that they emit the visible light having wavelengths between 400 nm and 800 nm to heat the substrate to a first temperature, such as between 100°C and 600°C, and causing etchant gases to flow into the chamber and etch the substrate. This may also include cooling, while the substrate is supported by only the plurality of substrate supports, the substrate by flowing the cooling gas onto the substrate, and / or moving the pedestal vertically so that the substrate is offset from a faceplate of a gas distribution unit by a first nonzero distance, and thereby causing heat to transfer from the substrate to the faceplate through noncontact radiation. This may also include controlling the chemistry delivered to the reaction chamber, as described herein.EXPERIMENTALEXPERIMENT 1

[0098] An experiment was done on various Si and SiGe materials using certain disclosed embodiments at different temperatures. FIG. 4 shows the results from these experiments. As shown, a temperature of about 60-80°C achieved etch selectivity of Si relative to SiGe.EXPERIMENT 2

[0099] An experiment was done on various Si and SiGe materials using certain disclosed embodiments at various flows of HF used in the gas mixture. FIG. 5 shows the results from these experiments. As shown, increasing HF flow increased Si etching.EXPERIMENT 3

[0100] An experiment was done on various Si and SiGe materials using certain disclosed embodiments at various flows of the gas mixture. FIG. 6 shows the results from these experiments. As shown, using the gas mixture affects etch selectivity substantially as shown with the peaks in the center of the graph.EXPERIMENT 4

[0101] An experiment was done on various Si, SiGe, and thermal oxide materials using certain disclosed embodiments using 5 cycles of etching, 10 cycles of etching, and 15 cycles of etching. One cycle of etching involved 2.5 g / min of a gas mixture followed by a 0.3:0.7 gas flow ratio of F2 to HF vapor at 60°C. FIG. 7 shows the etch rate of silicon increased linearly while the etch rate of SiGe and thermal oxide remained the same, which suggests that etch selectivity can be achievedbetween Si and SiGe, and between Si and thermal oxide, using increasing number of cycles of certain disclosed embodiments.DEFINITIONS AND PRECURSORSHA OGEN SOURCE

[0102] The halogen source may be any halogen-containing (e.g., X-containing, where X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)) compound that exists in vapor phase at the processing temperature. Examples include hydrogen fluoride (HF), hydrogen chloride (HC1), hydrogen bromide (HBr), fluorine (F2), chlorine (Ch), bromine (BL), chlorine trifluoride (CIF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCI3), and nitrogen tribromide (NB ). In some implementations, the halogen source is an organohalide, with examples including fluoroform (CHF3), chloroform (CHCI3), bromoform (CHBr ), carbon tetrafluoride (CF4), carbon tetrachloride (CCI4), carbon tetrabromide (CBr4), perfluorobutene (C4F8), and perchlorobutene (C4CI8). In some implementations, the halogen source is a silicon halide, with examples including silicon tetrafluoride (SiF4), silicon tetrachloride (SiCU), silicon tetrabromide (SiB ), and compounds that include SiXe such as ftSiXe. In some implementations, the halogen source is a metal halide with examples including molybdenum hexafluoride (MoFe), molybdenum hexachloride (MoCU), molybdenum hexabromide (MoBre), tungsten hexafluoride (WF&), tungsten hexachloride (WCk), tungsten hexabromide (WBre), titanium tetrafluoride (TiF4), titanium tetrachloride (TiCE), titanium tetrabromide (TiB ), zirconium fluoride (ZrF4), zirconium chloride (ZrCE). and zirconium bromide (ZrBr4). Metal halides may be used in some embodiments to selectively etch metal oxides.

[0103] In the description below, various examples include HF as the halogen source. However, any appropriate halogen source may be used. The volume and mass percentages described for HF can be used for other halogen sources. In some embodiments, two or more halogen sources may be used.ORGANIC SOLVENTAlcohols

[0104] In certain implementations, the organic solvent may be an alcohol. The alcohol can be an alcohol having a formula of X-C(R)n(OH)-Y, where: n is 1 ; each X and Y can be independently selected from hydrogen, -[C(R1)2]m-C(R2)3, or OH, wherein each R1and R2is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10; and each R independently is selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic,heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof.

[0105] In some embodiments, each R,R* and R2independently is selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkylheteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl- heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed embodiments, the alcohol may further be substituted with one or more substituents, such as alkoxy, amide, amine, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0106] In other embodiments, when at least one of X or Y = -[C(R1)2]m-C(R2)s or R is a hydrogen and m is 1, the alcohol can be a C3 alcohol. For instance, if at least one R1and one R2is absent, then the C3 alcohol can be a C3 alkenol (e.g., allyl alcohol). In another instance, R and one R2together can form a ring(such as, cycloaliphatic), then the C3 alcohol can be a cyclopropanol or 2- cyclopropenol.

[0107] In yet other embodiments, when at least one of X or Y = -[C(R1)2],n-C( R2)3 or R is a hydrogen and m is 2, the alcohol can be a C4 alcohol. For instance, if at least one R1and one R2is absent, then the C4 alcohol can be a C4 alkenol (e.g., 2-buten-l-ol or 3-buten-l-ol). In another instance, R and one R2together can form a ring (such as, cycloaliphatic), then the C4 alcohol can be a C4-cyclic alcohol (e.g., cyclobutanol or a cyclopropylmethanol). In yet another instance, if both X and Y are not OH , then the C4 alcohol can be a C4-branched alcohol (e.g., 2-butanol, isobutanol, or tert-butanol).

[0108] In some instances, when X = OH and Y = -[C(R1)2]m-C(R2)3, the alcohol can be a diol. In other instances, when at least one X or Y= -[C(R1)2]m-C(R2)3 and at least one R1= OH or one R2= OH, or when R= OH, the alcohol can be a diol. Example diols include, but are not limited to, 1,4-butane diol, propylene- 1,3-diol, and the like.

[0109] In other instances, when X = Y = OH, the alcohol can be a triol. In yet other instances, when X = R = OH, the alcohol can be a triol. In some instances, when at least one of X or Y is - [C(R1)2]m-C(R2)3 and one R1and at least one R2is OH, the alcohol can be triol. In other instances, when R = OH and X = -[C(R1)2]m-C(R2)3 and one R1and at least one R2is OH, the alcohol can be triol. Example triols include, but are not limited to, glycerol or glycerine derivatives thereof.

[0110] In particular embodiments, when R = cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol can be a heterocyclyl alcohol (e.g., an optionally substituted heterocyclyl substituted with or more hydroxyls, such as furfuryl alcohol). In other embodiments, when at least one of X or Y is -|QR' |,,,-C(R2h and one R1and at least one R2is cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol can be a heterocyclyl alcohol.

[0111] In various embodiments, the alcohol may have between 1-10 carbon atoms. The alcohol may be a primary alcohol, a secondary alcohol, or a tertiary alcohol. In some cases, the alcohol may be selected from the group consisting of: methanol, ethanol, 1 -propanol, 2-propanol, 1- butanol, 2-butanol, t-butanol, 1 -pentanol, 1 -hexanol, 1 -heptanol, 1 -octanol, 1 -nonanol, 1 -decanol, and combinations thereof.Laboratory Solvents

[0112] In these or other cases, the organic solvent may include a laboratory-type solvent such as acetonitrile, dichloromethane , carbon tetrachloride, or a combination thereof.Ketones

[0113] In some embodiments, the organic solvent may be a ketone.

[0114] The organic solvent can also be a ketone having a formula of X-[C(O)]n-Y, where: n is an integer from 1 to 2; each X and Y can be independently selected from-C R' , -R2, or -[C(R3)2]m-C(O)-R4, wherein each R1, R2, R3and R4can be independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof; in which R3and R4, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic, and in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic; and m is an integer from 0 to 10.

[0115] In some embodiments, each R1, R2, R3and R4, independently, are alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalky nyl-heteroaryl, or any combinations thereof. In particular disclosed embodiments, the organic solvent may further be substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=0), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof. One example ketone is acetone.

[0116] In some embodiments, when X and Y, taken together with the atom to which each are attached, forms a cycloaliphatic or cycloheteroaliphatic, the organic solvent can be a cyclic ketone. Example cyclic ketones include cyclohexanone, cyclopentanone, and the like.

[0117] In other embodiments, when at least one of X or Y = -[C(R3)2]™-C(O)-R4, the organic solvent can be a diketone. Example diketones include diacetyl, 2, 3 -pentanedione, 2,3- hexanedione, 3,4-hexanedione, acetylacetone, acetonylacetone, and the like, as well as halogenated forms thereof, such as hexafluoroacetylacetone.

[0118] In further embodiments, when at least one of X or Y = -[C(R3)2]m-C(O)-R4and X and Y, taken together with the atom to which each are attached, forms a cycloaliphatic or cycloheteroaliphatic, the organic solvent can be a cyclic diketone. Example cyclic diketones include dimedone, 1,3-cyclohexanedione, and the like.

[0119] In some instances, when X = -CH3, the organic solvent can have Y = -C(R*)3, in which at least one R1is C2-10 hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof. Example materials can include methyl propyl ketone, methyl butyl ketone, hydroxyacetone, and the like.

[0120] In other instances, when X = -CH3, the organic solvent can have Y = - R2, in which at least one R2is C2 alkenyl, C3-10 aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof. Example materials can include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, and the like.

[0121] In yet other instances, when at least one of X or Y = aromatic, or aliphatic-aromatic, or heteroaliphatic-aromatic, the organic solvent can be an aromatic ketone. Example materials include acetophenone, benzophenone, benzylacetone, 1,3-diphenylacetone, cyclopentyl phenyl ketone, and the like.

[0122] In certain embodiments where the organic solvent includes a ketone, the ketone may be selected from acetone and acetophenone. One or more additional ketones and / or other organic solvents described herein may be provided, as well.Alkanes

[0123] In some embodiments, the organic solvent may be an alkane. In certain embodiments, the alkane may be an acyclic branched or unbranched hydrocarbon having the general formula CnH2n+2. Example acyclic alkanes include, but are not limited to, pentane, hexane, octane, and combinations thereof. In certain other embodiments, the alkane may be a cyclic hydrocarbon. Example cyclic hydrocarbons include, but are not limited to, cyclopentane, cyclohexane, and combinations thereof.Aromatic Solvents

[0124] In some embodiments, the organic solvent may be an aromatic solvent. As used herein, “aromatic” means a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized ^-electron system. Typically, the number of out of plane 7i-electrons corresponds to the Hiickel rule (4n+2). The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system. In some cases, an aromatic solvent may be selected from toluene and benzene.Ethers

[0125] In some embodiments, the organic solvent may be an ether having a formula of X-O-Y or X-O-[C(R)2]n-O-Y, where: n is an integer from 1 to 4; each X and Y can be independently selected from -[C(R])2]m-C(R2)3 or -R3or -[C(R4)2]p- O-[C(R5)2](n-C(R6)3, wherein each of R1, R2, R3, R4, R5, R6and R is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10 and p is an integer from 1 to 10; in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic group.

[0126] In some embodiments, each R, R1, R2, R3, R4, R5and R6independently are selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl- heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl- heteroaryl, or any combinations thereof. In particular disclosed embodiments, the ether mayfurther be substituted with one or more substituents, such as alkoxy, amide, amine, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0127] In some embodiments, when X and Y are taken together with the atom to which each are attached in order form a cycloheteroaliphatic group, the organic solvent is a cyclic ether, such as, acetal, dioxane, dioxolane, etc. In some embodiments, when n - 1 and each R = H, X and Y taken together form a six, seven, eight, nine, or ten-membered ring. Example ethers include, but are not limited to, 1,3 -dioxolane, or derivatives thereof. In other embodiments, when n = 2 and R = H, X and Y form a seven, eight, nine, or ten-membered ring. Example ethers include, but are not limited to, 1,4-dioxane, or derivatives thereof. In yet other embodiments, when n = 1 or n = 2, then R is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof. Example cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 2-methyl-l,3-dioxolane, and the like.

[0128] In other embodiments, when at least one of X or Y = aromatic, the organic solvent can be an aromatic ether. Example aromatic ethers include anisole, diphenyl ether, and the like.

[0129] In some embodiments, when at least one of X or Y = cycloaliphatic, the organic solvent can be a cycloalkyl ether. Example cycloalkyl ethers include cyclopentyl methyl ether, cyclohexyl methyl ether, and the like.

[0130] In other embodiments, when at least one of X or Y = -[C(R4)2-O]P-C(R6)3, the organic solvent can be a glycol based ether. Example glycol based ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, etc., including methyl, ethyl, propyl, and butyl mono- and di-ethers of ethylene glycol, and the like.Nitriles

[0131] In some cases, the organic solvent is a nitrile having a formula R-C=N, whereR is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic- aromatic, or heteroaliphatic-aromatic.

[0132] In certain embodiments, R can be optionally substituted with a hydroxyl group (e.g., in one example R can be CH3-CH(OH)-CH2-, and the organic solvent will be CH3-CH(OH)-CH2- CN).

[0133] One example nitrile is acetonitrile, mentioned above.

[0134] In some embodiments, the organic solvent may include two or more of the organic solvents or types of organic solvents described herein. In some embodiments, water may be provided instead of, or in addition to, the organic solvent.CARRIER GAS

[0135] The carrier gas may be an inert gas. In some cases the carrier gas is a noble gas. In certain embodiments, the carrier gas may be selected from the group consisting of N2, He, Ne, Ar, Kr, and Xe. In some such embodiments, the carrier gas may be selected from the group consisting of N2, He, and Ar.ADDITIVE

[0136] The additive may be selected from a number of different types of additives. For instance, in some cases the additive may be a heterocycle compound, a heterocyclic aromatic compound, a halogen-substituted heterocyclic aromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidizer, a bifluoride source, ammonia, an aldehyde, a carbene, an organic acid, and / or a hydrogen fluoride complex forming chemical. In some cases, more than one additive may be used. In some embodiments, the additive may be a boron-containing Lewis acid or Lewis adduct. Boron trifluoride (BF3) is an example of a Lewis acid that forms the acid-base adduct BFT. In some cases, the additive may fall into two or more of the categories listed above. In various embodiments, the additive serves the purposes of accelerating the reaction rate and enhancing the reaction selectivity.Heterocyclic Aromatic Compounds

[0137] In certain embodiments, the additive is a heterocyclic aromatic compound. The term “aromatic” is defined above. A heterocyclic aromatic compound is an aromatic compound that includes a 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). Example heterocyclic aromatic compounds that may be used include, but are not limited to, picoline, pyridine, pyrrole, imidazole, thiophene, N- methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolonic acid, 2,6- lutidine, 4-N,N-dimethylaminopyridine, and azulene. In some cases, a heterocyclic aromatic compound may be methylated. In some cases, a heterocyclic aromatic compound may follow the Hiickel 4n + 2 rule. In some cases, the additive is a halogen-substituted aromatic compound. A halogen-substituted aromatic compound is an aromatic compound that includes at least one halogen bonded to the aromatic ring. As used herein, halogen or halo refers to F, Cl, Br, or I. Example halogen-substituted aromatic compounds include, but are not limited to, 4- bromopyridine, chlorobenzene, 4-chlorotoluene, fluorobenzene, etc.Heterocyclic Aliphatic Compounds

[0138] In some embodiments, the additive is a heterocyclic aliphatic compound. As used herein, “aliphatic” means a hydrocarbon group having at least one carbon atom to 50 carbon atoms (Ci- 50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (Ci- 10), and which includesalkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well. A heterocyclic aliphatic compound is an aliphatic compound that includes a 5-, 6- or 7- membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). Example heterocyclic aliphatic compounds include pyrrolidine, piperidine, etc.Amines

[0139] In some embodiments, the additive is an amine having a formula of NR R2R3, where: each of R1, R2, and R3is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic- aromatic, or any combinations thereof; in which R1and R2, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic; and in which R1, R2, and R3, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic.

[0140] In some embodiments, each of R1, R2, and R3is independently selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkylheteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl- heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed embodiments, the amine may further be substituted with one or more substituents, such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0141] In some embodiments, when at least one of R1, R2, and R3is aliphatic, haloaliphatic, haloheteroaliphatic, or heteroaliphatic, the additive is an alkyl amine. The alkyl amine can include dialkylamines, trialkyl amines, and derivatives thereof. Example alkyl amines include dimethylisopropylamine, A-ethyldiisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, t-butyl amine, and the like.

[0142] In other embodiments, when at least one of R1, R2, and R3includes a hydroxyl, the additive is an alcohol amine. In one instance, at least one of R1, R2, and R3is an aliphatic groupsubstituted with one or more hydroxyls. Example alcohol amines include 2- (dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(dipropylamino)ethanol, 2- (dibutylamino)ethanol, A-ethyldiethanol amine, / / -tertbutyldiethanolamine, and the like.

[0143] In some embodiments, when R1and R2, taken together with the atom to which each are attached, form a cycloheteroaliphatic, the additive can be a cyclic amine. Example cyclic amines include piperidine, yV-alkyl piperidine (e.g., / -methyl piperidine, / -propyl piperidine, etc.), pyrrolidine, IV-alkyl pyrrolidine (e.g., / / -methyl pyrrolidine, propyl pyrrolidine, etc.), morpholine, / / -alkyl morpholine (e.g., / -methyl morpholine, / / -propyl morpholine, etc.), piperazine, TV-alky 1 piperazine, / / , / / -dialkyl piperazine (e.g., 1,4-dimethylpiperazine), and the like.

[0144] In other embodiments, when at least one of R1, R2, and R3includes an aromatic, the additive is an aromatic amine. In some embodiments, at least one of R1, R2, and R3is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. In other embodiments, both R1and R2includes an aromatic. In yet other embodiments, R1and R2and optionally R3, taken together with the atom to which each are attached, from a cycloheteroaliphatic that is an aromatic. Example aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and the derivatives thereof.

[0145] In some embodiments, the additive may include an amine selected from the group consisting of: methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1 ,2-ethylenediamine, aniline (and aniline derivatives such as N,Ndimethylaniline), N-ethyldiisopropylamine, tert-butylamine, and combinations thereof.

[0146] In some embodiments, the additive may include a fluoramine. A fluoramine is an amine having one or more fluorinated substituents. Example fluoroamines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0147] In some embodiments, the additive can be a nitrogenous analogue of a carbonic acid, having a formula R*N-C(NR2)-NR3. Example additives can include, but are not limited to, guanidine or derivatives thereof.

[0148] In some embodiments, the additive may be a relatively low molecular weight amine, e.g., having a molecular weight of less than 200 g / mol or 100 g / mol in certain embodiments. Higher molecular weight amines, including those having long chains and / or heterocyclic compounds with aromatic rings, may be used in some embodiments.Amino Acids

[0149] In some embodiments, the additive may include an amino acid. The amino acid may have a formula of R-CH(NR'2)-COOH, where: each R and R' independently are hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0150] Example amino acids that may be used include, but are not limited to, histidine, alanine, and derivatives thereof.Organophosphorus Compounds

[0151] In some embodiments, the additive may include an organophosphorus compound. The organophosphorus compound may be a phosphate ester, a phosphate amide, a phosphonic acid, a phosphinic acid, a phosphonate, a phosphinate, a phosphine oxide, a phosphine imide, or a phosphonium salt. Example organophosphorus compounds include phosphoric acid and trialkylphosphate. In some cases, the organophosphorous compound is a phosphazene. A phosphazene is an organophosphorus compound that includes phosphorus (V) with a double bond between P and N. The phosphazene may have a formula of RN=P(NR2h (where each of R and R2 are independently selected from hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof). In some cases, the phosphazene may have a formula of [X2PN]n(where X is a halide, alkoxide, or amide). Other types of phosphazenes may be used as desired.Oxidizers

[0152] In some embodiments, the additive includes an oxidizer. As used herein, an oxidizer is a material that has the ability to oxidize (e.g., accept electrons from) another substance. Example oxidizers that may be used include, but are not limited to, hydrogen peroxide, sodium hypochlorate, and tetramethyl ammonium hydroxide.Bifluoride Sources

[0153] In some embodiments, the additive includes a bifluoride source. A bifluoride source is a material that includes or produces bifluoride (HF2 ). Example bifluoride sources that may be used include, but are not limited to, ammonium fluoride, aqueous HF, gaseous HF, buffered oxide etch mixture (e.g., a mixture of HF and a buffering agent such as ammonium fluoride), and hydrogen fluoride pyridine. In some embodiments, the bifluoride source (and / or one or more of the other additives listed herein) may react to form HF2" before or after delivery to the reaction chamber.Aldehydes

[0154] In some embodiments, the additive includes an aldehyde having a formula of X-[C(O)]- H, where:X can be selected from hydrogen, -R1, -C(R2)3 or -[C(R3)2]m-C(O)H, wherein each R1, R2and R3independently are selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof, and m is an integer from 0 to 10.

[0155] In some embodiments, each of R1, R2, and R3is, independently, alkyl, alkenyl, alkynyl,heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl-heterocyclyl, heteroalkylheteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed embodiments, the aldehyde or ketone may further be substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=0), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof.

[0156] In some embodiments, when X = aromatic, the additive can be an aromatic aldehyde. Example aromatic aldehydes include benzaldehyde, 1 -naphthaldehyde, phthalaldehyde, and the like.

[0157] In other embodiments, when X = aliphatic, the additive can be an aliphatic aldehyde. Example aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovalerylaldehyde, and the like.

[0158] In yet other embodiments, when X = -[C(R3)2]m-C(O)H and m is 0 to 10 or when X = aliphatic or heteroaliphatic substituted with -C(O)H, the additive can be a dialdehyde. Example dialdehydes include glyoxal, phthalaldehyde, glutaraldehyde, malondialdehyde, succinaldehyde, and the like.

[0159] In some examples, an aldehyde used as an additive may be selected from the group consisting of: acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other cases, an aldehyde used as an additive may be selected from the aldehydes discussed in this section and the aldehydes discussed in the organic solvent section.Carbenes

[0160] In some embodiments, the additive includes a carbene. The carbene may have a formula of X-(C:)-Y, where: each of X and Y can be independently selected from H, halo, -[C(R1)2]m-C(R2)3, -C(O)- R1, or -C(=NR1)-R2, -NR'R2, -OR2, -SR2, or -C(R2)3, wherein each of R1and R2is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic- aromatic, heteroaliphatic-aromatic, or any combinations thereof, and wherein m is an integer from 0 to 10;in which R1and R2, taken together with the atom to which each are attached, can optionally form a cycloheteroaliphatic group; and in which X and Y, taken together with the atom to which each are attached, can optionally form a cycloaliphatic or cycloheteroaliphatic group.

[0161] Furthermore, the additive can be a carbenium cation having a formula R'-CiRj-R2, wherein each of R, R1, and R2is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combinations thereof.

[0162] In some embodiments, each R, R1, and R2independently is selected from alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heterocyclyl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, alkylheteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, heteroalkynyl- heterocyclyl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combinations thereof. In particular disclosed embodiments, the carbene may further be substituted with one or more substituents, such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combinations thereof. In any embodiment of a carbene, each of R1and R2can be independently selected.

[0163] In some embodiments, when at least one of X or Y is halo, the additive can be a halocarbene. Example, non-limiting halocarbenes include dihalocarbene, such as dichlorocarbene, difluorocarbene, and the like.

[0164] In some embodiments, when both X = Y = -NR1R2, the additive can be a diaminocarbene. In one instance, each of R1and R2is independently aliphatic. Example diaminocarbenes include bis(diisopropylamino) carbene, and the like.

[0165] In other embodiments, when both at least one of X or Y = -NR1R2and both R1and R2within X or within Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive can be a cyclic diaminocarbene. Example cyclic diamino carbenes include bisW-piperidyl ) carbene, bis(7V- pyrrolidinyl) carbene, and the like.

[0166] In one instance, when both X = Y = -NRJR2and an R1group from X and an R2group from Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive is an -heterocyclic carbene. Example N-heterocyclic carbenes include imidazol-2-ylidenes (e.g., l,3-dimesitylimidazol-2-ylidene, l,3-dimesityl-4,5-dichloroimidazol-2-ylidene, 1 ,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1 ,3-di-tert- butylimidazol-2-ylidene, etc.), imidazolidin-2-ylidenes (e.g., l,3-bis(2,6- diisopropylphenyl)imidazolidin-2-ylidene), triazol-5-ylidenes (e.g., 1 ,3,4-triphenyl-4,5-dihydro- lH-l,2,4-triazol-5-ylidene), and the like.

[0167] In some embodiments, when X = -NR]R2and Y = -SR2and an R1group from X and an R2group from Y are taken together, with the nitrogen atom to which each are attached, to form a cycloheteroaliphatic group, the additive is acyclic thioalkyl amino carbene. Example cyclic thioalkyl amino carbenes include thiazol-2-ylidenes (e.g., 3-(2,6-diisopropylphenyl)thiazol-2- ylidene and the like).

[0168] In some embodiments, when X = -NR' R2and Y = -C(R2)3 and an R1group from X and an R2group from Y are taken together, with the atom to which each are attached, to form a cycloheteroaliphatic group, the additive is an cyclic alkyl amino carbene. Example cyclic alkyl amino carbenes include pyrrolidine-2-ylidenes (e.g., l,3,3,5,5-pentamethyl-pyrrolidin-2-ylidene and the like) and piperidin-2-ylidenes (e.g., l,3,3,6,6-pentamethyl-piperidin-2-ylidene and the like).

[0169] Further example carbenes and derivatives thereof include compounds having a thiazol- 2-ylidene moiety, a dihydroimidazoI-2-yIidene moiety, an imidazol-2-ylidene moiety, a triazol-5- ylidene moiety, or a cyclopropenylidene moiety. Yet other carbenes and carbene analogs include an aminothiocarbene compound, an aminooxycarbene compound, a diaminocarbene compound, a heteroamino carbene compound, a 1,3 -di thiolium carbene compound, a mesoionic carbene compound (e.g., an imidazoIin-4-ylidene compound, a 1,2,3-triazolylidene compound, a pyrazolinylidene compound, a tetrazol-5-ylidene compound, an isoxazol-4-ylidene compound, a thiazol-5-ylidene compound, etc.), a cyclic alkyl amino carbene compound, a boranylidene compound, a silylene compound, a stannylene compound, a nitrene compound, a phosphinidene compound, a foiled carbene compound, etc. Further example carbenes include dimethyl imidazol- 2-ylidene, l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene,(phosphanyl)(trifluoromethyl)carbene, bis(diisopropylamino) carbene, bis(diisopropylamino) cyclopropenylidene, 1 ,3-dimesityl-4,5-dichloroimidazol-2-ylidene, 1 ,3-diadamantylimidazol-2- ylidene, l,3,4,5-tetramethylimidazol-2-ylidene, l,3-dimesitylimidazol-2-ylidene, 1,3- dimesityIimidazol-2-yIidene, l,3,5-triphenyltriazol-5-ylidene, bis(diisopropylamino) cyclopropenylidene, bis(9-anthryl)carbene, norbornen-7-ylidene, dihydroimidazol-2-ylidene, methylidenecarbene, etc.Organic Acids

[0170] In some embodiments, the additive includes an organic acid. The organic acid may have a formula of R-CO2H, wherein R is selected from hydrogen, aliphatic, haloaliphatic,haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic or any combinations thereof. In certain embodiments, R is alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, haloalkyl, haloalkenyl, haloalkynyl, haloheteroalkyl, haloheteroalkenyl, haloheteroalkynyl, aryl, heteroaryl, alkyl-aryl, alkenyl-aryl, alkynyl-aryl, alkyl-heteroaryl, alkenyl-heteroaryl, alkynyl-heteroaryl, heteroalkyl-aryl, heteroalkenyl-aryl, heteroalkynyl-aryl, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl or any combinations thereof. In particular disclosed embodiments, R may further be substituted with one or more substituents such as, alkoxy, amide, amine, thioether, hydroxyl, thiol, acyloxy, silyl, cycloaliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, acyl halide, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl wherein the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide or any combinations thereof. In certain implementations, the organic acid may be selected from formic acid and acetic acid.Hydrogen Fluoride Complex Forming Chemicals

[0171] In some embodiments, the additive includes a chemical that forms a complex with hydrogen fluoride. Such chemicals are referred to herein as hydrogen fluoride complex forming chemicals. The complex that is formed may act to increase the rate at which the target material is etched from the substrate, while maintaining a high degree of selectivity.

[0172] In various embodiments herein, a hydrogen fluoride complex forming chemical may be provided in combination with hydrogen fluoride. In such embodiments, the additive includes the hydrogen fluoride complex forming chemical, and the halogen source includes the hydrogen fluoride. These may be combined with any of the organic solvents and / or water, and any of the carrier gases described herein. In a related embodiment, a hydrogen fluoride complex forming chemical may be used in combination with a halogen source other than hydrogen fluoride.

[0173] Hydrogen fluoride complex forming chemicals may have a variety of different formulas and / or properties. For instance, in various implementations a hydrogen fluoride complex forming chemical may be or include one or more amine group, urea group, phosphine group, alkyl group, imidazole group, heterocyclic aliphatic group, heterocyclic aromatic group, ether group, etc. In various embodiments, a hydrogen fluoride complex forming chemical may include two or more particular groups, for example two or more alkyl groups, three or more alkyl groups, or four or more alkyl groups. This also applies to the other types of groups listed above. A number of additives include more than one kind of group (e.g., an imidazole group and one or more alkyl group, etc.). Such groups may be combined in various ways, including but not limited to the particular examples provided below.

[0174] Examples of hydrogen fluoride complex forming chemicals that may be used as an additive include, but are not limited to, cyclic urea or other urea-containing compounds such asl,3-dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidinone (also referred to as N,N’ -dimethylpropylene urea or DMPU); alkyl-substituted ammonium compounds such as tetraethylammonium and tetrabutylammonium; heterocyclic aromatic amine-containing compounds such as melamine; heterocyclic aliphatic compounds or cyclic ether compounds such as tetrahydrofuran; alkylsubstituted imidazole compounds such as dialky limidazolium; alkyl-substituted ether compounds such as dimethyl ether; alkyl-substituted phosphine compounds such as trialkylphosphine; and combinations thereof. Various compounds may form complexes with HF in a similar manner, and may be used in the same or similar way.

[0175] Other examples of additives that may act as hydrogen fluoride complex forming chemicals include, but are not limited to, pyridine and triethylamine. These may be used in some embodiments. In other embodiments, the hydrogen fluoride complex forming chemical may exclude pyridine and / or triethylamine.Substitutions

[0176] Any of the example materials described herein include unsubstituted and / or substituted forms of the compound. Non-limiting example substituents include, e.g., one, two, three, four, or more substituents independently selected from the group consisting of: (1) Ci-6 alkoxy (e.g., -O- R, in which R is Ci-6 alkyl); (2) Ci-6 alkylsulfinyl (e.g., -S(O)-R, in which R is Ci-6 alkyl); (3) Ci-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (4) amine (e.g., -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 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., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (20) C1-6 thioalkoxy (e.g., -S-R, in which R is C1-6 alkyl); (21) thiol (e.g., -SH); (22) -CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(O)NR’R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) Ci-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl- C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) -SO2NR1R2, where each ofR1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) Ci-6 alkyl, (c) C4-18 aryl, and (d) Ci-6 alkyl-C4-is aryl (e.g., -L-R, in which L is Ci-6 alkyl and R is C4-18 aryl); and (26) -NR]R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4 i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-Cs-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group.

[0177] In certain embodiments, the additive may act as a proton acceptor and promote formation of HFf. In some such cases, the HF2- may actively etch one or more materials on the substrate such as an oxide material or another material.ADDITIONAL DEFINITIONS

[0178] This section presents additional definitions that may be used herein. Some of the materials described in this section may overlap with those presented elsewhere in the application.

[0179] The term “acyl,” or “alkanoyl,” as used interchangeably herein, represents groups of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of a straight, branched, cyclic configuration, saturated, unsaturated and aromatic, and combinations thereof, or hydrogen, attached to the parent molecular group through a carbonyl group, as defined herein. This group is exemplified by formyl, acetyl, propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, in which R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0180] By “acyl halide” is meant -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0181] By “aldehyde” is meant a -C(O)H group.

[0182] By “aliphatic” is meant a hydrocarbon group having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (Ci- 10), and which includes alkanes (or alkyl), alkenes (or alkenyl), alkynes (or alkynyl), including cyclic versions thereof, and further including straight- and branched-chain arrangements, and all stereo and position isomers as well.

[0183] By “alkyl-aryl,” “alkenyl-aryl,” and “alkynyl-aryl” is meant an aryl group, as defined herein, that is or can be coupled (or attached) to the parent molecular group through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl group can be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl group can be substituted with one or more substitution groups, as described herein for alkyl, alkenyl, alkynyl, and / or aryl. Example unsubstituted alkyl-aryl groups are of from 7 to 16 carbons (C7-16 alkyl-aryl), as well as those having an alkyl group with 1 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C1-6 alkyl-Cr-is aryl). Example unsubstituted alkenyl-arylgroups are of from 7 to 16 carbons (C7-16 alkenyl-aryl), as well as those having an alkenyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkenyl-C4-is aryl). Example unsubstituted alkynyl-aryl groups are of from 7 to 16 carbons (C7-16 alky nyl- aryl), as well as those having an alkynyl group with 2 to 6 carbons and an aryl group with 4 to 18 carbons (i.e., C2-6 alkynyl-C4-i8 aryl). In some embodiments, the alkyl-aryl group is -L-R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the alkenyl-aryl group is -L-R, in which L is an alkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the alkynyl-aryl group is -L-R, in which L is an alkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0184] By “alkenyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms (C2-10), and at least one carbon-carbon double bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group can be branched, straight-chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). An example alkenyl includes an optionally substituted C2-24 alkyl group having one or more double bonds. The alkenyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substitution groups, as described herein for alkyl.

[0185] By “alkyl-heteroaryl” is meant a heteroaryl group, as defined herein, attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the alkyl-heteroaryl group is -L-R, in which L is an alkyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0186] By “alkyLheterocyclyl,” “alkenyl-heterocyclyl,” and “alkynyl-heterocyclyl” is meant a heterocyclyl group, as defined herein, that is or can be coupled (or attached) to the parent molecular group through an alkyl, alkenyl, or alkynyl group, respectively, as defined herein. The alkyl- heterocyclyl, alkenyl-heterocyclyl, and / or alkynyl-heterocyclyl group can be substituted or unsubstituted. For example, the alkyLheterocyclyl, alkenyl-heterocyclyl, and / or alkynyl- heterocyclyl group can be substituted with one or more substitution groups, as described herein for alkyl, alkenyl, alkynyl, and / or heterocyclyl. Example unsubstituted alkyLheterocyclyl groups are of from 2 to 16 carbons (C2-16 alkyLheterocyclyl), as well as those having an alkyl group with 1 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., Ci-6 alkyLCi-is heterocyclyl). Example unsubstituted alkenyl-heterocyclyl groups are of from 3 to 16 carbons (C3-16 alkenyl- heterocyclyl), as well as those having an alkenyl group with 2 to 6 carbons and a heterocyclylgroup with 1 to 18 carbons (i.e., C2-6 alkenyl-Ci-is heterocyclyl). Example unsubstituted alkynyl- heterocyclyl groups are of from 3 to 16 carbons (C3-16 alkynyl-heterocyclyl), as well as those having an alkynyl group with 2 to 6 carbons and a heterocyclyl group with 1 to 18 carbons (i.e., C2-6 alkynyl-C 1-18 heterocyclyl). In some embodiments, the alkyl-heterocyclyl group is -L-R, in which L is an alkyl group, as defined herein, and R is a heterocyclyl group, as defined herein. In some embodiments, the alkenyl-heterocyclyl group is -L-R, in which L is an alkenyl group, as defined herein, and R is a heterocyclyl group, as defined herein. In some embodiments, the alkynyl-heterocyclyl group is -L-R, in which L is an alkynyl group, as defined herein, and R is a heterocyclyl group, as defined herein.

[0187] By “alkoxy” is meant -OR, where R is an optionally substituted aliphatic group, as described herein. Example alkoxy groups include, but are not limited to, methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, etc. The alkoxy group can be substituted or unsubstituted. For example, the alkoxy group can be substituted with one or more substitution groups, as described herein for alkyl. Example unsubstituted alkoxy groups include C1-3, C1-6, C1-12, C1-16, Ci-is, C1-20, or C1-24 alkoxy groups.

[0188] By “alkyl” is meant a saturated monovalent hydrocarbon having at least one carbon atom to 50 carbon atoms (C1-50), such as one to 25 carbon atoms (C1-25), or one to ten carbon atoms (Ci- 10), wherein the saturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., alkane). An alkyl group can be branched, straight-chain, or cyclic (e.g., cycloalkyl). An example alkyl includes a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, s-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. The alkyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. For example, the alkyl group can be substituted with one, two, three or, in the case of alkyl groups of two carbons or more, four substituents independently selected from the group consisting of: (1) C1-6 alkoxy (e.g., -O-R, in which R is C1-6 alkyl); (2) C1-6 alkylsulfinyl (e.g., - S(O)-R, in which R is C1-6 alkyl); (3) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is Ci-6 alkyl); (4) amine (e.g., -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (5) aryl; (6) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, in which R is aryl); (8) azido (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C3-8 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., -O-R, in which R is heterocyclyl, as defined herein); (15) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (16) hydroxyl (e.g., -OH); (17) N-protected amino; (18) nitro (e.g., -NO2); (19) oxo (e.g., =0); (20) C1-6 thioalkoxy (e.g., -S-R, in which R is alkyl); (21) thiol (e.g., -SH); (22) - CO2R1, where R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (23) -C(0)NR1R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4 is aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (24) -SO2R1, where R1is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (25) -SO2NR1R2. where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); and (26) -NR'R2, where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-is aryl (e.g., -L-R, in which L is Ci-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-Cs-8 cycloalkyl (e.g., -L-R, in which L is Ci-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group. The alkyl group can be a primary, secondary, or tertiary alkyl group substituted with one or more substituents (e.g., one or more halo or alkoxy). In some embodiments, the unsubstituted alkyl group is a C1-3, C1-6, Ci- 12, C1-16, Ci-is, C1-20, or Ci-24 alkyl group.

[0189] By “alkylsulfinyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, the unsubstituted alkylsulfinyl group is a C1-6 or C1-12 alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)- R, in which R is an alkyl group, as defined herein.

[0190] By “alkylsulfonyl” is meant an alkyl group, as defined herein, attached to the parent molecular group through an -SO2- group. In some embodiments, the unsubstituted alkylsulfonyl group is a Ci-6 or C 1-12 alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2- R, where R is an optionally substituted alkyl (e.g., as described herein, including optionally substituted Ci-12 alkyl, haloalkyl, or perfluoroalkyl).

[0191] By “alkynyl” is meant an unsaturated monovalent hydrocarbon having at least two carbon atom to 50 carbon atoms (C2-50), such as two to 25 carbon atoms (C2-25), or two to ten carbon atoms(C2 10), and at least one carbon-carbon triple bond, wherein the unsaturated monovalent hydrocarbon can be derived from removing one hydrogen atom from one carbon atom of a parent alkyne. An alkynyl group can be branched, straight-chain, or cyclic (e.g., cycloalkynyl). An example alkynyl includes an optionally substituted C2-24 alkyl group having one or more triple bonds. The alkynyl group can be cyclic or acyclic and is exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can be monovalent or multivalent (e.g., bivalent) by removing one or more hydrogens to form appropriate attachment to the parent molecular group or appropriate attachment between the parent molecular group and another substitution. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substitution groups, as described herein for alkyl.

[0192] By “amide” is mean -C(O)NR1R2or -NHCOR1, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein.

[0193] By “amine” is meant -NR1R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein.

[0194] By “aminoalkyl” is meant an alkyl group, as defined herein, substituted by an amine group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR1R2, in which L is an alkyl group, as defined herein, and each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -L-C(NR]R2)(R3)-R4, in which L is a covalent bond or an alkyl group, as defined herein; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or alkyl, as defined herein.

[0195] By “aromatic” is meant a cyclic, conjugated group or moiety of, unless specified otherwise, from 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple condensed rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl); that is, at least one ring, and optionally multiple condensed rings, have a continuous, delocalized 71-electron system. Typically, the number of out of plane 7t-electrons corresponds to the Huckel rule (4n+2).The point of attachment to the parent structure typically is through an aromatic portion of the condensed ring system.

[0196] By “aryl” is meant an aromatic carbocyclic group comprising at least five carbon atoms to 15 carbon atoms (C5-15), such as five to ten carbon atoms (C5-10), having a single ring or multiple condensed rings, which condensed rings can or may not be aromatic provided that the point of attachment to a remaining position of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. Aryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Example aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group that contains an aromatic group that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term non-heteroaryl, which is also included in the term aryl, defines a group that contains an aromatic group that does not contain a heteroatom. The aryl group can be substituted or unsubstituted. The aryl group can be substituted with one, two, three, four, or five substituents independently selected from the group consisting of: (1) C1-6 alkanoyl (e.g., -C(O)-R, in which R is C1-6 alkyl); (2) C1-6 alkyl; (3) C1-6 alkoxy (e.g., -O-R, in which R is Ci-6 alkyl); (4) C1-6 alkoxy-Ci-6 alkyl (e.g., -L-O-R, in which each of L and R is, independently, C1-6 alkyl); (5) C1-6 alkylsulfinyl (e.g., -S(O)-R, in which R is C1-6 alkyl); (6) C1-6 alkylsulfinyl-Ci-6 alkyl (e.g., -L-S(O)-R, in which each of L and R is, independently, Ci-6 alkyl); (7) C1-6 alkylsulfonyl (e.g., -SO2-R, in which R is C1-6 alkyl); (8) C1-6 alkylsulfonyl-Ci-6 alkyl (e.g., -L-SO2-R, in which each of L and R is, independently, C1-6 alkyl); (9) aryl; (10) amine (e.g., - NR' R2, where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein); (11) C1-6 aminoalkyl (e.g., -L'-NR' R2or -L2- C(NR1R2)(R3)-R4, in which L1is C1-6 alkyl; L2 is a covalent bond or C1-6 alkyl; each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the nitrogen atom to which each are attached, form a heterocyclyl group, as defined herein; and each of R3and R4is, independently, H or C1-6 alkyl); (12) heteroaryl; (13) C1-6 alkyl- C4-18 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (14) aryloyl (e.g., -C(O)-R, in which R is aryl); (15) azido (e.g., -N3); (16) cyano (e.g., -CN); (17) C 1-6 azidoalkyl (e.g., -L-N3, in which L is C1-6 alkyl); (18) aldehyde (e.g., -C(O)H); (19) aldehyde-Ci-6 alkyl (e.g., -L-C(O)H, in which L is C1-6 alkyl); (20) C3-8 cycloalkyl; (21) C1-6 alkyl-Cvs cycloalkyl (e.g., -L-R, in which Lis Ci-6 alkyl and R is C3-8 cycloalkyl); (22) halo; (23) C1-6 haloalkyl (e.g., -L'-X or -L2-C(X)(R1)- R2, in which L1is Ci-6 alkyl; L2is a covalent bond or Ci-6 alkyl; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or C1-6 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., -O-R, in which R is heterocyclyl, as defined herein); (26) heterocyclyloyl (e.g., -C(O)-R, in which R is heterocyclyl, as defined herein); (27) hydroxyl (- OH); (28) C1-6 hydroxyalkyl (e.g., -L'-OH or -L2-C(OH)(R])-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6 alkyl, as defined herein); (29) nitro; (30) C1-6 nitroalkyl (e.g., -L'-NO or -L2-C(NO)(R])-R2, in which L1is C1-6 alkyl; L2is a covalent bond or alkyl; and each of R1and R2is, independently, H or C1-6 alkyl, as defined herein); (31) N-protected amino; (32) N-protected amino-Ci-6 alkyl; (33) oxo (e.g., =0); (34) C1-6 thioalkoxy (e.g., -S-R, in which R is C1-6 alkyl); (35) thio-Ci-6 alkoxy-Ci-6 alkyl (e.g., -L-S-R, in which each of L and R is, independently, C1-6 alkyl); (36) -(CH2)rCO2R', where r is an integer of from zero to four, and R1is selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4-is aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (37) -(CH2)rCONR1R2, where r is an integer of from zero to four and where each R1and R2is independently selected from the group consisting of (a) hydrogen, (b) C1-6 alkyl, (c) C4-18 aryl, and (d) C1-6 alkyl-C4 i8 aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (38) -(CTDrSChR1, where r is an integer of from zero to four and where R1is selected from the group consisting of (a) C1-6 alkyl, (b) C4-18 aryl, and (c) Ci-6 alkyl-C4 -is aryl (e.g., -L-R, in which L is Ci-6 alkyl and R is C4-18 aryl); (39) -(C^XSChNR'R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) Ci-6 alkyl, (c) C4- 18 aryl, and (d) C1-6 alkyl-C4-is aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl); (40) - (CH2)rNR1R2, where r is an integer of from zero to four and where each of R1and R2is, independently, selected from the group consisting of (a) hydrogen, (b) an N-protecting group, (c) C1-6 alkyl, (d) C2-6 alkenyl, (e) C2-6 alkynyl, (f) C4-18 aryl, (g) C1-6 alkyl-C4-is aryl (e.g., -L-R, in which L is C1-6 alkyl and R is C4-18 aryl), (h) C3-8 cycloalkyl, and (i) C1-6 alkyl-Cs-8 cycloalkyl (e.g., -L-R, in which L is C1-6 alkyl and R is C3-8 cycloalkyl), wherein in one embodiment no two groups are bound to the nitrogen atom through a carbonyl group or a sulfonyl group; (41) thiol (e.g., -SH); (42) perfluoroalkyl (e.g., -(CF2)nCF3, in which n is an integer from 0 to 10); (43) perfluoroalkoxy (e.g., -O-(CF2)nCF3, in which n is an integer from 0 to 10); (44) aryloxy (e.g., -O-R, in which R is aryl); (45) cycloalkoxy (e.g., -O-R, in which R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -O-L- R, in which L is alkyl and R is cycloalkyl); and (47) arylalkoxy (e.g., -O-L-R, in which L is alkyl and R is aryl). In particular embodiments, an unsubstituted aryl group is a C4-18, C4-14, C4-12, C4- 10, C6-18, Ce-14, C6-12, or C6-10 aryl group.

[0197] By “arylalkoxy” is meant an alkyl-aryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -O-L- R, in which L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0198] By “aryloxy” is meant -OR, where R is an optionally substituted aryl group, as described herein. In some embodiments, an unsubstituted aryloxy group is a C4-18 or Ce-is aryloxy group.

[0199] By “aryloyl” is meant an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is a C7-11 aryloyl or C5-19 aryloyl group. In other embodiments, the aryloyl group is -C(O)-R, in which R is an aryl group, as defined herein.

[0200] By ‘ ‘azido” is meant an -N3 group.

[0201] By “azidoalkyl” is meant an azido group attached to the parent molecular group through an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, in which L is an alkyl group, as defined herein. By “azo” is meant an -N=N- group.

[0202] By “carbene” is meant H2C: and derivatives thereof having carbon bearing two nonbonding electrons or (C:). In some embodiments, the carbene is R1R2(C:), where each of R1and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2, taken together with the atom to which each are attached, form a cycloaliphatic group, as defined herein.

[0203] By “carbenium cation” is meant HsC+and derivatives thereof having carbon bearing a +1 formal charge or C+. In some embodiments, the carbenium cation is R -C+(R )-R2, where each of R, R1, and R2is, independently, selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof, or R1and R2and optionally R, taken together with the atom to which each are attached, form a cycloaliphatic group, as defined herein.

[0204] By “carbonyl” is meant a -C(O)- group, which can also be represented as >C=O.

[0205] By “carboxyl” is meant a -CO2H group or an anion thereof.

[0206] By ‘ ‘cyano” is meant a -CN group.

[0207] By “cycloaliphatic” is meant an aliphatic group, as defined herein, that is cyclic.

[0208] By “cycloalkoxy” is meant a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -O-R, in which R is a cycloalkyl group, as defined herein.

[0209] By “cycloalkylalkoxy” is meant an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is -O-L-R, in which L is an alkyl group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0210] By “cycloalkyl” is meant a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon group of from three to eight carbons, unless otherwise specified, and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1. heptyl, and the like. The cycloalkyl group can also be substituted or unsubstituted. For example, the cycloalkyl group can be substituted with one or more groups including those described herein for alkyl.

[0211] By “cycloheteroaliphatic” is meant a heteroaliphatic group, as defined herein, that is cyclic.

[0212] By “ester” is meant -C(O)OR or -OC(O)R, where R is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0213] By “ether” is meant R-O-R1, where each of R and R1is, independently, selected from an aryl or alkyl group, or where R and R1, taken together with the atom to which each are attached, form a heterocyclic ring, as defined herein.

[0214] By “halo” is meant F, Cl, Br, or I.

[0215] By “haloaliphatic” is meant an aliphatic group, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0216] By “haloalkyl” is meant an alkyl group, as defined herein, where one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In an independent embodiment, haloalkyl can be a -CX3 group, wherein each X independently can be selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -L-X, in which L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, the halooalkyl group is -L-CiXHR1)-R2, in which L is a covalent bond or an alkyl group, as defined herein; X is fluoro, bromo, chloro, or iodo; and each of R1and R2is, independently, H or alkyl, as defined herein.

[0217] By “haloheteroaliphatic” is meant a heteroaliphatic, as defined herein, in which one or more hydrogen atoms, such as one to 10 hydrogen atoms, independently is replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0218] By “heteroaliphatic” is meant an aliphatic group, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5 heteroatoms, which can be selected from, but not limited to oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group.

[0219] By “heteroalkyl,” “heteroalkenyl,” and “heteroalkynyl” is meant an alkyl, alkenyl, or alkynyl group (which can be branched, straight-chain, or cyclic), respectively, as defined herein, including at least one heteroatom to 20 heteroatoms, such as one to 15 heteroatoms, or one to 5heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the group.

[0220] By “heteroalkyl-aryl,” “heteroalkenyl-aryl,” and “heteroalkynyl-aryl” is meant an aryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the aryl group is or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-aryl group is -L-R, in which L is a heteroalkyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkenyl-aryl group is -L-R, in which L is a heteroalkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkynyl-aryl group is -L-R, in which L is a heteroalkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0221] By “heteroalkyl-heteroaryl,” “heteroalkenyl-heteroaryl,” and “heteroalkynyl-heteroaryl” is meant a heteroaryl group, as defined herein, that is or can be coupled to a compound disclosed herein, where the heteroaryl group is or becomes coupled through a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl- heteroaryl group is -L-R, in which L is a heteroalkyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkenyl-heteroaryl group is -L-R, in which L is a heteroalkenyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkynyl-heteroaryl group is -L-R, in which L is a heteroalkynyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0222] By “heteroaryl” is meant an aryl group including at least one heteroatom to six heteroatoms, such as one to four heteroatoms, which can be selected from, but not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorous, and oxidized forms thereof within the ring. Such heteroaryl groups can have a single ring or multiple condensed rings, where the condensed rings may or may not be aromatic and / or contain a heteroatom, provided that the point of attachment is through an atom of the aromatic heteroaryl group. Heteroaryl groups may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. An example heteroaryl includes a subset of heterocyclyl groups, as defined herein, which are aromatic, i.e., they contain 4n+2 pi electrons within the mono- or multicyclic ring system.

[0223] By “heteroatom” is meant an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorous. In particular disclosed embodiments, such as when valency constraints do not permit, a heteroatom does not include a halogen atom.

[0224] By “heterocyclyl” is meant a 5-, 6- or 7-membered ring, unless otherwise specified, containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from thegroup consisting of nitrogen, oxygen, phosphorous, sulfur, or halo). The 5-membered ring has zero to two double bonds and the 6- and 7 -membered rings have zero to three double bonds. The term “heterocyclyl” also includes bicyclic, tricyclic and tetracyclic groups in which any of the above heterocyclic rings is fused to one, two, or three rings independently selected from the group consisting of an aryl ring, a cyclohexane ring, a cyclohexene ring, a cyclopentane ring, a cyclopentene ring, and another monocyclic heterocyclic ring, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl and the like. Heterocyclics include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidiniyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl, and the like.

[0225] By “heterocyclyloxy’' is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -O-R, in which R is a heterocyclyl group, as defined herein.

[0226] By “heterocyclyloyl” is meant a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyloyl group is -C(O)-R, in which R is a heterocyclyl group, as defined herein.

[0227] By “hydroxyl” is meant -OH.

[0228] By “hydroxyalkyl” is meant an alkyl group, as defined herein, substituted by one to three hydroxyl groups, with the proviso that no more than one hydroxyl group may be attached to a single carbon atom of the alkyl group and is exemplified by hydroxymethyl, dihydroxypropyl, and the like. In some embodiments, the hydroxyalkyl group is -L-OH, in which L is an alkyl group, as defined herein. In other embodiments, the hydroxyalkyl group is -L-C(OH)(R])-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1and R2is, independently, H or alkyl, as defined herein.

[0229] By “ketone” is meant -C(O)R, where R is selected from aliphatic, heteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0230] By “nitro” is meant an -NO2 group.

[0231] By “nitroalkyl” is meant an alkyl group, as defined herein, substituted by one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, in which L is an alkyl group, as defined herein. In other embodiments, the nitroalkyl group is -L-C(NO)(R1)-R2, in which L is a covalent bond or an alkyl group, as defined herein, and each of R1and R2is, independently, H or alkyl, as defined herein.

[0232] By “oxo” is meant an =0 group.

[0233] By “oxy” is meant -O-.

[0234] By “perfluoroalkyl” is meant an alkyl group, as defined herein, having each hydrogen atom substituted with a fluorine atom. Example perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, etc. In some embodiments, the perfluoroalkyl group is -(CF2)nCF3, in which n is an integer from 0 to 10.

[0235] By “perfluoroalkoxy” is meant an alkoxy group, as defined herein, having each hydrogen atom substituted with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -O-R, in which R is a perfluoroalkyl group, as defined herein.

[0236] By “phosphine” is meant P-R*R2, where each of R1and R2is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, or aromatic, or R1and R2taken together with the atom to which each are attached, form a heterocyclic group, as defined herein.

[0237] By “salt” is meant an ionic form of a compound or structure (e.g., any formulas, compounds, or compositions described herein), which includes 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 S M et al., “Pharmaceutical salts,” J. Pharm. Sci. 1977 January; 66(1): 1-19; and in “Handbook of Pharmaceutical Salts: Properties, Selection, and Use,” Wiley-VCH, April 2011 (2nd rev. ed., eds. P. H. Stahl and C. G. Wermuth. The salts can be prepared in situ during the final isolation and purification of the compounds of the invention or separately by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or by reacting the acid group with a suitable metal or organic salt (thereby producing a cationic salt). Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecylsulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, lactobionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methylbromide, methylnitrate, methylsulfate, 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, triethiodide, toluenesulfonate, undecanoate, valerate salts, and the like. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, e.g., barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and the like; other metal salts, such as aluminum, bismuth, iron, and zinc; as well as nontoxic ammonium, quaternary ammonium, and amine cations, including, but not limited to ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine. Yet other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, etc., as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperazinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted indolium, optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinum, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted purinium).

[0238] By “sulfo” is meant an -S(O)2OH group.

[0239] By “sulfonyl” or “sulfonate” is meant an -S(O)2- group or a -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, as defined herein, or any combination thereof.

[0240] By “thioalkoxy” is meant an alkyl group, as defined herein, attached to the parentmolecular group through a sulfur atom. Example unsubstituted thioalkoxy groups include Ci-6 thioalkoxy. In some embodiments, the thioalkoxy group is -S-R, in which R is an alkyl group, as defined herein.

[0241] By “thiol” is meant an -SH group.

[0242] By ‘ ‘urea” is meant (R!NR2)2CO, where R1and R2are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, or aromatic, or R1and R2taken together with the atom to which each are attached, form a heterocyclic group, as defined herein.

[0243] A person of ordinary skill in the art would recognize that the definitions provided above are not intended to include impermissible substitution patterns (e.g., methyl substituted with 5 different groups, and the like). Such impermissible substitution patterns are easily recognized by a person of ordinary skill in the art. Any functional group disclosed herein and / or defined above can be substituted or unsubstituted, unless otherwise indicated therein.CONCLUSION

[0244] Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein.

Claims

1. CLAIMSWhat is claimed is:

1. A method for processing substrates, the method comprising: providing a substrate having a first material and a second material, wherein germanium content of the first material is less than the germanium content of the second material; introducing flow of a gas mixture to a process chamber housing the substrate; and after introducing the flow of the gas mixture, introducing flow of a halogen source to the process chamber in a plasma-free environment to thermally etch the first material selectively relative to the second material.

2. The method of claim 1 , wherein the first material comprises silicon, and the germanium content of the first material is less than 1%.

3. The method of claim 1, wherein the second material comprises silicon, and the germanium content of the second material is at least about 2%.

4. The method of any of claims 1-3, further comprising after introducing the flow of the gas mixture and prior introducing the flow of the halogen source, stopping the flow of the gas mixture.

5. The method of claim 4, further comprising repeating introducing the flow of the gas mixture, then stopping the flow of the gas mixture, then introducing the flow of the halogen source, and stopping the flow of the halogen source in cycles.

6. The method of claim 5, wherein during each cycle, flow of the halogen source is performed for a duration shorter than a duration of the flow of the gas mixture.

7. The method of claim 5, wherein during each cycle, flow of the halogen source is performed for a duration of about 10 seconds to about 40 seconds.

8. The method of claim 5, wherein during each cycle, flow of the gas mixture is performed for a duration of about 40 seconds to about 80 seconds.

9. The method of claim 1 , wherein the halogen source and gas mixture are co-flowed.

10. The method of claim 1 , further comprising modulating flow rate of at least one of the flow of the halogen source or the flow of the gas mixture.

11. The method of claim 1 , wherein the halogen source comprises a mixture of two halogencontaining gases, wherein a ratio of a first halogen-containing gas to a second halogencontaining gas is about 0.05 to about 0.6.

12. The method of claim 11, wherein the halogen source comprises fluorine (F2) and hydrogen fluoride (HF).

13. The method of claim 1, wherein the gas mixture is vapor phase and comprises: an organic solvent and / or water, an additive, and a carrier gas.

14. The method of claim 1 , wherein the halogen source is flowed with an inert gas.

15. The method of claim 1 , wherein the substrate further comprises a third material having a germanium content of at least about 30%, wherein germanium content of the second material is different from the germanium content of the third material.

16. The method of any of claims 1-15, wherein the method is performed at a temperature of about 60°C to about 80°C.

17. The method of any of claims 1-15, wherein a ratio of flow rate of the halogen source to flow rate of the gas mixture is about 0.1: 1.1 to about 0.5: 1.5.

18. The method of any of claims 1-15, wherein the first material comprises epitaxially deposited silicon.

19. The method of any of claims 1-15, wherein the second material comprises silicon germanium.

20. The method of claim 15, wherein the third material comprises silicon germanium.

21. The method of any of claims 1-15, wherein the halogen source comprises fluorine.

22. The method of any of claims 1-15, wherein the halogen source comprises chlorine.

23. The method of any of claims 1-15, wherein the gas mixture is introduced for a duration of about 5 seconds to about 20 seconds.

24. An apparatus for processing substrates, the apparatus comprising: one or more process chambers, each process chamber comprising a chuck; one or more halogen sources; one or more gas sources for generating a gas mixture; one or more gas inlets into the process chambers and associated flow-control hardware; and a controller having at least one processor and a memory, wherein the at least one processor and the memory are communicatively connected with one another, the at least one processor is at least operatively connected with 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: cause introduction of a halogen source to the one or more process chambers; and after introduction of the halogen source, cause introduction of a gas mixture to the one or more process chambers.

25. The apparatus of claim 24, wherein the one or more gas sources comprises a nitrogencontaining gas source.

26. The apparatus of claim 24, wherein the one or more gas sources comprises an organic solvent vapor.

27. The apparatus of claim 24, wherein the one or more gas sources comprises an additive.

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