Selective precision etching of semiconductor materials

Abstract

Various embodiments described herein relate to methods and apparatus for etching a semiconductor substrate to remove a target material from the surface of the substrate. In general, the techniques described herein are thermal techniques that do not rely on the use of a plasma. In many embodiments, a particular gas mixture is provided to a reaction chamber to react with the target material. The gas mixture may include a combination of a halogen source, such as hydrogen fluoride (HF), an organic solvent and / or water, an additive, and a carrier gas. Many different materials may be used for the organic solvent and / or additive. The additive may act to form a complex with the HF or another halogen source.

Description

[Technical field]

[0001] Incorporation by Reference The PCT Application Form is filed contemporaneously herewith as a part of this application. Each application to which this application claims benefit or priority, as identified in the contemporaneously filed PCT Application Form, is hereby incorporated by reference in its entirety for all purposes. [Background technology]

[0002] The fabrication of semiconductors involves many different types of processes. One type of process involves the deposition of material onto the surface of a substrate. Another type of process involves the etching of material from the surface of the substrate. In some cases, such etching is performed selectively to target one or more materials on the substrate for removal.

[0003] The background discussion provided herein is intended to generally present the context of the present disclosure. The work of the currently listed inventors to the extent described in this background section, and aspects of the present specification that may not otherwise be considered prior art at the time of filing, are not admitted expressly or impliedly as prior art to the present disclosure. Summary of the Invention

[0004] Various embodiments herein relate to methods and apparatus for etching semiconductor substrates.

[0005] In one aspect of the disclosed embodiments, a method of etching a substrate is provided that includes: (a) providing a substrate to a reaction chamber, the substrate comprising a target material to be partially or wholly removed from the substrate during etching; (b) providing a gas mixture to the reaction chamber and exposing the substrate to the gas mixture, the gas mixture being in a vapor phase and comprising: (i) a halogen source, (ii) an organic solvent and / or water, (iii) an additive comprising a hydrogen fluoride complexing chemical, and (iv) a carrier gas; and (c) providing thermal energy to the reaction chamber to drive a reaction that partially or wholly etches the target material from the substrate, the method including providing the thermal energy, the substrate not being exposed to a plasma during etching.

[0006] In various embodiments, the method may further include, prior to (b), providing a second gas mixture to the reaction chamber and exposing the substrate to thermal energy and the second gas mixture, where the thermal energy drives a second reaction between the second gas mixture and the target material to form a modified target material, and the reaction in (c) etches the modified target material, thereby partially or fully etching the target material.

[0007] A variety of chemicals may be used. In many embodiments, the hydrogen fluoride complexing chemical may include at least one group selected from the group consisting of an amine group, a urea group, a phosphine group, an alkyl group, an imidazole group, a heterocyclic aliphatic group, a heterocyclic aromatic group, an ether group, or a combination thereof. In some embodiments, the hydrogen fluoride complexing chemical may include a urea group. In some such embodiments, the hydrogen fluoride complexing chemical includes N,N'-dimethylpropylene urea (DMPU). In these or other embodiments, the hydrogen fluoride complexing chemical may include an alkyl substituted ammonium compound. In some such embodiments, the hydrogen fluoride complexing chemical includes a compound selected from the group consisting of tetraethylammonium, tetrabutylammonium, and combinations thereof. In these or other embodiments, the hydrogen fluoride complexing chemical may include a heterocyclic aromatic amine-containing compound. In some such embodiments, the hydrogen fluoride complexing chemical includes melamine. In these or other embodiments, the hydrogen fluoride complexing chemical may include a heterocyclic aliphatic compound and / or a cyclic ether compound. In some such embodiments, the hydrogen fluoride complexing chemical comprises tetrahydrofuran. In these or other embodiments, the hydrogen fluoride complexing chemical may comprise an alkyl-substituted imidazole compound, an alkyl-substituted ether compound, and / or an alkyl-substituted phosphine compound. In some such embodiments, the hydrogen fluoride complexing chemical comprises a compound selected from the group consisting of dialkylimidazolium, dimethyl ether, trialkylphosphine, and combinations thereof.

[0008] In another aspect of the disclosed embodiments, an apparatus for etching a substrate is provided, the apparatus comprising: a reaction chamber configured to withstand subatmospheric pressure; a substrate support configured to support a substrate during etching; an inlet for introducing a gas mixture into the reaction chamber, the gas mixture being in a vapor phase; and an outlet for removing vapor phase species from the reaction chamber; (a) providing a substrate to the reaction chamber, the substrate comprising a target material to be partially or wholly removed from the substrate during etching; (b) providing a gas mixture to the reaction chamber and exposing the substrate to the gas mixture, the gas mixture being in a vapor phase, the gas mixture comprising: (i) a halogen source; (ii) an organic solvent and / or water; (iii) an additive comprising a hydrogen fluoride complexing chemical; and (iv) a carrier gas; and (c) providing thermal energy to the reaction chamber to drive a reaction that partially or wholly etches the target material from the substrate, the substrate not being exposed to a plasma during etching. A controller configured to cause the provision of thermal energy.

[0009] The controller may be further configured to cause, prior to (b), the provision of a second gas mixture to the reaction chamber and exposing the substrate to thermal energy and the second gas mixture, where the thermal energy drives a second reaction between the second gas mixture and the target material to form a modified target material, and where the reaction in (c) etches the modified target material, thereby partially or fully etching the target material.

[0010] Additionally, the controller may be configured to cause the delivery of a particular chemical to the reaction chamber. In numerous embodiments, the hydrogen fluoride complexing chemical may include at least one group selected from the group consisting of an amine group, a urea group, a phosphine group, an alkyl group, an imidazole group, a heteroaliphatic group, a heteroaromatic group, an ether group, or a combination thereof. In some embodiments, the hydrogen fluoride complexing chemical may include a urea group. In some such embodiments, the hydrogen fluoride complexing chemical includes N,N'-dimethylpropylene urea (DMPU). In these or other embodiments, the hydrogen fluoride complexing chemical may include an alkyl-substituted ammonium compound. In some such embodiments, the hydrogen fluoride complexing chemical includes a compound selected from the group consisting of tetraethylammonium, tetrabutylammonium, and combinations thereof. In these or other embodiments, the hydrogen fluoride complexing chemical may include a heteroaromatic amine-containing compound. In some such embodiments, the hydrogen fluoride complexing chemical includes melamine. In these or other embodiments, the hydrogen fluoride complexing chemical may include a heterocyclic aliphatic compound and / or a cyclic ether compound. In some such embodiments, the hydrogen fluoride complexing chemical includes tetrahydrofuran. In these or other embodiments, the hydrogen fluoride complexing chemical may include an alkyl-substituted imidazole compound, an alkyl-substituted ether compound, and / or an alkyl-substituted phosphine compound. In some such embodiments, the hydrogen fluoride complexing chemical includes a compound selected from the group consisting of dialkylimidazolium, dimethyl ether, trialkylphosphine, and combinations thereof.

[0011] These and other aspects are further described below with reference to the drawings. [Brief description of the drawings]

[0012] [Figure 1] 1 is a flow chart illustrating a method for etching a semiconductor substrate in accordance with certain embodiments.

[0013] [Diagram 2] 1 is a flow chart illustrating a cyclical method for etching a semiconductor substrate in accordance with certain embodiments.

[0014] [Figure 3A] FIG. 3 illustrates a semiconductor substrate undergoing processing according to the method described in FIG. 2. [Figure 3B] FIG. 3 illustrates a semiconductor substrate undergoing processing according to the method described in FIG. 2. [Figure 3C] FIG. 3 illustrates a semiconductor substrate undergoing processing according to the method described in FIG. 2.

[0015] [Figure 4] FIG. 3 illustrates how temperature can be varied over time to achieve the method of FIG. 2.

[0016] [Diagram 5] FIG. 1 is a cross-sectional side view of an exemplary device according to disclosed embodiments.

[0017] [Figure 6] FIG. 1 is a top view of a substrate heater including multiple LEDs.

[0018] [Figure 7] FIG. 13 is a top view of another substrate heater including multiple LEDs.

[0019] [Figure 8] 6 illustrates the base of FIG. 5 having additional features according to various embodiments.

[0020] [Figure 9] 9 illustrates the substrate support of FIGS. 5 and 8 according to disclosed embodiments. FIG.

[0021] [Figure 10] FIG. 2 is a plan view of a faceplate of the first example.

[0022] [Figure 11] FIG. 13 is a plan view of a faceplate of the second example.

[0023] [Figure 12] 1 is a graph of four different active cooling experiments.

[0024] [Figure 13] FIG. 11 is a diagram showing an example of a temperature control sequence.

[0025] [Figure 14] FIG. 2 illustrates a first technique for heat treatment according to disclosed embodiments.

[0026] [Figure 15] FIG. 1 illustrates a second technique for heat treatment according to disclosed embodiments.

[0027] [Figure 16] FIG. 13 illustrates a third technique for heat treatment according to disclosed embodiments.

[0028] [Figure 17] 1 is a graph of silicon absorption at various wavelengths and temperatures.

[0029] [Figure 18] 9 illustrates the base of FIG. 8 having additional features according to various embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0031] In various embodiments herein, a semiconductor substrate is etched using a mixture of vapor phase reactants including (1) a halogen source such as hydrogen fluoride, (2) an organic solvent and / or water, (3) an additive, and (4) a carrier gas. The terms "vapor phase" and "gas phase" are used interchangeably in this disclosure. The additive may have specific properties or a specific composition, as further described 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 a 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 extent. One advantage of the disclosed technology is that it achieves a high degree of selectivity during etching. Another advantage of the disclosed technology is that it provides extremely precise control of the etch rate and amount of etch removal, especially compared to other thermally driven etching processes.

[0032] The techniques described herein may be used to etch a variety of substrate materials in many different contexts. Often, a substrate includes two or more different materials exposed on the 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, and the first material is selectively etched compared to the second material. In other cases, the substrate may include only a single material that is exposed, such that the etch does not need to be selective. In still other cases, the substrate may include multiple different materials that are all removed without the 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.), carbonates (e.g., silicon carbonate, etc.), and the like. 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, a high-k dielectric material is a dielectric material that has a high dielectric constant relative to silicon dioxide, and a low-k dielectric material is a dielectric material that has a low dielectric constant relative to silicon oxide. The dielectric constant of silicon oxide is about 3.7 to 3.9. Thus, high-k dielectric materials typically have a dielectric constant greater than about 3.9, while low-k dielectric materials typically have a dielectric constant less than about 3.7. Examples of low-k dielectric materials include carbon-doped silicon oxide, fluorine-doped silicon oxide, and 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 configurations, as desired for a particular application. The techniques described herein are broadly applicable to many different applications.The etch selectivity of a first material (eg, silicon dioxide) relative to a second material (eg, silicon nitride) is further discussed below.

[0033] In one particular embodiment, the methods described herein may be used in the context of trimming silicon fins. Figures 3A-3C, described further below, illustrate such an embodiment. In another particular embodiment, the methods described herein may be used in the context of removing native oxide on gate-all-around structures. Many other applications are possible.

[0034] One advantage of the disclosed techniques is that extremely precise control of etch rate is achieved. Such etch rate control is substantially improved compared to other thermal (e.g., non-plasma) etching techniques. Another advantage of the disclosed techniques is that a very high degree of etch selectivity is achieved. For example, oxide materials may be etched with a high degree of selectivity compared to nitride materials. Other materials may be etched in a selective manner as well.

[0035] As described above, the substrate is etched using a specific set of chemicals. The chemicals include (1) a halogen source, such as hydrogen fluoride (HF), (2) one or more organic solvents and / or water, (3) one or more additives, and (4) one or more carrier gases. The reactants are provided to the reaction chamber and exposed to the substrate while in the vapor phase. As described further below, appropriate hardware may be provided to ensure that the reactants are sufficiently vaporized before and during delivery to the reaction chamber. Two or more of the reactants may be mixed before being delivered 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] Halogen source 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 the vapor phase at the process temperature. Examples include hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), fluorine (F2), chlorine (Cl2), bromine (Br2), chlorine trifluoride (ClF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCl3), and nitrogen tribromide (NBr3). In some implementations, the halogen source is an organic halide, examples include fluoroform (CHF3), chloroform (CHCl3), bromoform (CHBr3), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), carbon tetrabromide (CBr4), perfluorobutene (C4F8), and perchlorobutene (C4Cl8). In some implementations, the halogen source is a silicon halide, examples of which include silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), silicon tetrabromide (SiBr4), and compounds containing SiX6, such as H2SiX6. In some implementations, the halogen source is a metal halide, examples of which include molybdenum hexafluoride (MoF6), molybdenum hexachloride (MoCl6), molybdenum hexabromide (MoBr6), tungsten hexafluoride (WF6), tungsten hexachloride (WCl6), tungsten hexabromide (WBr6), titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), zirconium fluoride (ZrF4), zirconium chloride (ZrCl4), and zirconium bromide (ZrBr4). In some embodiments, metal halides may be used to selectively etch metal oxides.

[0037] In the following description, various examples include HF as a halogen source. However, any suitable halogen source may be used. The volume and mass percentages described for HF may be used for other halogen sources. In some embodiments, two or more halogen sources may be used.

[0038] Organic solvents alcohol: In certain implementations, the organic solvent may be an alcohol. The alcohol may have the formula: XC(R) n (OH)-Y where n is 1, Each X and Y is independently hydrogen, -[C(R 1 )2] m -C(R 2 )3, or OH, and each R 1 and R 2 is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; m is an integer from 0 to 10; and each R is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0039] In some embodiments, each R, R 1 and R 2is 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, 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 combination thereof. In certain disclosed embodiments, the alcohol may be further 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0040] In another embodiment, X or Y=-[C(R 1 )2] m -C(R 2 When at least one of R is hydrogen and m is 1, the alcohol may be a C alcohol. For example, when at least one of R 1 and one R 2 When R is absent, the C3 alcohol may be a C3 alkenol (e.g., allyl alcohol). 2 may be taken together to form a ring (e.g., cycloaliphatic), and the C3 alcohol may be cyclopropanol or 2-cyclopropenol.

[0041] In yet another embodiment, X or Y=-[C(R 1 )2] m -C(R 2 When at least one of R 3 or R is hydrogen and m is 2, the alcohol may be a C4 alcohol. For example, when at least one of R 1 and one R 2 When R is not present, the C4 alcohol may be a C4 alkenol (e.g., 2-buten-1-ol or 3-buten-1-ol). In another example, R and one R 2 may be taken together to form a ring (e.g., cycloaliphatic), and the C4 alcohol may be a C4-cyclic alcohol (e.g., cyclobutanol or cyclopropylmethanol). In yet another example, when both X and Y are not OH, the C4 alcohol may be a C4-branched alcohol (e.g., 2-butanol, isobutanol, or tert-butanol).

[0042] In some examples, X=OH and Y=-[C(R 1 )2] m -C(R 2 In another example, when at least one of X or Y=-[C(R 1 )2] m -C(R 2 )3 and at least one R 1 =OH or one R 2 When =OH or when R=OH, the alcohol can be a diol. Exemplary diols include, but are not limited to, 1,4-butanediol, propylene-1,3-diol, and the like.

[0043] In other instances, when X=Y=OH, the alcohol may be a triol. In yet other instances, when X=R=OH, the alcohol may be a triol. In some instances, at least one of X or Y is -[C(R 1 )2] m -C(R 2)3 and one R 1 and at least one R 2 In another example, when R=OH and X=-[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When is OH, the alcohol may be a triol. Exemplary triols include, but are not limited to, glycerol or its glycerin derivatives.

[0044] In certain embodiments, when R=cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol may be a heterocyclyl alcohol (e.g., an optionally substituted or more hydroxyl-substituted heterocyclyl, such as furfuryl alcohol). In other embodiments, at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3 and one R 1 and at least one R 2 When is cycloheteroaliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol may be a heterocyclyl alcohol.

[0045] In various embodiments, the alcohol may have 1 to 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.

[0046] Laboratory solvents: In these or other cases, the organic solvent may include laboratory-type solvents such as acetonitrile, dichloromethane, carbon tetrachloride, or combinations thereof.

[0047] Ketones: In some embodiments, the organic solvent may be a ketone.

[0048] The organic solvent may also be a ketone having the formula: X-[C(O)] n -Y Here, n is an integer from 1 to 2, Each X and Y is -C(R 1 )3, -R 2 , or -[C(R 3 )2] m -C(O)-R 4 and each R 1 , R 2 , R 3 and R 4 may be independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; R 3 and R 4may optionally form a cycloaliphatic or cycloheteroaliphatic group together with the atom to which they are attached, and X and Y may optionally form a cycloaliphatic or cycloheteroaliphatic group together with the atom to which they are attached; m is an integer from 0 to 10.

[0049] In some embodiments, each R 1 , R 2 , R 3 and R 4 is 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, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. In certain disclosed embodiments, the organic solvent may be further substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=O), 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof. One exemplary ketone is acetone.

[0050] In some embodiments, when X and Y together with the atoms to which they are attached form a cycloaliphatic or cycloheteroaliphatic organic solvent, the organic solvent may be a cyclic ketone. Exemplary cyclic ketones include cyclohexanone, cyclopentanone, and the like.

[0051] In other embodiments, at least one of X or Y is -[C(R 3 )2] m -C(O)-R 4 In the case where the organic solvent is a diketone, exemplary diketones include diacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, acetylacetone, acetonylacetone, and the like, and halogenated forms thereof, such as hexafluoroacetylacetone.

[0052] In further embodiments, at least one of X or Y is -[C(R 3 )2] m -C(O)-R 4 and X and Y, taken together with the atoms to which they are attached, form a cycloaliphatic or cycloheteroaliphatic organic solvent, may be a cyclic diketone. Exemplary cyclic diketones include dimedone, 1,3-cyclohexanedione, and the like.

[0053] In some cases, when X=-CH3, the organic solvent is Y=-C(R 1 ) 3, wherein at least one R 1 is C 2~10 (hydroxylic, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.) Exemplary materials can include methyl propyl ketone, methyl butyl ketone, hydroxyacetone, and the like.

[0054] In other cases, when X=-CH3, the organic solvent is Y=-R 2 wherein at least one R 2 is C2 alkenyl, C3~10 (Aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.) Exemplary materials can include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, and the like.

[0055] In still other cases, when at least one of X or Y is aromatic, or aliphatic-aromatic, or heteroaliphatic-aromatic, the organic solvent may be an aromatic ketone. Exemplary materials include acetophenone, benzophenone, benzylacetone, 1,3-diphenylacetone, cyclopentyl phenyl ketone, and the like.

[0056] In certain embodiments where the organic solvent comprises a ketone, the ketone may be selected from acetone and acetophenone. One or more additional ketones and / or other organic solvents described herein may also be provided.

[0057] Alkanes: In some embodiments, the organic solvent may be an alkane. In certain embodiments, the alkane has the general formula C n H 2n+2 The alkane may be an acyclic branched or unbranched hydrocarbon having the formula: Exemplary 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. Exemplary cyclic hydrocarbons include, but are not limited to, cyclopentane, cyclohexane, and combinations thereof.

[0058] Aromatic Solvents: In some embodiments, the organic solvent may be an aromatic solvent. As used herein, unless otherwise specified, "aromatic" means a cyclic conjugated group or moiety of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings (e.g., naphthyl, indolyl, or pyrazolopyridinyl) in which at least one ring is aromatic, i.e., at least one ring, and optionally multiple fused rings, have a continuous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Huckel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system. In some cases, the aromatic solvent may be selected from toluene and benzene.

[0059] ether: In some embodiments, the organic solvent may be an ether having the formula: XOY or XO-[C(R)2] n -OY Here, n is an integer from 1 to 4, Each X and Y is -[C(R 1 )2] m -C(R 2 )3 or -R 3 or -[C(R 4 )2] p -O-[C(R 5 )2] m -C(R 6 ) 3 may be independently selected from R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and each of R is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; m is an integer from 0 to 10; and p is an integer from 1 to 10; X and Y, together with the atoms to which they are attached, may optionally form a cycloheteroaliphatic group.

[0060] In some embodiments, each R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is 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, 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 combination thereof. In certain disclosed embodiments, the ether may be further 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0061] In some embodiments, when X and Y together with the atoms to which they are in turn attached form a cycloheteroaliphatic group, the organic solvent is a cyclic ether, such as an acetal, dioxane, dioxolane, and the like. In some embodiments, when n=1 and each R=H, X and Y together form a 6-, 7-, 8-, 9-, or 10-membered ring. Exemplary ethers include, but are not limited to, 1,3-dioxolane or a derivative thereof. In other embodiments, when n=2 and R=H, X and Y form a 7-, 8-, 9-, or 10-membered ring. Exemplary ethers include, but are not limited to, 1,4-dioxane or a derivative thereof. In still other embodiments, when n=1 or n=2, R is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary cyclic ethers include tetrahydrofuran, 2-methyltetrahydrofuran, 2-methyl-1,3-dioxolane, and the like.

[0062] In other embodiments, the organic solvent may be an aromatic ether when at least one of X or Y is aromatic. Exemplary aromatic ethers include anisole, diphenyl ether, and the like.

[0063] In some embodiments, when at least one of X or Y is cycloaliphatic, the organic solvent may be a cycloalkyl ether. Exemplary cycloalkyl ethers include cyclopentyl methyl ether, cyclohexyl methyl ether, and the like.

[0064] In other embodiments, at least one of X or Y is -[C(R 4 )2-O] p -C(R 6)3, the organic solvent may be a glycol-based ether. Exemplary glycol-based ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, and the like, including the methyl, ethyl, propyl, and butyl mono- and di-ethers of ethylene glycol, and the like.

[0065] Nitrile: In some cases, the organic solvent is a nitrile having the formula RC≡N, where: R is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic.

[0066] In certain embodiments, R may be optionally substituted with a hydroxyl group (e.g., in one example, R may be CH3-CH(OH)-CH2- and the organic solvent is CH3-CH(OH)-CH2-CN).

[0067] One exemplary nitrile is acetonitrile, discussed above.

[0068] In some embodiments, the organic solvent may comprise two or more of the organic solvents or types of organic solvents described herein. In some embodiments, water may be provided in place of or in addition to the organic solvent.

[0069] Carrier Gas 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.

[0070] Additives The additive may be selected from a number of different types of additives. For example, in some cases, the additive may be a heterocyclic compound, a heteroaromatic compound, a halogen-substituted heteroaromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidizing agent, a bifluoride source, ammonia, an aldehyde, a carbene, an organic acid, and / or a hydrogen fluoride complexing 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 acid-base adduct BF4 - is an example of a Lewis acid that forms. In some cases, the additive may fall into more than one of the categories listed above. In various embodiments, the additive serves the purpose of accelerating the reaction rate and increasing the reaction selectivity.

[0071] Heteroaromatic compounds: In certain embodiments, the additive is a heteroaromatic compound. The term "aromatic" is defined above. A heteroaromatic compound is an aromatic compound that includes a 5-, 6-, or 7-membered ring that includes 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo), unless otherwise specified. Exemplary heteroaromatic compounds that may be used include, but are not limited to, picoline, pyridine, pyrrole, imidazole, thiophene, N-methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicoronic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, and azulene. In some cases, the heteroaromatic compound may be methylated. In some cases, the heteroaromatic compound may follow the Hückel 4n+2 rule. In some cases, the additive is a halogen-substituted aromatic compound. A halogen-substituted aromatic compound is an aromatic compound that contains at least one halogen bonded to an aromatic ring. As used herein, halogen or halo refers to F, Cl, Br or I. Exemplary halogen-substituted aromatic compounds include, but are not limited to, 4-bromopyridine, chlorobenzene, 4-chlorotoluene, fluorobenzene, and the like.

[0072] Heterocyclic Aliphatic Compounds: In some embodiments, the additive is a heterocyclic aliphatic compound. As used herein, "aliphatic" refers to a compound having at least 1 carbon atom and up to 50 carbon atoms (C 1~50 ), e.g., 1 to 25 carbon atoms (C 1~25 ), or 1 to 10 carbon atoms (C 1~10Heterocyclic aliphatic compounds refer to hydrocarbon groups having an alkyl, aryl, or aryl group, including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), including cyclic versions thereof, further including linear and branched chain arrangements, and all stereo- and positional isomers. Heterocyclic aliphatic compounds are aliphatic compounds containing a 5-, 6-, or 7-membered ring that contains 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo), unless otherwise specified. Exemplary heterocyclic aliphatic compounds include pyrrolidine, piperidine, and the like.

[0073] Amine: In some embodiments, the additive is an amine having the formula: NR 1 R 2 R 3 Here, R 1 , R 2 , and R 3 is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; R 1 and R 2 may optionally form a cycloheteroaliphatic ring together with the atom to which each is attached; R 1 , R 2 , and R 3 may optionally form a cycloheteroaliphatic group together with the atom to which they are attached.

[0074] In some embodiments, R 1 , R 2 , and R 3is 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, 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 combination thereof. In certain disclosed embodiments, the amine may be further 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0075] In some embodiments, R 1 , R 2 , and R 3 When at least one of is aliphatic, haloaliphatic, haloheteroaliphatic, or heteroaliphatic, the additive is an alkylamine. The alkylamine can include dialkylamine, trialkylamine, and derivatives thereof. Exemplary alkylamines include dimethylisopropylamine, N-ethyldiisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, t-butylamine, and the like.

[0076] In other embodiments, R1 , R 2 and R 3 If at least one of R contains a hydroxyl, the additive is an alcohol amine. 1 , R 2 and R 3 at least one of which is an aliphatic group substituted with one or more hydroxyls. Exemplary alcohol amines include 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(dipropylamino)ethanol, 2-(dibutylamino)ethanol, N-ethyldiethanolamine, N-tertbutyldiethanolamine, and the like.

[0077] In some embodiments, R 1 and R 2 When each of the groups taken together with the atom to which it is attached forms a cycloheteroaliphatic group, the additive may be a cyclic amine. Exemplary cyclic amines include piperidine, N-alkyl piperidine (e.g., N-methyl piperidine, N-propyl piperidine, etc.), pyrrolidine, N-alkyl pyrrolidine (e.g., N-methyl pyrrolidine, N-propyl pyrrolidine, etc.), morpholine, N-alkyl morpholine (e.g., N-methyl morpholine, N-propyl morpholine, etc.), piperazine, N-alkyl piperazine, N,N-dialkyl piperazine (e.g., 1,4-dimethyl piperazine), and the like.

[0078] In other embodiments, R 1 , R 2 and R 3 When at least one of R comprises an aromatic group, the additive is an aromatic amine. 1 , R 2 and R 3 At least one of R is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. 1 and R 2 In yet another embodiment, both R 1 and R 2 , and optionally R 3taken together with the atom to which each is attached form a cycloheteroaliphatic which is aromatic. Exemplary aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and derivatives thereof.

[0079] In some embodiments, the additive may comprise 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,N dimethylaniline), N-ethyldiisopropylamine, tert-butylamine, and combinations thereof.

[0080] In some embodiments, the additive may include a fluoramine. A fluoramine is an amine having one or more fluorinated substituents. Exemplary fluoramines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0081] In some embodiments, the additive has the formula R 1 NC(NR 2 )-NR 3 Exemplary additives include, but are not limited to, guanidine or its derivatives.

[0082] In some embodiments, the additive may be a relatively low molecular weight amine, for example, an amine having a molecular weight of less than 200 g / mol or 100 g / mol in certain embodiments. In some embodiments, higher molecular weight amines may be used, including those having heterocyclic compounds with long chains and / or aromatic rings.

[0083] amino acid: In some embodiments, the additive may include an amino acid. The amino acid may have the formula: R-CH(NR'2)-COOH wherein each R and R' is independently hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0084] Exemplary amino acids that may be used include, but are not limited to, histidine, alanine and derivatives thereof.

[0085] Organophosphorus compounds: In some embodiments, the additive may include an organophosphorus compound. The organophosphorus compound may be a phosphate ester, a phosphoric acid amide, a phosphonic acid, a phosphinic acid, a phosphinic acid salt, a phosphinic acid ester, a phosphine oxide, a phosphine imide, or a phosphonium salt. Exemplary organophosphorus compounds include phosphoric acid and trialkyl phosphates. In some cases, the organophosphorus compound is a phosphazene. A phosphazene is an organophosphorus compound that includes phosphorus(V) having a double bond between P and N. The phosphazene may have a formula of RN=P(NR2)3, where each of R and R2 is independently selected from hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. In some cases, the phosphazene is a phosphazene having a formula of [X2PN] n where X is a halide, alkoxide, or amide. Other types of phosphazenes may be used if desired.

[0086] Oxidizer: In some embodiments, the additive comprises an oxidizing agent. As used herein, an oxidizing agent is a material that has the ability to oxidize (e.g., accept electrons from) another substance. Exemplary oxidizing agents that may be used include, but are not limited to, hydrogen peroxide, sodium hypochlorite, and tetramethylammonium hydroxide.

[0087] Bifluoride Source: In some embodiments, the additive comprises a bifluoride source. The bifluoride source is bifluoride (HF2 - ) are materials that contain or produce bifluoride. Exemplary bifluoride sources that may be used include, but are not limited to, ammonium fluoride, aqueous HF, gaseous HF, buffered oxide etch mixtures (e.g., mixtures of HF and a buffer 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) reacts with HF2 either before or after delivery to the reaction chamber. - may be formed.

[0088] aldehyde: In some embodiments, the additive comprises an aldehyde having the formula: X-[C(O)]-H where X is hydrogen, -R 1 , -C(R 2 )3, or -[C(R 3 )2] m -C(O)H, each R 1 , R 2 and R 3 is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and m is an integer from 0 to 10.

[0089] In some embodiments, R 1 , R 2 and R 3is 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, heteroalkyl-heteroaryl, heteroalkenyl-heteroaryl, heteroalkynyl-heteroaryl, or any combination thereof. In certain disclosed embodiments, the aldehyde or ketone may be further substituted with one or more substituents, such as aldehyde (-C(O)H), oxo (=O), 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0090] In some embodiments, when X is aromatic, the additive may be an aromatic aldehyde. Exemplary aromatic aldehydes include benzaldehyde, 1-naphthaldehyde, phthalaldehyde, and the like.

[0091] In other embodiments, when X is aliphatic, the additive may be an aliphatic aldehyde. Exemplary aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovalerylaldehyde, and the like.

[0092] In yet other embodiments, X is -[C(R 3 )2] m When X is -C(O)H and m is 0-10, or when X is an aliphatic or heteroaliphatic substituted with -C(O)H, the additive may be a dialdehyde. Exemplary dialdehydes include glyoxal, phthalaldehyde, glutaraldehyde, malondialdehyde, succinaldehyde, and the like.

[0093] In some examples, the aldehyde used as the additive may be selected from the group consisting of acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other cases, the aldehyde used as the additive may be selected from the aldehydes discussed in the aldehydes and organic solvents section discussed in this section.

[0094] Carbene: In some embodiments, the additive comprises a carbene. The carbene may have the formula: X-(C:)-Y where each of X and Y is independently H, halo, -[C(R 1 )2] m -C(R 2 )3, -C(O)-R 1 , or -C(=NR 1 )-R 2 , -NR 1 R 2 , -OR 2 , -SR 2 , or -C(R 2 ) 3, R 1 and R 2 is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof; and m is an integer from 0 to 10; R 1 and R 2may optionally form a cycloheteroaliphatic group together with the atom to which they are attached; X and Y, together with the atoms to which they are each attached, may optionally form a cycloaliphatic or cycloheteroaliphatic group.

[0095] Further, the additive may be of the formula R 1 -C + (R)-R 2 and R, R 1 and R 2 Each of is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0096] In some embodiments, each R, R 1 and R 2is 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, 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 combination thereof. In certain disclosed embodiments, the carbene may be further 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof. In any embodiment of the carbene, R 1 and R 2 Each of may be independently selected.

[0097] In some embodiments, when at least one of X or Y is halo, the additive may be a halocarbene. Exemplary non-limiting halocarbenes include dihalocarbenes, such as dichlorocarbene, difluorocarbene, and the like.

[0098] In some embodiments, both X and Y are -NR 1 R 2 In one example, R 1 and R 2Each of is independently aliphatic. Exemplary diaminocarbenes include bis(diisopropylamino)carbene, and the like.

[0099] In other embodiments, at least one or both of X or Y is -NR 1 R 2 and R in X 1 and R 2 Both or R in Y 1 and R 2 When both of the groups taken together with the nitrogen atom to which they are each attached form a cycloheteroaliphatic group, the additive may be a cyclic diaminocarbene. Exemplary cyclic diaminocarbenes include bis(N-piperidyl)carbene, bis(N-pyrrolidinyl)carbene, and the like.

[0100] In one example, both X and Y are -NR 1 R 2 and R from X 1 R from the group and Y 2 When the groups are taken together with the nitrogen atom to which they are attached to form a cycloheteroaliphatic group, the additive is an N-heterocyclic carbene. Exemplary N-heterocyclic carbenes include imidazol-2-ylidene (e.g., 1,3-dimesityl imidazol-2-ylidene, 1,3-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-ylidene (e.g., 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), triazol-5-ylidene (e.g., 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene), etc.

[0101] In some embodiments, X=-NR 1 R 2 and Y=-SR 2 and R from X 1 R from the group and Y 2When the groups, taken together with the nitrogen atom to which each is attached, form a cycloheteroaliphatic group, the additive is an acyclic thioalkylaminocarbene. Exemplary cyclic thioalkylaminocarbenes include thiazol-2-ylidenes, such as 3-(2,6-diisopropylphenyl)thiazol-2-ylidene.

[0102] In some embodiments, X=-NR 1 R 2 and Y = -C(R 2 )3, and R from X 1 R from the group and Y 2 When the groups, taken together with the atoms to which they are attached, form a cycloheteroaliphatic group, the additive is a cyclic alkylaminocarbene. Exemplary cyclic alkylaminocarbenes include pyrrolidin-2-ylidene (e.g., 1,3,3,5,5-pentamethyl-pyrrolidin-2-ylidene, etc.), piperidin-2-ylidene (e.g., 1,3,3,6,6-pentamethyl-piperidin-2-ylidene, etc.), and the like.

[0103] Further exemplary carbenes and derivatives thereof include compounds having a thiazol-2-ylidene, dihydroimidazol-2-ylidene, imidazol-2-ylidene, triazol-5-ylidene, or cyclopropenylidene moiety. Still other carbenes and carbene analogs include aminothiocarbene compounds, aminooxycarbene compounds, diaminocarbene compounds, heteroaminocarbene compounds, 1,3-dithiolium carbene compounds, mesoionic carbene compounds (e.g., imidazoline-4-ylidene compounds, 1,2,3-triazolylidene compounds, pyrazolinylidene compounds, tetrazol-5-ylidene compounds, isoxazol-4-ylidene compounds, thiazol-5-ylidene compounds, etc.), cyclic alkylaminocarbene compounds, boranylidene compounds, silylene compounds, stannylene compounds, nitrene compounds, phosphinidene compounds, foily carbene compounds, and the like. Further exemplary carbenes include dimethylimidazol-2-ylidene, 1,3-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-diadamantyl imidazole. 1,3,4,5-tetramethylimidazol-2-ylidene, 1,3-dimesitylimidazol-2-ylidene, 1,3-dimesitylimidazol-2-ylidene, 1,3,5-triphenyltriazol-5-ylidene, bis(diisopropylamino)cyclopropenylidene, bis(9-anthryl)carbene, norbornene-7-ylidene, dihydroimidazol-2-ylidene, and methylidenecarbene.

[0104] Organic acids: In some embodiments, the additive comprises an organic acid. The organic acid may have the formula R-CO2H, where R is selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination 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 combination thereof. In certain disclosed embodiments, R may be further 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 functionalized at the nitrogen atom with an aliphatic or aryl group), alkyl halide, or any combination thereof. In certain implementations, the organic acid may be selected from formic acid and acetic acid.

[0105] Hydrogen Fluoride Complexing Chemicals In some embodiments, the additive comprises a chemical that forms a complex with hydrogen fluoride. Such chemicals are referred to herein as hydrogen fluoride complexing chemicals. The complexes formed can act to increase the rate at which target materials are etched from a substrate while maintaining a high degree of selectivity.

[0106] In various embodiments herein, the hydrogen fluoride complexing chemical may be provided in combination with hydrogen fluoride. In such embodiments, the additive comprises a hydrogen fluoride complexing chemical and the halogen source comprises hydrogen fluoride. These may be combined with any of the organic solvents and / or water described herein, and any of the carrier gases. In related embodiments, the hydrogen fluoride complexing chemical may be used in combination with a halogen source other than hydrogen fluoride.

[0107] The hydrogen fluoride complexing chemical may have a variety of different formulas and / or properties. For example, in various implementations, the hydrogen fluoride complexing chemical may be or may include one or more amine groups, urea groups, phosphine groups, alkyl groups, imidazole groups, heteroaliphatic groups, heteroaromatic groups, ether groups, etc. In various embodiments, the hydrogen fluoride complexing chemical may include two or more specific 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. Many additives include more than one type of group (e.g., an imidazole group and one or more alkyl groups, etc.). Such groups may be combined in various ways, including but not limited to the specific examples shown below.

[0108] Examples of hydrogen fluoride complexing chemicals that may be used as additives include, but are not limited to, cyclic ureas or other urea-containing compounds such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (also referred to as N,N'-dimethylpropyleneurea or DMPU), alkyl-substituted ammonium compounds such as tetraethylammonium and tetrabutylammonium, heteroaromatic amine-containing compounds such as melamine, heteroaliphatic or cyclic ether compounds such as tetrahydrofuran, alkyl-substituted imidazole compounds such as dialkylimidazolium, alkyl-substituted ether compounds such as dimethyl ether, alkyl-substituted phosphine compounds such as trialkylphosphines, and combinations thereof. A variety of compounds may complex with HF in a similar manner and may be used in the same or similar manner.

[0109] Other examples of additives that may act as hydrogen fluoride complexing chemicals include, but are not limited to, pyridine and triethylamine, which may be used in some embodiments. In other embodiments, the hydrogen fluoride complexing chemicals may exclude pyridine and / or triethylamine.

[0110] Replace with: Any of the exemplary materials described herein include unsubstituted and / or substituted forms of the compounds. Non-limiting exemplary substituents include, for example, one, two, three, four, or more substituents independently selected from the group consisting of: (1) C 1~6 Alkoxy (e.g., -OR (wherein R is C 1~6 alkyl) (2) C 1~6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1~6 alkyl) (3) C 1~6 Alkylsulfonyl (e.g., -SO-R, where R is C 1~6 alkyl) (4) Amines (e.g., -C(O)NR 1 R 2 or -NHCOR 1 (In the formula, R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 which, together with the nitrogen atom to which they are attached, form a heterocyclyl group, as defined herein; (5) aryl, (6) Arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3), (9) cyano (e.g., -CN), (10) Aldehydes (e.g., -C(O)H), (11) C 3~8 Cycloalkyl, (12) Halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein); (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein); (15) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein); (16) Hydroxyl (e.g., -OH), (17) N-protected amino, (18) Nitro (e.g., -NO2), (19) oxo (e.g., ═O), (20)C 1~6 Thioalkoxy (e.g., -SR, where R is C 1~6 alkyl) (21) Thiol (e.g., -SH), (22)-CO2R 1 (In the formula, R 1 is (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl))) (23)-C(O)NR 1 R 2 (In the formula, R 1 and R 2 each of which is independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 Aryl) (24)-SO2R 1 (In the formula, R 1 (a)C 1~6 Alkyl, (b) C 4~18 aryl, and (c) C 1~6 Alkyl-C 4~18 aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl))) (25)-SO2NR 1 R 2 (In the formula, R 1 and R 2 each of which is independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), and (26)-NR 1 R 2(In the formula, R 1 and R 2 each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1~6 Alkyl, (d) C 2~6 alkenyl, (e) C 2~6 Alkynyl, (f) C 4~18 Aryl, (g) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 (h) C 3~8 cycloalkyl, and (i) C 1~6 Alkyl-C 3~8 Cycloalkyl (e.g., -LR, where L is C 1~6 alkyl and R is C 3~8 cycloalkyl) In one embodiment, the two groups are not attached to the nitrogen atom through a carbonyl or sulfonyl group.

[0111] In certain embodiments, the additive acts as a proton acceptor and HF - In some such cases, HF2 - may actively etch one or more materials on the substrate, such as an oxide material or another material.

[0112] etching Vapor phase species delivered to the reaction chamber may be collectively referred to as a gas mixture. Non-inert species (e.g., reactants other than the carrier gas) delivered to the reaction chamber 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. For example, hydrogen fluoride or other halogen source may be provided in the reactant mixture at a concentration of about 20-100% (by volume), or about 20-99% (by volume). In these or other cases, hydrogen fluoride or other halogen source may be provided in the gas mixture at a concentration of about 0.5-20% (by volume). Organic solvent and / or water may be provided in the reactant mixture at a concentration of about 10-100% (by volume), or about 10-99% (by volume). In these or other cases, organic solvent and / or water may be provided in the gas mixture at a concentration of about 0-10% (by volume). The additive may be provided in the reactant mixture at a concentration of about 0.2-5% (by volume). In these or other cases, the additive may be provided in the gas mixture at a concentration of about 0-0.2%, or about 0.0001-0.2% (by volume). The carrier gas may be provided in the gas mixture at a concentration of about 0-99% (by volume).

[0113] In some embodiments, the additive and organic solvent and / or water are mixed such that the additive is about 0.1-5% (by weight) of the additive / organic solvent and / or water mixture. The reactant mixture may be characterized by the additive being about 0.1-5% (by weight) of the sum of the amounts of additive and organic solvent and / or water, regardless of the mixing order.

[0114] In the same or alternative embodiments, the reactant mixture may be characterized by the halogen source:additive ratio (by volume). As described further below, in some embodiments, the selectivity may be adjusted by the halogen source:additive volume ratio, with the selectivity increasing as the amount of additive increases (and thus the ratio decreases). In some embodiments, the halogen source:additive ratio is 10 or less. In some embodiments, the halogen source:additive ratio is greater than 10.

[0115] According to various embodiments, the reactant mixture may include a halogen source, an alcohol, and an amine, where the amine is 0.1-5% wt of the total amount of the alcohol and amine. In some embodiments, the volume ratio of the halogen source:amine is 10 or less. In other embodiments, the volume ratio of the halogen source:amine is 10 or more. In some embodiments, the amine is pyridine. In some embodiments, the alcohol is isopropyl alcohol. In some embodiments, the halogen source is HF.

[0116] As mentioned above, according to various implementations, the etch may be selective to one material on the substrate relative to another material, while in other implementations, the etch may be non-selective to multiple materials on the substrate.

[0117] In some embodiments, oxides are selectively etched relative to one or more of nitrides and epitaxial materials such as Si and SiGe. The etch selectivity of the reactant mixture relative to silicon oxide may be adjusted by the amount of additive in the mixture. For example, very high (at least 50:1) etch selectivity of silicon oxide relative to silicon nitride is achieved with a reactant mixture of halogen source:additive (e.g., HF:pyridine) of 10 or less. The etch selectivity decreases as the ratio increases, such that no selectivity is observed in the absence of additive. A similar effect may be observed with the etch selectivity of silicon oxide relative to Si and SiGe.

[0118] In some embodiments, the low-k material is selectively etched relative to the barrier material, for example, a carbon-doped silicon oxide material may be selectively etched relative to a barrier material such as a titanium nitride layer.

[0119] Examples of target materials, second materials, and etching chemistries for achieving selective or non-selective etching of the target material relative to the second material are listed in the table below. The ratio in parentheses indicates the approximate etch rate of the target material relative to the second material. [Table 1]

[0120] FIG. 1 illustrates a flow chart of a method for etching a substrate according to various embodiments herein. The method begins with operation 101, in which a substrate is provided to a reaction chamber. The substrate includes one or more materials thereon to be removed. Exemplary materials are listed above. In operation 103, a gas mixture is flowed into the reaction chamber. The gas mixture may have a composition and other properties as described herein. Similarly, one or more process variables, such as pressure, temperature, absolute and relative flow rates, may be controlled as described herein. In operation 105, the substrate is exposed to the gas mixture, and one or more of the materials on the substrate are etched as a result of such exposure. These operations may overlap in time.

[0121] In some examples, the gas mixture is prepared by first creating a mixture of (1) the additive, and (2) an organic solvent and / or water. The mixture of the additive and the organic solvent and / or water may be added to a carrier gas, and then hydrogen fluoride gas or other halogen source may be added. In other examples, hydrogen fluoride or other halogen source gas, a carrier gas, and an alcohol may be mixed together to form a gas stream, and then the additive is added to the gas stream. A variety of mixing schemes are possible and are all considered to be within the scope of the disclosed embodiments.

[0122] In some implementations, one or more process variables may be controlled during etching. For example, the pressure in the reaction chamber may be controlled at about 10 Torr or less, such as about 0.2-10 Torr in some embodiments. The temperature in the reaction chamber may be controlled, for example, by controlling the temperature of the 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 the showerhead used to deliver the gas mixture into the reaction chamber. In some embodiments, the temperature of one or more of the reaction chamber, substrate support, and showerhead may be controlled during etching, for example, at a temperature of about 20-500° C. In some embodiments, the temperature of one or more of these elements may cycle between two or more different temperatures. An example is discussed further below in the context of FIGS. 2-4. In some embodiments, the duration for which the substrate is exposed to the gas mixture may be controlled. For example, this duration may be about 0-10 minutes. In some cases, the duration of exposure to the gas mixture can control the extent to which material on the substrate is etched. In other cases, the etching process is self-limiting, such that additional periods of exposure do not lead to additional etching of the target material. One such example is considered in the context of Figs.

[0123] Figure 2 is a flow chart illustrating a cyclic etching method that may be used in some embodiments. Figures 3A-3C show a partially fabricated semiconductor substrate as it undergoes the processing method of Figure 2. Figure 4 illustrates how temperature can be controlled during the method of Figure 2 in certain embodiments. For clarity, these figures are described with reference to each other.

[0124] The method of Figure 2 begins with operation 201 where a substrate 301 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 relative to other materials present on the substrate. In the particular example shown in Figure 3A, the substrate 301 includes a silicon fin 302 and an exposed spacer layer (not shown) that includes a spacer material such as SiN, SiCN, SiCO, or SiCON. In this example, it is desired to trim the fin to be smaller.

[0125] Next, in operation 203, a first reactant or first gas mixture is flowed into the reaction chamber. The first reactant or first gas mixture includes one or more species that act to modify one or more materials present on the surface of the substrate 301. In some cases, the modification includes the formation of an oxide material. In these or other cases, the modification includes fluorination of the exposed material, adsorption of organic molecules to the exposed material, and the like. A variety of surface modifications are available. In the context of the embodiment shown in FIGS. 3A-3C, the first reactant or first gas mixture includes an oxidizing species (e.g., O2, or other oxidizing species) that acts to modify the silicon fin 302 to form silicon oxide 303, as described below. In many embodiments, the first reactant or first gas mixture may selectively modify one or more of the materials on the substrate 301 relative to other materials on the substrate 301. For example, in the context of Figures 3A-3C, oxygen provided to the reaction chamber selectively modifies the silicon fins 302 with substantially less (or no) modification occurring to other materials, such as the spacer material.

[0126] In operation 205, the substrate 301 is exposed to a first reactant or a first gas mixture to modify one or more of the materials on the surface of the substrate 301. In the embodiment of Figures 3A-3C, exposure to the first reactant or first gas mixture modifies the exposed surface of the silicon fin 302 to form a thin layer of silicon oxide 303, as shown in Figure 3B.

[0127] In operation 207, a second gas mixture is provided to the reaction chamber. The second gas mixture may have a composition and properties as described herein. For example, it may include (1) HF or other halogen source, (2) one or more organic solvents and / or water, (3) one or more additives as described above, and (4) a carrier gas.

[0128] In operation 209, the substrate 301 is exposed to a second gas mixture to etch away the modified material formed in operation 205 (e.g., silicon oxide 303 in FIG. 3B). If the substrate 301 includes more than one material exposed, the modified material formed in operation 205 may be selectively etched away relative to other materials, such as the spacer material. At this point, the portion of the material targeted for removal is modified and then removed from the substrate 301. In the context of FIGS. 3A-3C, this means that the silicon fin 302 is now smaller / narrower than before, as shown in FIG. 3C.

[0129] Next, in 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 removed, etc. If it is determined that a sufficient amount of material has been removed from the substrate 301, the method is complete. If not, the method repeats starting with operation 203. The surface modification and etching steps are repeated with each other until it is determined that a sufficient amount of material has been removed from the substrate 301.

[0130] Figure 4 illustrates how the temperature within a reaction chamber may be controlled over time when performing cyclic etching techniques such as those described in Figures 2 and 3A-3C. Although Figure 4 is described in the context of Figures 2 and 3A-3C, it will be understood that the embodiments are not so limited and that the temperature control described in Figure 4 may be used in many different contexts, including those utilizing other structures and / or other materials.

[0131] The temperature may be controlled using a number of techniques, which may be combined as desired, for example, by controlling the temperature of the substrate support, showerhead, reaction chamber walls, process gases, etc. The process sequence of FIG. 4 begins at time t0, where a substrate is introduced into the reaction chamber, as described in operation 201 of FIG. 2. The substrate includes one or more materials to be removed or otherwise etched. For example, in the example of FIGS. 3A-3C, substrate 301 includes silicon fin 302 to be trimmed, as shown in FIG. 3A. At time t0, the temperature is at an initial starting temperature of T0. Between times t0 and t1, the temperature increases from T0 to T2, as shown in FIG. 4. Because the temperature is increasing, this period may be referred to as the ramp-up period. Between times t1 and t2, the temperature is maintained at T2. This period may be referred to as the modification period. During the modification period, the substrate is exposed to a first reactant or first gas mixture, as described in operations 203 and 205 of FIG. 2, thereby modifying one or more materials on the substrate. In some cases, the first reactant or first gas mixture may begin flowing into the reaction chamber at or shortly after time t1, while in other cases, the first reactant or first gas mixture may begin flowing into the reaction chamber at a time between times t0 and t1. In the example of Figures 3A-3C, during the modification period, exposed portions of silicon fin 302 are converted to silicon oxide 303, as shown in Figure 3B.

[0132] Returning to FIG. 4, between times t2 and t3, the temperature is decreased from T2 to T1. T1 may be greater than T0, as shown. In other cases, T1 may be equal to or less than T0. The period between times t2 and t3 may be referred to as a cool down period, since the temperature is decreasing. Between times t3 and t4, the temperature is maintained at T1. This period may be referred to as a steam etch period. During the steam etch period, the substrate is exposed to a second gas mixture, as described in operations 207 and 209 of FIG. 2, thereby etching some or all of the modified material on the substrate surface. In some cases, the second gas mixture may begin to flow into the reaction chamber at or shortly after time t3, while in other cases, the second gas mixture may begin to flow into the reaction chamber at a time between times t2 and t3. In the context of FIGS. 3A-3C, the silicon oxide 303 may be partially or entirely removed during the steam etch period. After the steam etch period, the substrate 301 may be as shown in FIG. 3C. By time t3, at least a portion of the material targeted for removal (e.g., silicon fin 302 in FIGS. 3A-3C) has been removed. However, further etching may be desired. Thus, at time t4, it is determined whether the etching is sufficiently complete, as described in operation 211 of FIG. 2. If the etching is sufficiently complete, the process sequence is complete and the substrate may be removed from the reaction chamber (not shown in FIG. 4). If the etching is not yet sufficiently complete, the method may iteratively return to the previous stage, as indicated by arrow 400. At this point, the temperature is raised to T2 in a second ramp-up period, followed by a second reforming period, a second cooling period, and a second steam etch period. The ramp-up period, reforming period, cooling period, and steam etch period may be repeated as desired until the etching is sufficiently complete.

[0133] As shown in FIG. 4, when a cyclic etching technique is used, the temperature may cycle between two or more different settings. In some embodiments, the temperature during the modification period (e.g., T2) may be about 100-500° C., while the temperature during the steam etching period (e.g., T1) may be about 20-200° C. In various implementations, the substrate is not exposed to plasma during any of the periods described in FIG. 4. In such embodiments, both the reactions occurring during the modification period and the reactions occurring during the steam etching period are driven by thermal energy.

[0134] The etching operations described in Figures 2-4 may be performed in a self-limiting manner. For example, the second gas mixture provided during the steam etching period may selectively etch the modified material formed during the modification period. Once the modified material is consumed, the etching rate may substantially decrease or even stop as a result of the selective nature of the etching process. Thus, the etching process may be considered to be self-limiting in certain embodiments. Additionally, as described above, the etching process may selectively target the material to be removed without substantially removing other materials present on the substrate, such as the spacer material or other materials not targeted for etching. In some cases, the material targeted for removal may be etched with a selectivity of at least about 2:1 compared to another material on the substrate, such as the spacer material. As used herein, an etching process having a selectivity of at least about 2:1 is considered to be selective. In some embodiments, the selectivity may be at least about 1000:1.

[0135] Additional definitions This section provides additional definitions that may be used herein. Some of the material described in this section may overlap with material provided elsewhere in this application.

[0136] The terms "acyl" or "alkanoyl," as used interchangeably herein, refer to radicals of 1, 2, 3, 4, 5, 6, 7, 8 or more carbon atoms of a straight chain, branched, cyclic configuration, saturated, unsaturated, and aromatic, and combinations thereof, attached to the parent molecular group by a carbonyl group, as defined herein, or hydrogen. This radical is exemplified by formyl, acetyl, propionyl, isobutyryl, butanoyl, and the like. In some embodiments, the acyl or alkanoyl group is -C(O)-R, where R is hydrogen, an aliphatic group, or an aromatic group, as defined herein.

[0137] "Acyl halide" means -C(O)X, where X is a halogen, such as Br, F, I, or Cl.

[0138] "Aldehyde" means a -C(O)H group.

[0139] "Aliphatic" refers to a group of amino acids having at least 1 carbon atom and at least 50 carbon atoms (C 1~50 ), e.g., 1 to 25 carbon atoms (C 1~25 ), or 1 to 10 carbon atoms (C 1~10 ), including alkanes (or alkyls), alkenes (or alkenyls), and alkynes (or alkynyls), including cyclic versions thereof, and further including straight-chain and branched-chain arrangements, and all stereo- and positional isomers.

[0140] "Alkyl-aryl", "alkenyl-aryl", and "alkynyl-aryl" refer to an aryl group, as defined herein, that is or may be linked (or bonded) to a parent molecular group via an alkyl, alkenyl, or alkynyl group, as defined herein, respectively. The alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted or unsubstituted. For example, the alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted with one or more substituents described herein for alkyl, alkenyl, alkynyl, and / or aryl. Exemplary unsubstituted alkyl-aryl groups are those containing 7 to 16 carbon atoms (C 7~16 alkyl-aryl), and those having an alkyl group having 1 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 1~6 Alkyl-C 4~18 Exemplary unsubstituted alkenyl-aryl groups are those containing 7 to 16 carbon atoms (C 7~16 alkenyl-aryl), and those having an alkenyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2~6 Alkenyl-C 4~18 Exemplary unsubstituted alkynyl-aryl groups are those containing 7 to 16 carbon atoms (C 7~16 alkynyl-aryl), and those having an alkynyl group with 2 to 6 carbon atoms and an aryl group with 4 to 18 carbon atoms (i.e., C 2~6 Alkynyl-C 4~18 In some embodiments, the alkyl-aryl group is -LR, where L is an alkyl group as defined herein and R is an aryl group as defined herein. In some embodiments, the alkenyl-aryl group is -LR, where 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 -LR, where L is an alkynyl group as defined herein and R is an aryl group as defined herein.

[0141] "Alkenyl" refers to an alkyl group having at least 2 carbon atoms and at least 50 carbon atoms (C 2~50 ), e.g., 2 to 25 carbon atoms (C 2~25 ), or 2 to 10 carbon atoms (C 2~10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon double bond, where the unsaturated monovalent hydrocarbon may be derived from removing one hydrogen atom from one carbon atom of a parent alkene. An alkenyl group may be branched, straight chain, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls include optionally substituted C 2~24 Including alkyl groups. Alkenyl groups can be made monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkenyl groups can also be substituted or unsubstituted. For example, alkenyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0142] "Alkyl-heteroaryl" means a heteroaryl group, as defined herein, attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the alkyl-heteroaryl group is -LR, where L is an alkyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0143] "Alkyl-heterocyclyl", "alkenyl-heterocyclyl" and "alkynyl-heterocyclyl" refer to a heterocyclyl group, as defined herein, that is or may be linked (or bonded) to a parent molecular group via an alkyl, alkenyl or alkynyl group, as defined herein, respectively. The alkyl-heterocyclyl, alkenyl-heterocyclyl and / or alkynyl-heterocyclyl groups may be substituted or unsubstituted. For example, the alkyl-heterocyclyl, alkenyl-heterocyclyl and / or alkynyl-heterocyclyl groups may be substituted with one or more substituents, as described herein for alkyl, alkenyl, alkynyl and / or heterocyclyl. Exemplary unsubstituted alkyl-heterocyclyl groups are those containing 2 to 16 carbon atoms (C 2~16 alkyl-heterocyclyl), and those having an alkyl group having 1 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 1~6 Alkyl-C 1~18 Exemplary unsubstituted alkenyl-heterocyclyl groups are those containing 3 to 16 carbon atoms (C 3~16 alkenyl-heterocyclyl), and those having an alkenyl group having 2 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 2~6 Alkenyl-C 1~18 Exemplary unsubstituted alkynyl-heterocyclyl groups are those containing 3 to 16 carbon atoms (C 3~16 alkynyl-heterocyclyl), and those having an alkynyl group having 2 to 6 carbon atoms and a heterocyclyl group having 1 to 18 carbon atoms (i.e., C 2~6 Alkynyl-C 1~18In some embodiments, the alkyl-heterocyclyl group is -LR, where 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 -LR, where 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 -LR, where L is an alkynyl group as defined herein and R is a heterocyclyl group as defined herein.

[0144] "Alkoxy" means -OR, where R is an optionally substituted aliphatic group as described herein. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, sec-butoxy, n-pentoxy, trihaloalkoxy, such as trifluoromethoxy, and the like. Alkoxy groups may be substituted or unsubstituted. For example, alkoxy groups may be substituted with one or more of the substituents described herein for alkyl. Exemplary unsubstituted alkoxy groups include C 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 , or C 1~24 Examples of the alkyl group include alkoxy groups.

[0145] "Alkyl" refers to an alkyl group having at least 1 carbon atom and at least 50 carbon atoms (C 1~50 ), e.g., 1 to 25 carbon atoms (C 1~25 ), or 1 to 10 carbon atoms (C 1~10), where the saturated monovalent hydrocarbon may be derived from removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). The alkyl group may be branched, straight chain, or cyclic (e.g., cycloalkyl). Exemplary alkyls include branched or unbranched saturated hydrocarbon groups having 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 may also be substituted or unsubstituted. The alkyl group may be made monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form an appropriate bond to the parent molecular group or between the parent molecular group and another substituent. For example, an alkyl group may be substituted with one, two, three, or, in the case of alkyl groups having two or more carbon atoms, four substituents independently selected from the group consisting of: (1) C 1~6 Alkoxy (e.g., -OR (wherein R is C 1~6 alkyl) (2) C 1~6 Alkylsulfinyl (e.g., -S(O)-R, where R is C 1~6 alkyl) (3) C 1~6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1~6 alkyl) (4) Amines (e.g., -C(O)NR 1 R 2 or -NHCOR 1 (In the formula, R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 which, together with the nitrogen atom to which they are attached, form a heterocyclyl group, as defined herein; (5) aryl, (6) Arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aryloyl (e.g., -C(O)-R, where R is aryl); (8) azides (e.g. -N3), (9) cyano (e.g. -CN), (10) Aldehydes (e.g., -C(O)H), (11) C 3~8 Cycloalkyl, (12) Halo, (13) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing, e.g., 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein); (14) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein); (15) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein); (16) Hydroxyl (e.g. -OH), (17) N-protected amino, (18) Nitro (e.g. -NO2), (19) oxo (e.g. =O), (20)C 1~6 thioalkoxy (e.g., -SR, where R is alkyl); (21) Thiols (e.g., -SH), (22)-CO2R 1 (In the formula, R 1 is (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl) (23)-C(O)NR 1 R 2 (In the formula, R 1 and R2 each of which is independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (24)-SO2R 1 (In the formula, R 1 (a)C 1~6 Alkyl, (b) C 4~18 aryl, and (c) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (25)-SO2NR 1 R 2 (In the formula, R 1 and R 2 each of which is independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), and (26)-NR 1 R 2 (In the formula, R 1 and R 2 each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1~6 Alkyl, (d) C 2~6 alkenyl, (e) C 2~6 Alkynyl, (f) C 4~18 Aryl, (g) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 (h) C 3~8cycloalkyl, and (i) C 1~6 Alkyl-C 3~8 Cycloalkyl (e.g., -LR, where L is C 1~6 alkyl and R is C 3~8 (cycloalkyl). In one embodiment, the two groups are not attached to the nitrogen atom via a carbonyl or sulfonyl group. The alkyl group may 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 1~3 , C 1~6 , C 1~12 , C 1~16 , C 1~18 , C 1~20 or C 1~24 It is an alkyl group.

[0146] "Alkylsulfinyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through an -S(O)- group. In some embodiments, an unsubstituted alkylsulfinyl group is 1~6 or C 1~12 In another embodiment, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group, as defined herein.

[0147] "Alkylsulfonyl" refers to an alkyl group, as defined herein, attached to the parent molecular group through a -SO- group. In some embodiments, an unsubstituted alkylsulfonyl group is 1~6 or C 1~12 In other embodiments, the alkylsulfonyl group is -SO-R, where R is an optionally substituted alkyl (e.g., optionally substituted C as described herein). 1~12 alkyl, haloalkyl, or perfluoroalkyl).

[0148] "Alkynyl" refers to an alkyl group having at least 2 carbon atoms and at least 50 carbon atoms (C 2~50), e.g., 2 to 25 carbon atoms (C 2~25 ), or 2 to 10 carbon atoms (C 2~10 ), and an unsaturated monovalent hydrocarbon having at least one carbon-carbon triple bond, where 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). Exemplary alkynyls include optionally substituted C 2~24 Alkyl groups are included. Alkynyl groups may be cyclic or acyclic, and are exemplified by ethynyl, 1-propynyl, and the like. Alkynyl groups can be made monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecular group or between the parent molecular group and another substituent. Alkynyl groups can also be substituted or unsubstituted. For example, alkynyl groups can be substituted with one or more of the substituents described herein for alkyl.

[0149] "Amide" is -C(O)NR 1 R 2 or -NHCOR 1 (wherein R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 together with the nitrogen atom to which they are attached form a heterocyclyl group, as defined herein.

[0150] "Amine" is -NR 1 R 2 (wherein R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2together with the nitrogen atom to which they are attached form a heterocyclyl group, as defined herein.

[0151] "Aminoalkyl" means an alkyl group, as defined herein, substituted with an amine group, as defined herein. In some embodiments, the aminoalkyl group is -L-NR 1 R 2 where L is an alkyl group as defined herein and R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein. In other embodiments, the aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 where L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 together with the nitrogen atom to which each is attached form a heterocyclyl group, as defined herein; R 3 and R 4 Each of is independently H or alkyl as defined herein.

[0152] "Aromatic" means, unless otherwise specified, a cyclic conjugated group or moiety of 5 to 15 ring atoms having a single ring (e.g., phenyl) or multiple fused rings in which at least one ring is aromatic (e.g., naphthyl, indolyl, or pyrazolopyridinyl), i.e., at least one ring, and optionally multiple fused rings, have a contiguous delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Huckel's rule (4n+2). The point of attachment to the parent structure is typically through the aromatic portion of the fused ring system.

[0153] "Aryl" refers to an alkyl group having at least 5 carbon atoms and at least 15 carbon atoms (C 5~15 ), e.g., 5 to 10 carbon atoms (C 5~10 ), meaning an aromatic carbocyclic group having a single ring or multiple fused rings, which may or may not be aromatic, provided that the point of attachment to the remainder of the compounds disclosed herein is through an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, such as aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term aryl also includes heteroaryl, which is defined as a group containing an aromatic group with at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term non-heteroaryl, which is also included in the term aryl, defines a group containing an aromatic group that does not contain a heteroatom. The aryl group may be substituted or unsubstituted. The aryl group may be substituted with 1, 2, 3, 4, or 5 substituents independently selected from the group consisting of: (1) C 1~6 Alkanoyl (e.g., -C(O)-R, where R is C 1~6 alkyl) (2) C 1~6 Alkyl, (3) C 1~6Alkoxy (e.g., -OR (wherein R is C 1~6 alkyl) (4) C 1~6 Alkoxy-C 1~6 Alkyl (e.g., -LOR, where L and R are each independently C 1~6 alkyl) (5) C 1~6 Alkyl sulfinyl (e.g. -S(O)-R (R is C 1~6 alkyl) (6) C 1~6 Alkylsulfinyl-C 1~6 Alkyl (e.g., -LS(O)-R, where L and R are each independently C 1~6 alkyl) (7) C 1~6 Alkylsulfonyl (e.g., -SO2-R, where R is C 1~6 alkyl) (8) C 1~6 Alkylsulfonyl-C 1~6 Alkyl (e.g., -L-SO2-R, where L and R are each independently C 1~6 alkyl) (9) aryl, (10) Amines (e.g., -NR 1 R 2 (In the formula, R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a heterocyclyl group, as defined herein); (11) C 1~6 Aminoalkyl (e.g. -L 1 -NR 1 R 2 or -L 2 -C(NR 1 R 2 )(R 3 )-R 4 (In the formula, L 1 is C1~6 is alkyl, and L 2 is a covalent bond or C 1~6 is alkyl, R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 may be taken together with the nitrogen atom to which they are attached to form a heterocyclyl group as defined herein; R 3 and R 4 Each of is independently H or C 1~6 alkyl) (12) heteroaryl, (13) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl) (14) aryloyl (e.g., -C(O)-R, where R is aryl); (15) azides (e.g. -N3), (16) cyano (e.g. -CN), (17) C 1~6 Azidoalkyl (e.g., -L-N3, where L is C 1~6 alkyl) (18) Aldehydes (e.g., -C(O)H), (19) Aldehyde-C 1~6 Alkyl (e.g., -LC(O)H, where L is C 1~6 alkyl) (20)C 3~8 Cycloalkyl, (21)C 1~6 Alkyl-C 3~8 Cycloalkyl (e.g., -LR, where L is C 1~6 alkyl and R is C 3~8 cycloalkyl) (22) Halo, (23)C 1~6 Haloalkyl (e.g. -L1 -X or -L 2 -C(X)(R 1 )-R 2 (In the formula, L 1 is C 1~6 is alkyl, and L 2 is a covalent bond or C 1~6 alkyl, X is fluoro, bromo, chloro or iodo, R 1 and R 2 Each of is independently H or C 1~6 alkyl) (24) heterocyclyl (e.g., a 5-, 6-, or 7-membered ring containing, e.g., 1, 2, 3, or 4 non-carbon heteroatoms, as defined herein); (25) heterocyclyloxy (e.g., -OR, where R is heterocyclyl as defined herein); (26) heterocyclyl (e.g., -C(O)-R, where R is heterocyclyl as defined herein); (27) Hydroxyl (-OH), (28)C 1~6 Hydroxyalkyl (e.g. -L 1 -OH or -L 2 -C(OH)(R 1 )-R 2 (In the formula, L 1 is C 1~6 is alkyl, and L 2 is a covalent bond or alkyl, and R 1 and R 2 Each of is independently H or C as defined herein. 1~6 alkyl) (29) Nitro, (30)C 1~6 Nitroalkyl (e.g. -L 1 -NO or -L 2 -C(NO)(R 1 )-R 2 (In the formula, L 1 is C 1~6 is alkyl, and L 2 is a covalent bond or alkyl, and R 1 and R 2Each of is independently H or C as defined herein. 1~6 alkyl) (31) N-protected amino, (32) N-Protected Amino-C 1~6 Alkyl, (33) oxo (e.g. =O), (34)C 1~6 Thioalkoxy (e.g., -SR, where R is C 1~6 alkyl) (35) Thio-C 1~6 Alkoxy-C 1~6 Alkyl (e.g., -LSR, where each of L and R is independently C 1~6 alkyl) (36)-(CH2) r CO2R 1 (In the formula, r is an integer of 0 to 4, and R 1 is (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (37)-(CH2) r CONR 1 R 2 (In the formula, r is an integer of 0 to 4, and each R 1 and R 2 are independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl- (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (38)-(CH2) r SO2R 1 (In the formula, r is an integer of 0 to 4, and R 1 (a)C 1~6 Alkyl, (b) C 4~18aryl, and (c) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (39)-(CH2) r SO2NR 1 R 2 (In the formula, r is an integer of 0 to 4, and R 1 and R 2 each of which is independently (a) hydrogen, (b) C 1~6 Alkyl, (c) C 4~18 aryl, and (d) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 aryl), (40)-(CH2) r NR 1 R 2 (In the formula, r is an integer of 0 to 4, and R 1 and R 2 each of which is independently (a) hydrogen, (b) an N-protecting group, (c) C 1~6 Alkyl, (d) C 2~6 alkenyl, (e) C 2~6 Alkynyl, (f) C 4~18 Aryl, (g) C 1~6 Alkyl-C 4~18 Aryl (e.g., -LR, where L is C 1~6 alkyl and R is C 4~18 (h) C 3~8 cycloalkyl, and (i) C 1~6 Alkyl-C 3~8 Cycloalkyl (e.g., -LR, where L is C 1~6 alkyl and R is C 3~8 cycloalkyl), in one embodiment the two groups are not attached to the nitrogen atom via a carbonyl or sulfonyl group; (41) Thiols (e.g., -SH), (42) Perfluoroalkyl (e.g. -(CF2) n CF3 (wherein n is an integer from 0 to 10), (43) Perfluoroalkoxy (e.g. -O-(CF2) n CF3 (wherein n is an integer from 0 to 10), (44) Aryloxy (e.g. -OR, where R is aryl); (45) cycloalkoxy (e.g. -OR, where R is cycloalkyl); (46) cycloalkylalkoxy (e.g., -OLR, where L is alkyl and R is cycloalkyl), and (47) Arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is 4~18 , C 4~14 , C 4~12 , C 4~10 , C 6~18 , C 6~14 , C 6~12 , or C 6~10 It is an aryl group.

[0154] "Arylalkoxy" means an alkylaryl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the arylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is an aryl group, as defined herein.

[0155] "Aryloxy" refers to -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, an unsubstituted aryloxy group is 4~18 or C 6~18 It is an aryloxy group.

[0156] "Aryloyl" refers to an aryl group that is attached to the parent molecular group through a carbonyl group. In some embodiments, an unsubstituted aryloyl group is 7~11 Aryloyl or C 5~19In another embodiment, the aryloyl group is -C(O)-R, where R is an aryl group, as defined herein.

[0157] "Azido" refers to the -N3 group.

[0158] "Azidoalkyl" refers to an azido group attached to the parent molecular group via an alkyl group, as defined herein. In some embodiments, the azidoalkyl group is -L-N3, where L is an alkyl group, as defined herein. "Azo" refers to a -N=N- group.

[0159] "Carbene" refers to a carbon having HC and two non-bonding electrons or a derivative thereof having (C). In some embodiments, a carbene is R 1 R 2 (C:)(wherein, R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 each taken together with the atom to which it is attached forms a cycloaliphatic group, as defined herein.

[0160] "Carbenium cation" is H3C + and carbon with a +1 formal charge, or C + In some embodiments, the carbenium cation is R 1 -C + (R)-R 2 (wherein R, R 1 , and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2and optionally R, taken together with the atom to which they are attached, form a cycloaliphatic group, as defined herein.

[0161] "Carbonyl" means the group -C(O)-, which can also be represented as >C=O.

[0162] "Carboxyl" means the -CO2H group or its anion.

[0163] "Cyano" refers to the radical -CN.

[0164] "Cycloaliphatic" means an aliphatic group, as defined herein, that is cyclic.

[0165] "Cycloalkoxy" means a cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkoxy group is -OR, where R is a cycloalkyl group, as defined herein.

[0166] "Cycloalkylalkoxy" refers to an alkyl-cycloalkyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the cycloalkylalkoxy group is -OLR, where L is an alkyl group, as defined herein, and R is a cycloalkyl group, as defined herein.

[0167] "Cycloalkyl" means, unless otherwise specified, a monovalent saturated or unsaturated non-aromatic cyclic hydrocarbon radical having from 3 to 8 carbon atoms and is exemplified by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1.heptyl, and the like. Cycloalkyl groups may also be substituted or unsubstituted. For example, cycloalkyl groups may be substituted with one or more groups, including those described herein for alkyl.

[0168] "Cycloheteroaliphatic" means a heteroaliphatic group, as defined herein, that is cyclic.

[0169] "Ester" means -C(O)OR or -OC(O)R, where R is selected from aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0170] "Ether" is ROR 1 (wherein R and R 1 are each independently selected from an aryl or alkyl group, or R and R 1 each taken together with the atom to which it is attached forms a heterocycle as defined herein.

[0171] "Halo" means F, Cl, Br, or I.

[0172] "Haloaliphatic" means an aliphatic group, as defined herein, in which one or more hydrogen atoms, for example 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0173] "Haloalkyl" refers to an alkyl group, as defined herein, in which one or more hydrogen atoms, for example 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo. In a separate embodiment, the haloalkyl can be a -CX group, where each X can be independently selected from fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl group is -LX, where L is an alkyl group, as defined herein, and X is fluoro, bromo, chloro, or iodo. In other embodiments, the haloalkyl group is -LC(X)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein, X is fluoro, bromo, chloro, or iodo, and R 1 and R 2Each of is independently H or alkyl as defined herein.

[0174] "Haloheteroaliphatic" means heteroaliphatic, as defined herein, in which one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently replaced with a halogen atom, such as fluoro, bromo, chloro, or iodo.

[0175] "Heteroaliphatic" means an aliphatic group, as defined herein, containing at least one heteroatom and up to 20 heteroatoms, e.g., 1-15 heteroatoms, or 1-5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, in the group.

[0176] "Heteroalkyl", "heteroalkenyl", and "heteroalkynyl" mean an alkyl, alkenyl, or alkynyl group, respectively, as defined herein, which may be branched, straight chain, or cyclic, containing at least one heteroatom and up to 20 heteroatoms, e.g., 1 to 15 heteroatoms, or 1 to 5 heteroatoms, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof, in the group.

[0177] "Heteroalkyl-aryl", "heteroalkenyl-aryl", and "heteroalkynyl-aryl" refer to an aryl group, as defined herein, that is or can be linked to a compound disclosed herein, where the aryl group is or can be linked via a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-aryl group is -LR, where 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 -LR, where L is a heteroalkenyl group, as defined herein, and R is an aryl group, as defined herein. In some embodiments, the heteroalkynylaryl group is -LR, where L is a heteroalkynyl group, as defined herein, and R is an aryl group, as defined herein.

[0178] "Heteroalkyl-heteroaryl", "heteroalkenyl-heteroaryl", and "heteroalkynyl-heteroaryl" refer to a heteroaryl group, as defined herein, that is or can be linked to a compound disclosed herein, where the heteroaryl group is or can be linked via a heteroalkyl, heteroalkenyl, or heteroalkynyl group, respectively, as defined herein. In some embodiments, the heteroalkyl-heteroaryl group is -LR, where 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 -LR, where L is a heteroalkenyl group, as defined herein, and R is a heteroaryl group, as defined herein. In some embodiments, the heteroalkynylaryl group is -LR, where L is a heteroalkynyl group, as defined herein, and R is a heteroaryl group, as defined herein.

[0179] "Heteroaryl" refers to an aryl group containing at least one heteroatom to six heteroatoms, e.g., one to four heteroatoms, in the ring, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and oxidized forms thereof. Such heteroaryl groups can have a single ring or multiple fused rings, which may or may not be aromatic and / or contain heteroatoms, 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. Exemplary heteroaryls include a subset of heterocyclyl groups, as defined herein, which are aromatic, i.e., contain 4n+2 pi-electrons in a monocyclic or polycyclic ring system.

[0180] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, heteroatoms do not include halogen atoms, for example, unless permitted by valence constraints.

[0181] "Heterocyclyl" means, unless otherwise specified, a 5-, 6-, or 7-membered ring containing 1, 2, 3, or 4 non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Five-membered rings have 0-2 double bonds, and 6- and 7-membered rings have 0-3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings are fused to 1, 2, or 3 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. Heterocyclic rings include thiiranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinoline, and the like. Linyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazolyl, triazolyl, tetrazolyl, oxadiazolyl, urisyl, thiadiazolyl, pyrimidyl, tetrahydrofuranyl, dihydrofuranyl, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dithiazolyl, dioxanyl, dioxinyl, dithianyl, trithianyl, oxazinyl, thiazinyl, oxothiolanyl, triazinyl, benzofuranyl, benzothienyl and the like.

[0182] "Heterocyclyloxy" means a heterocyclyl group, as defined herein, attached to the parent molecular group through an oxygen atom. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group, as defined herein.

[0183] "Heterocyclyl" means a heterocyclyl group, as defined herein, attached to the parent molecular group through a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group, as defined herein.

[0184] "Hydroxyl" means --OH.

[0185] "Hydroxyalkyl" means an alkyl group, as defined herein, substituted with 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, where L is an alkyl group, as defined herein. In other embodiments, the hydroxyalkyl group is -LC(OH)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0186] "Ketone" means -C(O)R, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0187] "Nitro" refers to the -NO2 group.

[0188] "Nitroalkyl" refers to an alkyl group, as defined herein, substituted with one to three nitro groups. In some embodiments, a nitroalkyl group is -L-NO, where L is an alkyl group, as defined herein. In other embodiments, a nitroalkyl group is -LC(NO)(R 1 )-R 2 where L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of is independently H or alkyl as defined herein.

[0189] "Oxo" means the group ═O.

[0190] "Oxy" means --O--.

[0191] "Perfluoroalkyl" refers to an alkyl group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, a perfluoroalkyl group is -(CF2) n CF3, and n is an integer from 0 to 10.

[0192] "Perfluoroalkoxy" means an alkoxy group, as defined herein, in which each hydrogen atom is replaced with a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group, as defined herein.

[0193] "Phosphine" is a PR 1 R 2 (wherein R 1 and R 2 each is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, or aromatic, or R 1 and R 2 each taken together with the atom to which it is attached forms a heterocyclic group as defined herein.

[0194] "Salt" refers to an ionic form of a compound or structure (e.g., any formula, compound or composition described herein) that contains a cationic or anionic compound to form an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in Berge SM et al., "Pharmaceutical salts", J.Pharm.Sci. January 1977, 66(1):1-19, and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use" Wiley-VCH, April 2011 (2nd rev. ed., P.H. Stahl and C.G. Wermuth, eds.). Salts may be prepared in-situ during the final isolation and purification of the compounds of the present invention, or separately, by reacting the free base group with a suitable organic acid (thereby producing an anionic salt) or the acid group with a suitable metal or organic acid salt (thereby producing a cationic salt).Representative anionic salts include acetate, adipate, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, bitartrate, borate, bromide, butyrate, camphorate, camphorsulfonate, chloride, citrate, cyclopentanepropionate, digluconate, dihydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptonate, gluconate, glutamate, glycerophosphate, hemisulfate, heptonate, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate ... Examples of the salts include bionate, laurate, lauryl sulfate, malate, maleate, malonate, mandelate, mesylate, methanesulfonate, methyl bromide, methyl nitrate, methyl sulfate, mucate, 2-naphthalenesulfonate, nicotinate, nitrate, oleate, oxalate, palmitate, pamoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, polygalacturonate, propionate, salicylate, stearate, basic acetate, succinate, sulfate, tannate, tartrate, theophylline, thiocyanate, triethiodide, toluenesulfonate, undecanoate, and valerate. Representative cationic salts include metal salts, such as alkali or alkaline earth salts, such as barium, calcium (e.g., calcium edetate), lithium, magnesium, potassium, sodium, and other metal salts, such as aluminum, bismuth, iron, and zinc, as well as non-toxic ammonium, quaternary ammonium, and amine cations, including, but not limited to, ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, pyridinium, and the like. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Still other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphazinium, phosphazenium, pyridinium, and the like, as well as other cationic groups described herein (e.g., optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrrolium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazolium, optionally substituted isothiazolium, optionally substituted triazolium, optionally substituted tetrazolium, optionally substituted furazanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, 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 Optionally substituted isoindolium, optionally substituted indolizinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolizinium, optionally substituted dehydroquinolizinium, optionally substituted quinolinium, optionally substituted isoindolinium, optionally substituted benzimidazolinium, and optionally substituted prenium.

[0195] "Sulfo" refers to the group -S(O)2OH.

[0196] "Sulfonyl" or "sulfonate" means a -S(O)- group or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0197] "Thioalkoxy" means an alkyl group, as defined herein, attached to the parent molecular group through a sulfur atom. Exemplary unsubstituted thioalkoxy groups include, 1~6 In some embodiments, the thioalkoxy group is -SR, where R is an alkyl group, as defined herein.

[0198] "Thiol" refers to a -SH group.

[0199] "Urea" is (R 1 NR 2 )CO, where R 1 and R 2 are each independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, or aromatic, or R 1 and R 2 each taken together with the atom to which it is attached forms a heterocyclic group as defined herein.

[0200] Those skilled in the art will recognize that the definitions given above are not intended to include impermissible substitution patterns (such as, for example, methyl substituted with five different groups). Such impermissible substitution patterns are easily recognized by those skilled in the art. The functional groups disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise indicated therein.

[0201] Device The methods described herein may be implemented in any suitable apparatus. The following description provides an example of a suitable apparatus. The apparatus described herein allows for rapid and accurate control of substrate 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, an etch that relies primarily on chemical reactions coupled with thermal energy, rather than plasma, to drive the chemical reactions in the modification and removal operations may be considered a "thermal etch." This etch is not limited to ALE (atomic layer etch) and is applicable to any etch technique.

[0202] In certain embodiments, thermal etching processes, such as those utilizing one or more thermal cycles, have relatively fast heating and cooling, and relatively precise temperature control. In some cases, these features can be utilized to provide good throughput and / or reduce non-uniformity and wafer defects.

[0203] Many conventional etching apparatuses do not have the ability to adjust and control the temperature of the substrate at an adequate rate. For example, some etching apparatuses may be able to heat the substrate to multiple temperatures, but may only heat slowly or may not be able to reach the desired temperature range, or may not be able to maintain the substrate temperature for the desired time and in the desired temperature range. Similarly, typical etching apparatuses often are unable to cool the substrate or to the desired temperature range quickly enough to allow high throughput. In some applications, it is desirable to shorten the temperature ramp time as much as possible, for example, to less than about 120 seconds in some embodiments, but many conventional etching apparatuses are unable to heat, cool, or both the substrate in less than that time, and some apparatuses may take several minutes to cool and / or heat the substrate, thereby reducing throughput.

[0204] In various embodiments, the apparatus described herein is designed or configured to rapidly heat and cool the wafer and precisely control the temperature of the wafer. In some embodiments, the wafer is rapidly heated and its temperature precisely controlled using in part visible light emitted from light emitting diodes (LEDs) positioned in a pedestal below the wafer. The visible light may have a wavelength ranging from, including, 400 nanometers (nm) to 800 nm. The pedestal may include various features to enable temperature control of the wafer, such as a transparent window that may have a lens to advantageously direct or focus the emitted light, a reflector to advantageously direct or focus the emitted light, and temperature control elements to aid in temperature control of the LEDs, the pedestal, and the chamber.

[0205] The apparatus can also thermally isolate or "float" the wafer within the processing chamber so that only minimal thermal mass is heated, with the ideal minimal thermal mass being just the substrate itself, thereby allowing for faster heating and cooling. The wafer may be rapidly cooled using 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 cases, the apparatus also includes temperature control elements within the processing chamber walls, pedestal and top plate (or other gas distribution element), allowing for further temperature control of the wafer and processing conditions within the chamber, such as preventing unwanted condensation of processing gases and vapors.

[0206] The apparatus may also be configured to implement various control loops (e.g., by a controller configured to execute instructions that cause the apparatus to implement these loops) to precisely control the wafer and chamber temperatures. This may include the use of various sensors to determine the wafer and chamber temperatures as part of open-loop and feedback control loops. These sensors may include non-contact sensors such as temperature sensors on the wafer support that contact the wafer and measure its temperature, photodetectors that measure the light output of LEDs, and pyrometers configured to measure the temperature of different types of wafers. As described in more detail below, conventional pyrometers determine the temperature of an article by emitting an infrared or other optical signal at the article and measuring the signal reflected or emitted by the article. However, many silicon wafers cannot be measured by conventional pyrometers because silicon can be optically transparent at various temperatures and with various processes, e.g., doped or low-doped silicon. For example, low-doped silicon wafers at temperatures below 200° C. are transparent to infrared signals. The novel pyrometers provided herein are capable of measuring multiple types of silicon wafers at various temperatures.

[0207] 5 shows a cross-sectional side view of an exemplary apparatus according to disclosed embodiments. The apparatus may be used to perform any of the methods described herein, for example, using the chemicals described herein. As described in more detail below, the apparatus 100 is capable of rapidly and precisely controlling the temperature of a substrate, including performing thermal etching operations. The apparatus 100 includes a process chamber 102, a pedestal 104 having a substrate heater 106 and a plurality of substrate supports 108 configured to support a substrate 118, and a gas distribution unit 110.

[0208] The processing chamber 102 includes a sidewall 112A, a top 112B, and a bottom 112C that at least partially define a chamber interior 114, which may be considered a plenum volume. As described herein, in some embodiments, it may be desirable to actively control the temperatures of the processing chamber walls 112A, top 112B, and bottom 112C to prevent unwanted condensation on their surfaces. Some new semiconductor processing operations flow vapors, such as water and / or alcohol vapors, onto the substrate, which may also undesirably adsorb onto the interior surfaces of the chamber. This may result in unwanted deposition and etching of the chamber interior surfaces, which may damage the chamber surfaces, and particulate matter may flake off onto the substrate, which may result in substrate defects. To reduce and prevent unwanted condensation on the chamber interior surfaces, the temperatures of the chamber walls, top, and bottom may be maintained at temperatures at which condensation of chemicals used in the processing operations does not occur.

[0209] This active temperature control of the chamber surfaces may be achieved by using heaters to heat the chamber walls 112A, the top 112B, and the bottom 112C. As shown in FIG. 5, the chamber heater 116A is positioned on the chamber wall 112A and configured to heat the chamber wall 112A, the chamber heater 116B is positioned on the top 112B and configured to heat the top 112B, and the chamber heater 116C is positioned on the bottom 112C and configured to heat the bottom 112C. The chamber heaters 116A-116C may be resistive heaters configured to generate heat when a current is passed through a resistive element. The chamber heaters 116A-116C may also be fluid conduits through which a heat transfer fluid, such as a heating fluid that may include heated water, may be passed. In some examples, the chamber heaters 116A-116C may be a combination of both a heating fluid and a resistive heater. The chamber heaters 116A-116C are configured to generate heat to bring the inner surfaces of the chamber walls 112A, top 112B, and bottom 112C, respectively, to a desired temperature, which may range from about 40° C. to about 150° C., including, for example, about 80° C. to about 130° C., or about 90° C., or about 120° C. It has been discovered that under some conditions, water and alcohol vapors do not condense on surfaces maintained at or above about 90° C.

[0210] The chamber walls 112A, top 112B, and bottom 112C may also be constructed from a variety of materials that can withstand chemicals used in processing techniques. These chamber materials may include, for example, aluminum, anodized aluminum, aluminum with a polymer such as plastic, a metal or metal alloy with a yttria coating, a metal or metal alloy with a zirconia coating, a metal or metal alloy with an aluminum oxide coating, and in some examples, the coating material may be a blend or layer of a combination of different materials, such as alternating layers of aluminum oxide and yttria, or aluminum oxide and zirconia. These materials are configured to withstand chemicals used in processing techniques, such as anhydrous HF, water vapor, methanol, isopropyl alcohol, chlorine, fluorine gas, nitrogen gas, hydrogen gas, helium gas, and mixtures thereof.

[0211] The apparatus 100 may also be configured to perform processing operations at or near a vacuum, such as 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. It may include a vacuum pump 184 configured to evacuate the chamber interior 114 to a low pressure, such as a vacuum having a pressure of about 0.1 Torr to about 100 Torr, or another pressure range described herein.

[0212] Various features of the pedestal 104 will now be considered. The pedestal 104 includes a heater 122 (enclosed by the dashed rectangle in FIG. 5) having a plurality of LEDs 124 configured to emit visible light having wavelengths between and including 400 nm and 800 nm, including 450 nm. The heater LEDs emit this visible light to the backside of the substrate, thereby heating the substrate. Visible light having wavelengths between about 400 nm and 800 nm can quickly and efficiently heat a silicon wafer to ambient temperatures, e.g., from about 20° C. to about 600° C., because silicon absorbs light in this range. In contrast, radiative heating, including infrared radiative heating, may not effectively heat silicon at temperatures up to about 400° C., because silicon tends to be transparent to infrared radiation at temperatures below about 400° C. Additionally, radiative heaters that directly heat the topside of the wafer, as in many conventional semiconductor processes, may cause damage or other adverse effects to the topside film. Conventional "hot plate" heaters, which rely on solid-to-solid heat transfer between the substrate and a heated platen such as a pedestal with a heating coil, have relatively slow heating and cooling rates, resulting in uneven heating that can be caused by substrate warping and inconsistent contact with the heated platen. For example, it can take several minutes to heat a conventional pedestal to a desired temperature, heat it from the first temperature to a second, higher temperature, and then cool the pedestal to a lower temperature.

[0213] FIG. 17 shows a graph of silicon absorption at various wavelengths and temperatures. The x-axis is the wavelength of light, the y-axis is absorption with 1.0 as the maximum (i.e., 100%), and the data is the light absorption of silicon at different temperatures. As can be seen, in region 1, silicon's absorption of light from 400 nm to 800 nm remains relatively constant as the temperature of the silicon changes. However, silicon's absorption of infrared light, i.e., light having wavelengths above about 1 micron, changes with the temperature of the silicon, and as a result, silicon's absorption is inconsistent until the temperature reaches 600°C. Furthermore, the absorption range for various wavelengths and temperatures is reduced compared to the visible range. For example, silicon at 270°C has very low absorptivity, about 0.05 or 5%, for infrared emissions from about 1.8 microns to about 6 microns, and inconsistent absorptivity from about 6 microns to 10 microns. Silicon at 350°C has the next lowest absorptivity of infrared light, ranging from about 10% to 20% from about 1.8 microns to about 5 microns. Therefore, when using visible light, consistent absorption is obtained regardless of the temperature of the silicon.

[0214] The heater's LEDs may be arranged, electrically connected, and electrically controlled in various manners. Each LED may be configured to emit visible blue light and / or visible white light. In certain embodiments, white light (generated using a wavelength range in the visible portion of the EM spectrum) is used. In some semiconductor processing operations, white light can reduce or prevent unwanted thin film interference. For example, some substrates have backside films that reflect different wavelengths of light in varying amounts, resulting in non-uniform and potentially inefficient heating. Using white light can reduce this unwanted reflection variation by averaging out the thin film interference over the broad visible spectrum provided by the white light. In some instances, depending on the material on the backside of the substrate, it may be advantageous to use a visible non-white light, such as blue light having a wavelength of 450 nm, to provide a single or narrow wavelength band, thereby allowing more efficient and powerful direct heating of some substrates that may absorb the narrow wavelength band better than white light.

[0215] Various types of LEDs may be utilized. Examples include chip-on-board (COB) LEDs or surface-mounted diode (SMD) LEDs. For SMD LEDs, the LED chip may be fused to a printed circuit board (PCB) that may have multiple electrical contacts that allow control of each diode on the chip. For example, one SMD chip is typically limited to having three diodes (e.g., red, blue or green) that may be individually controllable to produce different colors. SMD LED chips may range in size from 2.8×2.5 mm, 3.0×3.0 mm, 3.5×2.8 mm, 5.0×5.0 mm, and 5.6×3.0 mm, etc. For COB LEDs, each chip may have more than three diodes, such as 9, 12, tens, hundreds or more, printed on the same PCB. COB LED chips typically have one circuit and two contacts regardless of the number of diodes, thereby providing a concise design and efficient single-color applications. The ability and performance of the LEDs to heat the substrate may be measured by the watts of heat emitted by each LED, which may contribute directly to heating the substrate.

[0216] FIG. 6 shows a top view of a substrate heater with a plurality of LEDs. The substrate heater 122 includes a printed circuit board 126 and a plurality of LEDs 124, some of which are labeled. The illustrated plurality includes approximately 1,300 LEDs. External connections 128 are connected by traces to provide power to the plurality of LEDs 124. As shown in FIG. 6, the LEDs may be arranged along multiple arcs radially offset by different radii from a center 130 of the substrate heater 122, and in each arc, the LEDs may be equally spaced from one another. For example, one arc 132 is surrounded by a partially shaded dotted shape, includes 16 LEDs 124, and is a portion of a circle of radius R extending around the center 130. The 16 LEDs 124 may be considered to be equally spaced from one another along this arc 132.

[0217] In some embodiments, the LEDs may also be arranged along a circle around the center of the substrate heater. In some examples, some LEDs may be arranged along a circle, while other LEDs may be arranged along an arc. FIG. 7 shows a top view of another example of a substrate heater with multiple LEDs. This substrate heater 322 includes a printed circuit board 326 and multiple LEDs 324, some of which are labeled. Here, the LEDs 324 may be arranged along multiple circles radially offset by different radii from the center 330 of the substrate heater 322, and in each circle, the LEDs may be equally spaced from one another. For example, one circle 334 is surrounded by a partially shaded ring and includes 78 LEDs 324, a radius R extending around the center 330. The 78 LEDs 324 may be considered to be equally spaced from one another along this circle 334. The LED array of FIG. 7 may provide a more uniform light and heat distribution pattern across the backside of the substrate, particularly because the substrate and heater remain stationary relative to one another during processing and the substrate and substrate heater do not rotate, as areas of the substrate heater 122 of FIG. 6 that include external connections may result in unheated cold spots on the wafer.

[0218] In some embodiments, the plurality of LEDs may include at least about 1,000 LEDs, including, for example, more than about 1,200, 1,500, 2,000, 3,000, 4,000, 5,000, or 6,000. Each LED may be configured to use 4 watts or less at 100% power, including, in some examples, 3 watts at 100% power, and 1 watt at 100% power. The LEDs may be arranged and electrically connected into individually controllable zones to allow for temperature tuning and fine-tuning across the substrate. In some examples, the LEDs may be grouped into at least 20, for example, independently controllable zones, including, for example, at least about 25, 50, 75, 80, 85, 90, 95, or 100 zones. The zones may allow for radial and azimuthal (i.e., angular) temperature tuning. The zones may be arranged in a defined pattern, such as a rectangular grid, a hexagonal grid, or other suitable pattern to generate a desired temperature profile. The zones may also have various shapes, such as squares, trapezoids, rectangles, triangles, ovals, ellipses, circles, annuli (e.g., rings), partial annuli (i.e., annular sectors), arcs, segments, and sectors that are centered on the center of the heater and may have a radius equal to or less than the overall radius of the PCB of the substrate heater. For example, in FIG. 6, the LEDs have 88 zones organized into at least 20, e.g., 20 or 21 concentric rings. These zones can adjust the temperature at multiple locations across the wafer to generate a more uniform temperature distribution and a desired temperature profile, such as a higher temperature around the edge of the substrate than the center of the substrate. Independent control of these zones may also include the ability to control the power output of each zone. For example, each zone may have at least 15, 20, or 25 adjustable power outputs. In some examples, each zone may have one LED, which allows each LED to be individually controlled and adjusted, thereby resulting in a more uniform heating profile on the substrate. Thus, in some embodiments, each LED of the multiple LEDs in the substrate heater may be individually controllable.

[0219] In certain embodiments, the substrate heater 122 is configured to heat the substrate to multiple temperatures and maintain each such temperature for various periods of time. These periods may include the following non-limiting examples: at least about 1 second, at least about 5 seconds, at least about 10 seconds, at least about 30 seconds, at least about 60 seconds, at least about 90 seconds, at least about 120 seconds, at least about 150 seconds, or at least about 180 seconds. The substrate heater may be configured to heat the substrate to, for example, about 50°C to 600°C, including about 50°C to about 150°C, or about 150°C to 350°C, including about 130°C. Other possible temperature ranges are discussed above. The substrate heater may be configured to maintain the substrate at a temperature within these ranges for various periods of time, including the following non-limiting examples: at least about 1 second, at least about 5 seconds, at least about 10 seconds, at least about 30 seconds, at least about 60 seconds, at least about 90 seconds, at least about 120 seconds, at least about 150 seconds, or at least about 180 seconds. Further, in some embodiments, the substrate heater 122 is configured to heat the substrate to any temperature within these ranges, for example, in less than about 60 seconds, less than about 45 seconds, less than about 30 seconds, or less than about 15 seconds. In certain embodiments, the substrate heater 122 is configured to heat the substrate at one or more heating rates, such as, for example, at least about 0.1° C. / sec to at least about 20° C. / sec.

[0220] The substrate heater can increase the temperature of the substrate by causing the LEDs to emit visible light at one or more power levels, including at least about 80%, at least about 90%, at least about 95%, or at least about 100% power. In some embodiments, the substrate heater is configured to emit about 10 W to about 4000 W, including at least about 10 W, at least about 30 W, at least about 0.3 kilowatts (kW), at least about 0.5 kW, at least about 2 kW, at least about 3 kW, or at least about 4 kW. The apparatus is configured to provide about 0.1 kW to 9 kW of power to the pedestal, with the power source being connected to the substrate heater through the pedestal but not shown in the figures. During the temperature increase, the substrate heater may operate at a high power or at a lower power level (e.g., including about 5 W to about 0.5 kW) to maintain the temperature of the heated substrate.

[0221] The pedestal may include a reflective material on its inner surface that, during operation, reflects light emitted by the LEDs and directs it to the backside of the substrate supported by the pedestal. In some such embodiments, the substrate heater may include such a reflective material positioned on the top surface 140 of the PCB 126 on which the plurality of LEDs 124 are positioned, as shown in FIG. 5. The reflective material may be comprised of aluminum, e.g., polished aluminum, stainless steel, aluminum alloys, nickel alloys, and other protective layers that may prevent oxidation of the metal and / or increase reflectivity at certain wavelengths, e.g., may reach reflectivity greater than 99% for certain wavelengths, as well as other durable reflective coatings. Additionally or alternatively, the pedestal 104 may have a bowl 146 in which the substrate heater 122 is at least partially positioned. The bowl 146 may have an exposed inner surface 148 of the pedestal sidewall 149 on which the reflective material may be positioned. This reflector increases the heating efficiency of the substrate heater and advantageously directs light that would otherwise be absorbed by the PCB 126 and pedestal 104 back onto the substrate, thereby reducing unwanted heating of the PCB 126 and pedestal 104.

[0222] In some embodiments, the substrate heater may also include a pedestal cooler that is thermally connected to the LEDs such that heat generated by the LEDs can be transferred from the LEDs to the pedestal cooler. This thermal connection is such that heat can be conducted from the LEDs to the pedestal cooler along one or more heat flow paths between these components. In some examples, the pedestal cooler is in direct contact with one or more elements of the substrate heater, while in other examples, other conductive elements, such as a thermally conductive plate (e.g., including metal), are interposed between the substrate heater and the pedestal cooler. Referring again to FIG. 5, the substrate heater includes a pedestal cooler 136 that is in direct contact with the bottom of the PCB 126. Heat is configured to flow from the LEDs to the PCB 126 and to the pedestal cooler 136. The pedestal cooler 136 also includes a number of fluid conduits 138 configured to allow a heat transfer fluid, such as water, to flow through in order to receive heat and thus cool the LEDs in the substrate heater 122. The fluid conduit 138 may be connected to a reservoir and pump, not shown, located outside the chamber. In some examples, the pedestal cooler may be configured to flow chilled water, such as at about 5°C to 20°C.

[0223] As provided herein, it may be advantageous to actively heat the exterior surface of the processing chamber 102. In some examples, it may be advantageous to heat the exterior surface of the pedestal 104 to prevent unwanted condensation and deposition on its exterior surface as well. As shown in FIG. 5, the pedestal 104 may further include a pedestal heater 144 inside the pedestal 104 configured to heat the exterior surface of the pedestal 104, including its sides 142A and bottom 142B. The pedestal heater 144 may include one or more heating elements, such as one or more resistive heating elements, and a fluid conduit configured to allow a heating fluid to flow through. In some examples, the pedestal cooler and the pedestal heater may both have fluid conduits fluidly connected to each other such that the same heat transfer fluid can flow through both the pedestal cooler and the pedestal heater. In these embodiments, the fluid may be heated to between 50° C. and 130° C., including between about 90° C. and 120° C.

[0224] The pedestal may also include a window to protect the substrate heater, including the multiple LEDs, from damage caused by exposure to the process chemicals and pressures used during processing operations. As shown in FIG. 5, a window 150 may be positioned above the substrate heater 122 and sealed to the sidewall 149 of the pedestal 104 to create a plenum volume within the pedestal that is fluidly isolated from the chamber interior. This plenum volume may also be considered the interior of the bowl 146. The window may be constructed of one or more materials that are optically transparent to the visible light emitted by the LEDs, including light having wavelengths in the range of 400 nm to 800 nm. In some embodiments, the material may be quartz, sapphire, quartz with a sapphire coating, or calcium fluoride (CaF). The window may also have no holes or openings therein. In some embodiments, the heater may have a thickness of 15 to 30 mm, including 20 mm and 25 mm.

[0225] FIG. 8 illustrates the pedestal of FIG. 5 with additional features according to various embodiments. As identified in FIG. 8, the window 150 includes a top surface 152 that faces the substrate 118 supported by the pedestal 104, and a bottom surface 154 that faces the substrate heater 122. In some embodiments, the top surface 152 and the bottom surface 154 may be flat planar (or substantially flat, e.g., within ±10% or 5% of flat). In some other examples, the top surface 152, the bottom surface 154, or both the top surface 152 and the bottom surface 154 may be non-planar. The non-planarity of these surfaces may be configured to refract and / or direct light emitted by the LEDs 124 of the substrate heater 122 to more efficiently and / or effectively heat the wafer. The non-planarity may also be along some or all of the surface. For example, the entire bottom surface may have a convex or concave curvature, while in another example, an outer annular region of the bottom surface may have a convex or concave curvature, while the remainder of the surface is planar. In further examples, the surfaces may have multiple, but different, non-planar portions, such as a conical portion in the center of the surface adjacent a planar annular portion that is adjacent a conical frustum surface at the same or different angle as the conical portion. In some embodiments, window 150 may have features that act as an array of lenses oriented to focus the light emitted by one or more LEDs, such as each LED.

[0226] When the window 150 is positioned above the substrate heater 122, the window 150 may be heated by the substrate heater 122, thereby affecting the thermal environment around the substrate. Depending on the material or materials used for the window 150, such as quartz, the window may retain heat and may retain progressively more heat in the course of processing one or more substrates. This heat may be radiatively transferred to the substrate, thus directly heating the substrate. In some examples, the window may cause a temperature increase of 50° C. to 80° C. above the heater temperature. This heat may also cause a temperature gradient through the thickness of the window or vertically. In some examples, the top surface 152 is 30° C. hotter than the bottom surface 154. It may therefore be advantageous to tune and configure the chamber to account for and reduce the thermal effects of the window. As described in more detail below, this may include sensing the temperature of the substrate and adjusting the substrate heater to account for the heat retained by the window.

[0227] This may also include various configurations of the pedestal to actively cool the window. In some embodiments, such as shown in Figures 5 and 8, the window 150 may be offset from the substrate heater 122 by a first distance 156. In some embodiments, this first distance may be between about 2 mm and 50 mm, including between about 5 mm and 40 mm. A cooling fluid, such as an inert gas, may be flowed between the window 150 and the substrate heater 122 to cool both the window 150 and the substrate heater 122. The pedestal may have one or more inlets and one or more outlets for flowing this gas into the plenum volume or bowl 146 of the pedestal 104. The one or more inlets are fluidly connected to a source of inert gas outside the chamber 102, which may include via a fluid conduit that may be routed at least partially to the interior of the pedestal 104. The one or more outlets are fluidly connected to an exhaust or other environment outside the chamber 102, which may also be through a fluid conduit that runs through the pedestal. In FIG. 18, which shows the pedestal of FIG. 8 with additional features according to various embodiments, one or more inlets 151 are positioned in the sidewall 149 and extend through the surface 148, and the one or more inlets are also fluidly connected to an inert gas source 1472 via a fluid conduit 155 that is also partially threaded through the pedestal 104. A single outlet 153 is positioned in a central region of the substrate heater 122, i.e., close to but not exactly in the center. In some embodiments, the gas inlet(s) and the outlet(s) may be switched such that one or more outlets extend through the sidewall 149 (i.e., they are item 151 in FIG. 18) and one or more inlets may be in the central region of the substrate heater 122 (i.e., they are item 153 in FIG. 18). In some embodiments, there may be more than one outlet, and in some embodiments, there may be only a single gas inlet. In some embodiments, one or more gas inlets extend through the inner surface 148 of the pedestal sidewall 149 below the LED heater 122, and one or more gas outlets extend through another portion of the pedestal sidewall 149, such as a mounting bracket between the LED heater 122 and the pedestal sidewall 149.

[0228] In some embodiments, the window may be placed in direct thermal contact with the substrate heater, and a pedestal cooler may be configured to cool both the PCB and the window. In some embodiments, the window 150 may be thermally connected to the sidewall 149 of the pedestal 104 to transfer a portion of the retained heat in the window 150 to the pedestal 104, as also shown in FIG. 5 and FIG. 8. This transferred heat may be further transferred from the pedestal using, for example, a pedestal heater 144 that may flow a fluid heated to about 20° C. to 100° C. to the pedestal 104. This heated fluid may be at a lower temperature than the temperature of the pedestal 104 in thermal connection with the window 150. In some embodiments, the window 150 may have one or more fluid conduits within the window 150 through which a transparent cooling fluid may be configured to flow. These conduits may be in various arrangements to provide uniform cooling and temperature distribution within the window, such as a single inlet, a single outlet, and a single flow path with a serpentine section. The fluid may be passed from a fluid source or reservoir external to the chamber through the pedestal to the window.

[0229] As shown in Figures 5 and 8, the substrate support 108 of the pedestal 104 is configured to support the substrate 118 above and offset from the window 150 and the substrate heater 122. In certain embodiments, by thermally floating or isolating the substrate within the chamber, the temperature of the substrate can be rapidly and precisely controlled. Heating and cooling of the substrate is directed to both the thermal mass of the substrate and the thermal mass of other objects in contact with the substrate. For example, if the substrate is in thermal contact with a large object, e.g., the entire backside of the substrate rests on a large surface of a pedestal or electrostatic chuck, as in many conventional etching apparatus, this object acts as a heat sink for the substrate, thereby affecting the ability to precisely control the temperature of the substrate and reducing the rapidity of heating and cooling of the substrate. It is therefore desirable to position the substrate such that a minimum of thermal mass is heated and cooled. This thermal floating is configured to position the substrate to minimize thermal contact (including direct and radiative) with other objects within the chamber.

[0230] Thus, the pedestal 104 is configured in some embodiments to support the substrate 118 by thermally floating or thermally isolating the substrate within the chamber interior 114. The multiple substrate supports 108 of the pedestal 104 are configured to support the substrate 118 such that the thermal mass of the substrate 118 is reduced as much as possible to the thermal mass of the substrate 118 alone. Each substrate support 108 may have a substrate support surface 120 that minimizes contact with the substrate 118. The number of substrate supports 108 may range from at least three, e.g., at least six or more. The surface area of ​​the support surface 120 may also be the minimum area required to adequately support the substrate during processing operations (e.g., to support the weight of the substrate and prevent inelastic deformation of the substrate). In some embodiments, the surface area of ​​one support surface 120 may be, for example, less than about 0.1%, less than about 0.075%, less than about 0.05%, less than about 0.025%, or less than about 0.01%.

[0231] The substrate support is also configured to prevent the substrate from contacting other elements of the pedestal, including the surface and features of the pedestal that underlie the substrate. As seen in Figures 5 and 8, the substrate support 108 holds the substrate 118 above and offset from the next adjacent surface of the pedestal 104 that underlies the substrate 118, which is the top surface 152 of the window 150 (identified in Figure 8). As can be seen in these figures, there is a volume or gap below the substrate, except for contact with the substrate support. As shown in Figure 8, the substrate 118 is offset from the top surface 152 of the window 150 by a distance 158. This distance 158 can affect the thermal effect caused by the window 150 on the substrate 118. The greater the distance 158, the smaller the effect. It has been found that a distance 158 of 2 mm or less results in significant thermal coupling between the window and the substrate. Therefore, it may be desirable to have the distance 158 be greater than 2 mm, such as, for example, at least about 5 mm, about 10 mm, about 15 mm, about 20 mm, about 30 mm, about 50 mm, or about 100 mm.

[0232] The substrate 118 is also offset from the substrate heater 122 by a distance 160 (measured from the top surface of the substrate heater 122, which in some examples may be the top surface of the LEDs 124). This distance 160 affects many aspects of the heating of the substrate 118. In some examples, the LEDs 124 provide a non-uniform heating pattern that increases as the distance 160 decreases, and conversely, this non-uniform heating pattern is reduced by increasing the distance 160. In some examples, as the distance 160 increases, the heating efficiency decreases across the substrate and more at the edge regions, causing non-uniform heating of the substrate. In some embodiments, a distance 160 of about 5 mm to about 100 mm, such as about 10 mm to about 90 mm, or about 10 mm to about 30 mm, or about 15 mm to about 25 mm, provides a substantially uniform heating pattern and acceptable heating efficiency.

[0233] As described, the substrate supports 108 are configured to support the substrate 118 above the window. In some embodiments, these substrate supports are stationary and fixed in position and are not lift pins or support rings. In some embodiments, at least a portion of each substrate support 108, including the support surface 120, may be constructed from a material that is transparent to at least the light emitted by the LEDs 124. This material may be quartz or sapphire in some examples. The transparency of such substrate supports 108 may allow visible light emitted by the LEDs of the substrate heater 122 to pass through the substrate support 108 to the substrate 118, such that the substrate support 108 does not block this light and can heat the substrate 118 in the supported area. This may result in more uniform heating of the substrate 118 than using a substrate support that includes a material that is opaque to visible light. In some other embodiments, the substrate support 108 may be constructed from a non-transparent material, such as zirconium dioxide (ZrO2).

[0234] 8, the substrate supports 108 may be positioned closer to the central axis 162 of the window 150 than the outer diameter 164 of the window 150. In some examples, some of these substrate supports may extend beyond and above the window 150 to overlap the window 150 such that the support surface 120 is above the window 150.

[0235] In some embodiments, the substrate supports may each include a temperature sensor configured to detect the temperature of a substrate positioned on the support surface of the substrate support. FIG. 9 illustrates the substrate support of FIGS. 5 and 8 according to a disclosed embodiment. Here, the support surface 120 of the substrate support 108 is identified with a temperature sensor 166. In some embodiments, the temperature sensor 166 extends through the support surface 120 such that the temperature sensor 166 is in direct contact with a substrate held by the support surface 120. In some other embodiments, the temperature sensor 166 is positioned within the substrate support 108, below the support surface 120. In some embodiments, the temperature sensor 166 is a thermocouple. In some other embodiments, the temperature sensor 166 may be a thermistor, a resistance temperature detector (RTD), and a semiconductor sensor. Electrical wiring 168 for the temperature sensor 166 may be routed through the substrate support 108 and through the pedestal 104.

[0236] Referring again to FIG. 5, in some embodiments, the pedestal is also configured to move vertically. This may include moving the pedestal such that the gap 186 between the faceplate 176 of the gas distribution unit 110 and the substrate 118 can be in the range of 2 mm to 70 mm. As provided in more detail below, moving the pedestal vertically can enable active cooling of the substrate and rapid cycle times for processing operations including gas flow and purging due to the low volume created between the gas distribution unit 110 and the substrate 118. This movement also allows for the creation of a small process volume between the substrate and the gas distribution unit, which reduces purge and gas movement times and increases throughput due to smaller purge and process volumes.

[0237] The gas distribution unit 110 is configured to flow process gases, which may include liquids and / or gases, such as reactants, modification molecules, transformation molecules, or removal molecules, onto a substrate 118 in the chamber interior 114. As seen in FIG. 5, the gas distribution unit 110 includes one or more fluid inlets 170 that are fluidly 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 undesired condensation of vapors and gases flowing therethrough. 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 to be vaporized. Vaporization may be a direct injection vaporizer, a flow-over vaporizer, or both. The gas distribution unit 110 also includes a faceplate 176 that includes a number of through-holes 178 that fluidly connect the gas distribution unit 110 and the chamber interior 114. These through-holes 178 are fluidly connected to one or more fluid inlets 170 and extend through a front surface 177 of the faceplate 176, which is 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.

[0238] The through-holes 178 may be configured in various ways to deliver a uniform flow of gas over the substrate. In some embodiments, the through-holes may all have the same outer diameter, such as about 0.03 inches to 0.05 inches, including about 0.04 inches (1.016 mm). The faceplate through-holes may also be arranged across the faceplate to create a uniform flow exiting the faceplate.

[0239] 10 shows a plan view of a first example faceplate 176 with a front surface 177 (the surface configured to face a substrate) and through-holes 178 visible. As can be seen, the through-holes 178 of the faceplate 176 extend through the faceplate 176 and the front surface 177. Also, the through-holes are arranged along a plurality of circles centered on the central axis of the faceplate, such that the holes are offset from one another. For example, the faceplate 176 may have a through-hole 178A centered on the central axis of the faceplate 176. Immediately adjacent to the central through-hole 178A there may be a plurality of holes arranged equally spaced along a first circle 179 having a first diameter, and immediately radially outward from this circle there may be another circle 181 having a second plurality of holes having more holes than the first plurality of holes, and the second plurality of holes may be equally spaced along the second circle. This even spacing is not necessarily precise and may be considered to be substantially evenly spaced, which may be due to manufacturing or other inconsistencies such that the spacing may be within about ±5% of evenness. As shown, some circles of through holes 178 may be centered on a reference datum 183, while other circles of through holes are offset from the reference datum 183 by angles of about 15°, 7.5°, etc. Here, the through holes along a first circle 179 are two through holes centered on the reference datum 183, while the through holes along a second circle are not centered on the reference datum 183 and are offset from the reference datum 183 by about 15°. The concentric circles of through holes may alternate between holes centered on the datum 183 and holes offset from the datum 183.

[0240] FIG. 11 shows a plan view of a faceplate 176 of a second example, with the front surface 177 (the surface configured to face the substrate) and through-holes 178 visible. As can be seen, the through-holes 178 of the faceplate 176 extend through the faceplate 176 and the front surface 177. These through-holes are arranged differently than in FIG. 10, with one through-hole 178 centered on the central axis of the faceplate 176, and the through-holes 178 arranged in six sectors, whereby in each sector the through-holes are equally spaced along arcs within the sector. For example, one sector 191 is contained by a dashed shape, with the holes arranged along multiple arcs within the sector that increase with increasing radial distance from the center of the faceplate 176. A circular arc 193A in the first example is identified along which six through-holes 178 are equally spaced, and a circular arc 193B in the second example is identified along which twelve through-holes are equally spaced. The arc 193B of the second example is larger than the arc 193A of the first example and has a radial distance R2 that is larger than the radial distance R1 of the first arc 193A.

[0241] Referring again to FIG. 5, the gas distribution unit 110 may also include a unit heater 180 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 a fluid conduit through which a heat transfer fluid may be flowed. As above, the heat transfer fluid may be heated, for example, to a temperature range of about 20° C. to 120° C. In some examples, the unit heater 180 may be used to heat the gas distribution unit 110 to prevent unwanted condensation of vapors and gases, and in some such examples, this temperature may be at least about 90° C. or 120° C.

[0242] In some embodiments, the gas distribution unit 110 may include a second unit heater 182 configured to heat the faceplate 176. This second unit heater 182 may include one or more resistive heating elements, fluid conduits for flowing a heated fluid, or both. The use of two heaters 180 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 to provide a temperature controlled chamber as described above to reduce or prevent unwanted condensation on the elements of the gas distribution unit 110.

[0243] The apparatus 100 may also be configured to cool the substrate. This cooling may include flowing a cooling gas over the substrate, moving the substrate closer to the faceplate to allow heat transfer between the substrate and the faceplate, or both. Actively cooling the substrate allows for more precise temperature control and faster transitions between temperatures, thereby reducing processing time and increasing throughput. In some embodiments, a first unit heater 180 flowing a heat transfer fluid through a fluid conduit may be used to cool the substrate 118 by transferring heat transferred from the substrate 119 away from the faceplate 176. Thus, the substrate 118 may be cooled by being positioned in close proximity to the faceplate 176, such as with a gap 186 of 5 mm or 2 mm or less, such that 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. Thus, the faceplate 176 may be considered a heat sink for the substrate 118 for cooling the substrate 118 .

[0244] In some embodiments, the apparatus 100 may further include a cooling fluid source 173, which may include a cooling fluid (gas or liquid), and a chiller (not shown) configured to cool the cooling fluid to a desired temperature, such as, for example, 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. or lower. The apparatus 100 includes piping that delivers the cooling fluid to one or more fluid inlets 170 and a gas distribution unit 110 configured to flow the cooling fluid over the substrate. In some embodiments, the fluid may be in a liquid state when flowed into the chamber 102 and may change to a vapor state when it reaches the chamber interior 114, for example, when the chamber interior 114 is at a low pressure state as described above, for example, 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. The cooling fluid may be an inert element, such as nitrogen, argon, or helium. In some examples, the cooling fluid may include or have only 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, for example, at least about 0.25 liters per minute, at least about 0.5 liters per minute, at least about 1 liter 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. In certain embodiments, the apparatus may be configured to cool the substrate at one or more cooling rates, such as at least about 5° C. / sec, at least about 10° C. / sec, at least about 15° C. / sec, at least about 20° C. / sec, at least about 30° C. / sec, or at least about 40° C. / sec.

[0245] In some embodiments, the apparatus 100 may actively cool the substrate by both moving the substrate closer to the faceplate and by flowing a cooling gas over the substrate. In some instances, active cooling may be more effective by flowing a cooling gas while the substrate is in close proximity to the faceplate. The effectiveness of the cooling gas may also depend on the type of gas used. FIG. 12 shows a graph of four different active cooling experiments. In these four experiments, the substrate was cooled from about 400° C. to about 25° C. using different gases and gaps between the substrate and the faceplate. In a first experiment, the substrate was positioned 2 mm from the faceplate and the 400° C. substrate was actively cooled by flowing helium gas over the substrate ("He2mm"), in a second experiment, the substrate was positioned 20 mm from the faceplate and the 400° C. substrate was actively cooled by flowing helium gas over the substrate ("He20mm"), in a third experiment, the substrate was positioned 2 mm from the faceplate and the 400° C. substrate was actively cooled by flowing nitrogen gas over the substrate ("N2 2mm"), and in a fourth experiment, the substrate was positioned 20 mm from the faceplate and the 400° C. substrate was actively cooled by flowing nitrogen gas over the substrate ("N2 20mm"). As can be seen, the first experiment cooled the substrate in the fastest time of approximately 150 seconds, and the third experiment was the next fastest at approximately 450 seconds. These first and third experiments used both cooling gas and a 2 mm gap, while in the later second and fourth experiments the gap was 20 mm.

[0246] Thus, the apparatus provided herein can rapidly heat and cool the substrate. FIG. 13 shows an exemplary temperature control sequence. At time 0, the substrate is at approximately 20 or 25° C., and the LEDs of the substrate heater provided herein emit visible light having a wavelength of 400 nm to 800 nm, raising the substrate temperature to approximately 400° C. in approximately 30 seconds. This heating was achieved using 1 kW to 2 kW of heating power provided by approximately 9 kW of power supplied to the substrate heater. From approximately 30 seconds to approximately 95 seconds, the substrate heater 122 held the substrate at 400° C. using less power, such as 0.3 to approximately 0.5 kW of heating power provided by approximately 2 kW of power supply. From approximately 30 to approximately 60 seconds, the substrate was actively cooled using both a cooling gas (e.g., hydrogen or helium) flowed over the substrate and heat transfer to the faceplate. Once cooled, the substrate heater was heated to maintain the substrate at a temperature of approximately 70° C. using approximately 10-30 W of heating power provided by a power supply of approximately 100 W. Various processing techniques can use this type of sequence once or repeatedly to process the substrate.

[0247] In some embodiments, the apparatus 100 may include a mixing plenum to blend and / or condition the process gases for delivery before reaching the fluid inlet 170. One or more mixing plenum inlet valves can control the introduction of the process gases into 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 channels fluidly connected to the through-holes 178 that can evenly distribute the received fluids to the through-holes 178 to provide a uniform flow over the substrate.

[0248] 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 novel pyrometer capable of detecting multiple temperature ranges of silicon substrates. It is desirable to detect the temperature of substrates having different processes, e.g., whether the silicon is doped or undoped, in different temperature ranges where processing operations may be performed, such as below about 200° C., above about 200° C. and below about 600° C., or above about 600° C. However, conventional pyrometers cannot detect different substrates within these ranges. Conventional pyrometers measure optical signals reflected or emitted by the surface of an article and determine the temperature of the article according to some calibration. However, many silicon wafers cannot be measured by such pyrometers because silicon is optically transparent to different processes at different temperatures. As discussed above, FIG. 17 shows the different absorptivities of substrates at different temperatures. For example, while conventional pyrometers can detect emissions in the range of about 8-15 microns, most silicon substrates, at least below about 200° C., do not have a consistent emission signal in the range of about 8-15 microns and therefore cannot be detected by conventional pyrometers below about 200° C.

[0249] A lightly doped or undoped silicon substrate has an emission signal of approximately 0.95 to 1.1 microns when the substrate is at or below about 300° C., the doped silicon substrate has an emission signal of approximately 1 to 4 microns when the substrate is below about 200° C., the silicon substrate has an emission signal of approximately 1 micron when the substrate is near room temperature, e.g., below about 100° C., including 20° C., and the silicon substrate has an emission signal of approximately 8 to 15 microns when the substrate is at a temperature above about 600° C. Thus, the novel pyrometer is configured to detect multiple emission ranges, e.g., to detect multiple doped, lightly doped, or undoped substrates at various temperature ranges. This includes configurations to detect emission ranges of approximately 0.95 microns to approximately 1.1 microns, approximately 1 micron, approximately 1 to approximately 4 microns, and / or approximately 8 to 15 microns. The novel pyrometer is also configured to detect the temperature of the substrate at shorter wavelengths to distinguish the signal from thermal noise of the chamber.

[0250] The novel pyrometer may include an emitter configured to emit an infrared signal and a detector configured to receive the emission. With reference to FIG. 5, the apparatus includes a novel pyrometer 188 having an emitter in the pyrometer 188 and a detector 190. The novel pyrometer may be configured to emit a signal on one side of the substrate, either the top or bottom, and receive the signal on the other side of the substrate. For example, the emitter may emit a signal on the top of the substrate and the detector is below the substrate and receives the signal emitted through the substrate below the substrate. Thus, the apparatus may have at least a first port 192A on the top of the chamber 102, such as port 192A through the center of the gas distribution unit 110, and a second port 192B through the pedestal 104 and the substrate heater 122. An emitter in the pyrometer 188 may be connected to one of the ports 192A or 192B via a fiber optic connection, such as the first port 192A shown in FIG. 5, and a detector is optically connected to the other port, such as the second port 192B in FIG. 5. The first port 192A may include a port window 194 to seal the first port 192A from chemicals in the chamber interior 114. In FIG. 5, a second port 192B is seen extending through the pedestal 104 and the substrate heater so that emitter emissions can pass through the substrate, through the window 150, into the second port 192B, and to a detector 190 that may be located at the second port or optically connected to the second port via another fiber optic connection (not shown). In some other embodiments, the emitter and detector are reversed, such that the emitter emits through the second port 192B and the detector detects through the first port 192A.

[0251] The apparatus 100 may also include one or more light sensors 198 for detecting one or more indications of visible light emitted by the LEDs. In some embodiments, these light sensors may be one or more photodetectors configured to detect the light intensity and / or thermal radiation of visible light emitted by the LEDs of the substrate heater. In FIG. 5, a single light sensor 198 is shown connected to the chamber interior 114 via a fiber optic connection such that the light sensor 198 can detect light emitted by the substrate heater 122. The light sensor 198, as well as additional light sensors, may be positioned at various locations of the chamber 102, for example on the top and sides, to detect light emitted at various locations within the chamber 102. As discussed below, this may enable measurement and adjustment of the substrate heater, such as adjustment of one or more independently controllable zones of the LEDs. In some embodiments, there may be multiple light sensors 198 arranged along a circle or multiple concentric circles to measure various areas of the LEDs throughout the chamber 102. In some embodiments, the light sensor may be positioned within the chamber interior 114.

[0252] In some embodiments, the apparatus may be further configured to generate plasma and use the plasma for some processes in various embodiments, which may include having a plasma source configured to generate plasma within the chamber, such as capacitively coupled plasma (CCP), inductively coupled plasma (ICP), remote upper plasma, and remote lower plasma.

[0253] The devices described herein are not limited to ALE etching operations and may be used with any etching technique.

[0254] Heat Treatment Technology This section provides further details regarding heat treatment methods applicable in various embodiments. In some implementations, the above-mentioned chemicals are used in the context of carrying out the methods described in this section. In some embodiments, the methods described in connection with Figures 1-4 may be carried out according to some or all of the details provided in this section.

[0255] 14 illustrates a first technique for thermal processing according to disclosed embodiments. In operation 1001, a substrate is provided to a chamber and thermally suspended within the chamber by positioning the substrate on a pedestal substrate support. As described above, only the substrate supports contact the substrate and not other elements of the processing chamber. Each substrate support contacts an edge region of the substrate as provided herein and shown, for example, in FIGS. 5 and 8.

[0256] In operation 1003, the substrate is heated to a first temperature while thermally floating in the chamber, i.e., supported only by the substrate support, using a substrate heater described herein emitting visible light having a wavelength between 400 nm and 800 nm from a plurality of LEDs. The first temperature may be any temperature provided herein, including, for example, about 50° C. to about 600° C., including about 20° C. to about 500° C., including about 100° C. to about 500° C., including about 20° C. to about 200° C., including about 50° C. to about 150° C., including about 130° C., or about 150° C. to about 350° C. The substrate may be rapidly heated to the first temperature, for example, in less than about 60 seconds, less than about 45 seconds, less than about 30 seconds, or less than about 15 seconds. This may include powering the LEDs to their maximum power, which may be a combined delivered power of at least about 1 kW, at least about 2 kW, at least about 3 kW, at least about 4 kW, or at least about 9 kW or more. As provided herein, this heating does not include plasma or plasma generation.

[0257] In operation 1005, the substrate is maintained at a first temperature. This may include operating the substrate heater at a lower power to maintain the substrate at a particular temperature. Thus, the LEDs may be at a lower non-zero power level than at the temperature ramp to provide some heating and maintain the substrate at the desired temperature. Examples may include about 5 W to about 0.5 kW, including at least about 10 W, at least about 30 W, at least about 0.3 kW, or at least about 0.5 kW.

[0258] In operation 1007, the substrate is etched while at the first temperature. The etch may include flowing one or more gases to remove one or more modified layers of material. The etch also does not include a plasma or plasma generation. In various embodiments herein, the etch chemistry includes the above-mentioned species, e.g., HF, an organic solvent and / or water, an additive, and a carrier gas.

[0259] In operation 1009, which may be optional in some embodiments, the substrate is actively cooled. This active cooling may include flowing a cooling gas over the substrate, moving the substrate in close proximity to the faceplate, or both, as described herein. In some examples, the proximity is 5 mm or less, including 2 mm. The cooling gas may also include helium and nitrogen, for example. Following operation 1009, in some examples, operations 1003 through 1009 may be repeated, with each sequence being considered a cycle.

[0260] In some embodiments, operations 1003, 1005, and 1007 may also be performed while the chamber walls, faceplate, and / or exterior surface of the pedestal are actively heated as described above. These items may be heated to between about 80° C. and about 130° C., including at least about 90° C. or at least about 120° C. Operations 1003, 1005, 1007, and 1009 may also be performed while the chamber interior is at a vacuum, which may be at a pressure of between about 0.1 Torr and about 10 Torr, or between about 0.2 Torr and about 10 Torr.

[0261] The techniques provided herein can make various adjustments to process conditions. In some embodiments, these adjustments may be based on various received measurements, such as substrate temperature and LED measurements. In some other embodiments, these adjustments may be based on empirical or calculated data and performed in an open-loop manner. In some embodiments, the techniques may follow a sequence similar to, for example, FIG. 13 and FIG. 14. In some other embodiments, the sequence involves performing an etch or a portion of one etch cycle with a substrate at a first temperature, followed by a temperature increase to a higher second temperature where another etch cycle or another portion of the same etch cycle is performed. After this, the substrate may be actively cooled, and the etch may be repeated with the same substrate or a new substrate.

[0262] FIG. 15 illustrates a second technique according to disclosed embodiments. Here, operations 1101 to 1107 are the same as operations 1001 to 1007. After the etching of operation 1007, the heater power is adjusted in operation 1113 to a different power than that used during the maintenance of operation 1005 to heat the substrate to a second, higher temperature provided in operation 1115. The temperature of the substrate may be maintained at this second temperature during another etching or modification of the substrate, as indicated by operations 1117 and 1119. In various embodiments herein, the etching chemistry for operation 1119 includes the species described above, e.g., HF, an organic solvent and / or water, an additive, and a carrier gas. In some cases, the substrate may be modified at the second temperature, e.g., as described in connection with operation 205 of FIG. 2. In such cases, the chemistry used in operation 1107 may be selected to modify the material at the substrate surface in a desired manner. After these operations, the substrate may be actively cooled in operation 1109. In some examples, the etching operations 1103 to 1109 may be repeated on the same substrate or on different substrates. Although the first temperature is described as being lower than the second temperature, this feature is not limiting. In some embodiments, the first temperature (which may be used to drive the modification of material on the substrate surface) may be higher than the second temperature (which may be used to drive the etching of the modified material on the substrate surface), for example, as described in connection with Figures 2 and 4.

[0263] In some embodiments, the heating and maintaining operations may be based on empirical and measured data, such as empirically derived temperature drift of the device, such as the window of the pedestal. As mentioned above, the window may retain heat during processing and act as an independent heater to the substrate. To account for this drift, adjustments may be made to the substrate heater, such as decreasing the overall power delivered to the LEDs of the substrate heater during maintaining and etching operations, such as 1005, 1105, 1007, and 1107. These adjustments may be linear or non-linear, such as stepped or curvilinear. This may also include adjustments to only some of the LEDs, such as one or more of the independently controlled zones. For example, the center of the window may generate the most heat over time because it may not be able to remove heat, while the edges of the window generate the least heat because some of this heat is transferred to the pedestal. Thus, to maintain uniform heating, one or more independently controllable zones of the LEDs in the center of the substrate heater may be lowered to account for the increased heat in the center of the window. This allows for the same heat to be transferred to the substrate in the center region with heat generated by both the window and the substrate heater. Similarly, one or more independently controllable zones of LEDs in the outer regions of the substrate heater can be lowered or kept the same to account for additional heating caused by the outer edge of the window, if present.

[0264] As mentioned above, in some embodiments, each LED may be individually controllable, and in some such embodiments, a single LED may be adjusted to emit more or less light than one or more other LEDs. This adjustment may be made to account for hot or cold spots on the substrate. For example, a spot on the wafer may be hotter or colder in temperature than other parts of the substrate, and one LED located under or proximate to that spot on the substrate may be adjusted to adjust the temperature of that spot. This may include decreasing the light emitted by one LED to decrease the temperature of that spot, or increasing the light emitted by one LED to increase the temperature of that spot.

[0265] The techniques provided herein may also include feedback control loops to adjust operational parameters such as the power of one or more zones of LEDs. These feedback loops may be implemented during the heating, maintaining, and etching operations described herein. This may include using one or more of the sensors described herein to determine the temperature at the edge and one or more locations within the substrate and adjusting the substrate heater based on these measurements.

[0266] FIG. 16 illustrates a third technique according to disclosed embodiments, where operations 1201 through 1211 are the same as operations 1001 through 1011, except that the technique here measures the substrate temperature during one or more of these operations and adjusts the substrate heater based on these measurements. The temperature measurement is represented by operation 1221, and the adjustment(s) is represented by operation 1223. The adjustment to the substrate heater may include increasing or decreasing the power to one or more of the independently controllable zones of the LEDs, including all of the LEDs. For example, as described above with respect to FIG. 9, a temperature sensor on the substrate support may indicate that an edge of the substrate has reached or is above a first temperature during one or more of operations 1203, 1205, and 1207, and the power delivered to all of the LEDs may be decreased to reduce the temperature of the substrate. This may indicate a determination that at least one of the sensors indicates that the temperature of the substrate is above a certain threshold, e.g., above a first temperature. In another example, only one of the substrate supports may indicate that the substrate temperature is higher than a first temperature, and adjustments can be made to an independently controllable LED zone around that one sensor to reduce heat delivered to that location rather than the entire substrate.

[0267] Similarly, the pyrometer described above can also detect the temperature of the substrate at a location on the substrate, such as the center of the substrate. This temperature measurement can also be used alone or in combination with a temperature sensor in the substrate support to adjust the substrate heater. For example, the pyrometer may indicate that the center of the substrate is higher than a first temperature, and adjustments can be made to the independently controllable LED zones around the center of the substrate, or to the entire substrate, to reduce the temperature of the substrate at this location. Although these examples are made with respect to decreasing the power of the LEDs, adjustments are not limited to such examples and the power of one or more independently controllable LED zones can be adjusted to increase the temperature at one or more locations on the substrate.

[0268] Another technique may measure light emitted by the LEDs and adjust one or more independently controllable LED zones based on the measurement. This may include emitting emitted visible light from the LEDs having a wavelength between 400 nm and 800 nm, and measuring one or more indicators of the visible light emitted by the LEDs using one or more sensors configured to detect the visible light emitted from the LEDs. These sensors may include the photodetectors described above. Based on this measured visible light, the power of one or more LED zones may be adjusted.

[0269] In some embodiments, the apparatus described herein may include a controller configured to control various aspects of the apparatus to implement the techniques described herein. For example, referring again to FIG. 5, the apparatus 100 includes a controller 131 (which may include one or more physical or logical controllers) communicatively connected to and controlling some or all of the operation of the 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, for example, flow rates and durations, substrate heating units, substrate cooling units, loading and unloading of substrates in the chamber, thermal floating of the substrate, and process gas units when the disclosed embodiments are implemented. In some embodiments, the apparatus may have a switching time of up to about 500 ms, or up to about 750 ms. The switching time may depend on the flow chemistry, the selected recipe, the reactor configuration, and other factors.

[0270] In some implementations, the controller 131 is part of an apparatus or system that may be part of the examples described above. Such a system or apparatus may include semiconductor processing equipment, including one or more processing tools, one or more chambers, one or more processing platforms, and / or specific processing components (gas flow systems, substrate heating units, substrate cooling units, etc.). These systems may be integrated with electronics for controlling operations before, during, and after processing of semiconductor wafers or substrates. The electronics may be referred to as "controllers" and may control various components or sub-parts of one or more systems. The controller 131 may be programmed to control any of the processes disclosed herein, including delivery of process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow settings, fluid delivery settings, position and operation settings, wafer transport to and from the tool, and other transport tools and / or load locks connected or interfaced to the particular system, depending on the processing parameters and / or type of system.

[0271] In general, the controller 131 may be defined as an electronic device having various integrated circuits, logic, memory and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute the program instructions (e.g., software). The program instructions may be instructions communicated to the controller in the form of various individual settings (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for the system. The operational parameters may, in some embodiments, be part of a recipe defined by a process engineer 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 the wafer.

[0272] The controller 131 may be part of or coupled to a computer that is integrated with, coupled to, or otherwise networked to the system, or a combination thereof, in some implementations. For example, the controller may be in all or part of a "cloud" or fab host computer system, which may enable remote access of wafer processing. The computer may enable remote access to the system to monitor the current progress of a fabrication operation, examine the history of past fabrication operations, examine trends or performance indicators from multiple fabrication operations, modify parameters of a current process, set up processing operations following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) may provide a process recipe to the system over a network, which may include a local network or the Internet. The remote computer may include a user interface that allows for entry or programming of parameters and / or settings, which are communicated from the remote computer to the system. In some examples, the controller 131 receives instructions in the form of data that 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 being performed and the type of tool the controller is configured to interface with or control. Thus, as described above, the controller 131 may be distributed, such as by including one or more individual controllers networked together and operating toward a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes is one or more integrated circuits on the chamber that communicate with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer) that are combined to control the process on the chamber.

[0273] As described above, depending on the process operation or operations being performed by the equipment, the controller 131 may communicate with one or more of other equipment circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools located throughout the factory, a main computer, another controller, or tools used in material transport to carry containers of wafers to and from tool locations and / or load ports within a semiconductor manufacturing factory.

[0274] Also as described above, the controller is configured to implement the techniques described above. This may include having the substrate transport robot position the substrate on the plurality of substrate supports in the chamber, delivering power to the LEDs to heat the substrate to a first temperature, such as 100° C. to 600° C., such that the LEDs emit visible light having a wavelength of 400 nm to 800 nm, and flowing an etchant gas into the chamber to etch the substrate. This may also include cooling the substrate by flowing a cooling gas over the substrate while the substrate is supported only by the plurality of substrate supports, and / or vertically moving the pedestal such that the substrate is offset a first non-zero distance from a faceplate of the gas distribution unit, thereby transferring heat from the substrate to the faceplate by non-contact radiation. This may also include controlling chemicals delivered to the reaction chamber as described herein.

[0275] conclusion Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it is apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the process, system and apparatus of the present embodiments. Thus, the present embodiments should be considered as illustrative and not restrictive, and the embodiments should not be limited to the details given herein.

Claims

1. 1. A method of etching a substrate, comprising: a. providing the substrate in a reaction chamber, the substrate comprising a target material to be partially or wholly removed from the substrate during etching; b. providing a gas mixture to the reaction chamber and exposing the substrate to the gas mixture, the gas mixture being in a vapor phase; i. a halogen source; ii. an organic solvent and / or water; iii. an additive comprising a hydrogen fluoride complexing chemical; and iv. Carrier gas providing a gas mixture comprising: c. providing thermal energy to the reaction chamber to drive a reaction that partially or fully etches the target material from the substrate, wherein the substrate is not exposed to a plasma during etching; A method comprising:

2. 2. The method of claim 1 , prior to (b), providing a second gas mixture to the reaction chamber and exposing the substrate to thermal energy and the second gas mixture, wherein the thermal energy drives a second reaction between the second gas mixture and the target material to form a modified target material; The method of claim 1, wherein the reaction in (c) etches the modified target material, thereby partially or completely etching the target material.

3. 2. The method of claim 1, wherein the hydrogen fluoride complexing chemical comprises at least one group selected from the group consisting of an amine group, a urea group, a phosphine group, an alkyl group, an imidazole group, a heterocyclic aliphatic group, a heterocyclic aromatic group, an ether group, or a combination thereof.

4. 4. The method of claim 3, wherein the hydrogen fluoride complexing chemical comprises the urea group.

5. 5. The method of claim 4, wherein the hydrogen fluoride complexing chemical comprises N,N'-dimethylpropylene urea (DMPU).

6. 4. The method of claim 3, wherein the hydrogen fluoride complexing chemical comprises an alkyl substituted ammonium compound.

7. 7. The method of claim 6, wherein the hydrogen fluoride complexing chemical comprises a compound selected from the group consisting of tetraethylammonium, tetrabutylammonium, and combinations thereof.

8. 4. The method of claim 3, wherein the hydrogen fluoride complexing chemical comprises a heteroaromatic amine-containing compound.

9. 9. The method of claim 8, wherein the hydrogen fluoride complexing chemical comprises melamine.

10. 4. The method of claim 3, wherein the hydrogen fluoride complexing chemical comprises a heterocyclic aliphatic compound and / or a cyclic ether compound.

11. 11. The method of claim 10, wherein the hydrogen fluoride complexing chemical comprises tetrahydrofuran.

12. 4. The method of claim 3, wherein the hydrogen fluoride complexing chemical comprises an alkyl substituted imidazole compound, an alkyl substituted ether compound, and / or an alkyl substituted phosphine compound.

13. 13. The method of claim 12, wherein the hydrogen fluoride complexing chemical comprises a compound selected from the group consisting of dialkylimidazolium, dimethyl ether, trialkylphosphine, and combinations thereof.

14. 1. An apparatus for etching a substrate, comprising: a reaction chamber configured to withstand subatmospheric pressure; a substrate support configured to support the substrate during etching; an inlet for introducing a gas mixture into the reaction chamber, the gas mixture being in a vapor phase; and an outlet for removing vapor phase species from the reaction chamber; A controller; The controller comprises: (a) providing the substrate in the reaction chamber, the substrate including a target material to be partially or wholly removed from the substrate during etching; (b) providing the gas mixture to the reaction chamber and exposing the substrate to the gas mixture, the gas mixture being in a vapor phase; i. a halogen source; ii. an organic solvent and / or water; iii. an additive comprising a hydrogen fluoride complexing chemical; iv. A carrier gas; providing said gas mixture, (c) providing thermal energy to the reaction chamber to drive a reaction that partially or fully etches the target material from the substrate, wherein the substrate is not exposed to a plasma during etching; and The apparatus is configured to cause

15. 15. The device of claim 14, wherein the hydrogen fluoride complexing chemical comprises at least one group selected from the group consisting of an amine group, a urea group, a phosphine group, an alkyl group, an imidazole group, a heterocyclic aliphatic group, a heterocyclic aromatic group, an ether group, or a combination thereof.

16. 16. The method of claim 15, wherein the hydrogen fluoride complexing chemical comprises the urea group.

17. 17. The method of claim 16, wherein the hydrogen fluoride complexing chemical comprises N,N'-dimethylpropylene urea (DMPU).

18. 16. The method of claim 15, wherein the hydrogen fluoride complexing chemical comprises an alkyl substituted ammonium compound.

19. 20. The method of claim 18, wherein the hydrogen fluoride complexing chemical comprises a compound selected from the group consisting of tetraethylammonium, tetrabutylammonium, and combinations thereof.

20. 16. The method of claim 15, wherein the hydrogen fluoride complexing chemical comprises a heteroaromatic amine-containing compound.

21. 21. The method of claim 20, wherein the hydrogen fluoride complexing chemical comprises melamine.

22. 16. The method of claim 15, wherein the hydrogen fluoride complexing chemical comprises a heterocyclic aliphatic compound and / or a cyclic ether compound.

23. 23. The method of claim 22, wherein the hydrogen fluoride complexing chemical comprises tetrahydrofuran.

24. 16. The method of claim 15, wherein the hydrogen fluoride complexing chemical comprises an alkyl substituted imidazole compound, an alkyl substituted ether compound, and / or an alkyl substituted phosphine compound.

25. 25. The method of claim 24, wherein the hydrogen fluoride complexing chemical comprises a compound selected from the group consisting of dialkylimidazolium, dimethyl ether, trialkylphosphine, and combinations thereof.

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