Precise and selective etching of semiconductor materials

Abstract

The present invention provides a method and apparatus for etching a semiconductor substrate to remove a target material from the substrate surface. [Solution] A thermal technology that does not rely on the use of plasma, the method involves supplying a specific gas mixture to a reaction chamber and reacting it with a target material. The gas mixture may include a mixture of a halogen source such as hydrogen fluoride (HF), an organic solvent and / or water, an additive, and a carrier gas. Multiple different materials may be used for the organic solvent and / or the additive.

Description

[Technical Field]

[0001] Built-in by reference As part of this application, a PCT application is filed concurrently with this specification. As confirmed in the concurrently filed PCT application, each application on which this application claims benefit or priority is incorporated herein by reference in its entirety for any purpose. [Background technology]

[0002] Semiconductor fabrication involves many different types of processes. Some types of processes involve depositing material onto a substrate surface. Other types of processes involve etching material from the substrate surface. In some cases, such etching is performed selectively to target the removal of one or more materials on the substrate.

[0003] The description of background art provided herein is intended to provide a general context for this disclosure. The work of the inventors named herein, as well as aspects of this specification that may not be considered prior art at the time of filing, are not, expressly or implicitly, considered prior art to this disclosure. [Overview of the Initiative]

[0004] Various embodiments herein relate to methods and apparatus for etching semiconductor substrates. In one embodiment of the disclosed embodiments, a method for etching a substrate is provided, the method comprising: (a) providing a substrate in a reaction chamber, the substrate comprising a target material to be partially or completely removed from the substrate during etching; (b) supplying a gas mixture into the reaction chamber while the pressure of the reaction chamber is about 0.2 to 10 Torr, thereby exposing the substrate to the gas mixture, the gas mixture being a vapor phase and comprising (i) a halogen source such as hydrogen fluoride (HF), (ii) an organic solvent and / or water, (iii) an additive, and (iv) a carrier gas; and (c) supplying thermal energy to the reaction chamber to induce a reaction that partially or completely etches the target material from the substrate, the substrate not being exposed to plasma during etching.

[0005] In some embodiments, the method may further include, prior to (b), supplying a second gas mixture into a reaction chamber and exposing the substrate to thermal energy and the second gas mixture, the thermal energy causing a second reaction between the second gas mixture and the target material to form a modified target material, and the reaction in (c) etching the modified target material, thereby partially or completely etching the target material.

[0006] Various materials may be used for organic solvents and / or water. In certain realizations, the organic solvents and / or water may include alcohols. In some cases, the alcohols 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. In these or other cases, the organic solvents and / or water may include laboratory solvents. Laboratory solvents may be selected from the group consisting of acetonitrile, dichloromethane, carbon tetrachloride, and combinations thereof. In these or other cases, the organic solvents and / or water may include ketones. In some cases, the ketones may be selected from the group consisting of acetone, acetophenone, and combinations thereof. In these or other cases, the organic solvents and / or water may include water. In some such cases, the organic solvents and / or water do not contain any organic solvents. In these or other embodiments, the organic solvent and / or water may include an alkane. In some embodiments, the alkane may be selected from the group consisting of pentane, hexane, octane, cyclopentane, cyclohexane, and combinations thereof. In these or other embodiments, the organic solvent and / or water may include an aromatic solvent. In some cases, the aromatic solvent is an aromatic solvent selected from the group consisting of toluene and benzene. In these or other embodiments, the organic solvent and / or water may include an ether. In some such cases, the ether may include tetrahydrofuran. In these or other embodiments, the organic solvent and / or water may include a nitrile. In some cases, the nitrile may include acetonitrile.

[0007] In various embodiments, the carrier gas may include a gas selected from the group consisting of N2, He, Ne, Ar, Kr, and Xe.

[0008] Multiple different materials and types of materials may be used as additives. In some realizations, the additive may include a heterocycle. In some embodiments, the heterocycle may be a heterocyclic aromatic compound. In some such embodiments, the heterocyclic aromatic compound may include a heterocyclic aromatic compound selected from the group consisting of picoline, pyridine, pyrrole, imidazole, thiophene, N-methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolinic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, azulene, and combinations thereof. In some embodiments, the heterocycle may be a halogen-substituted aromatic compound. In some cases, the halogen-substituted aromatic compound may include a halogen-substituted aromatic compound selected from the group consisting of 4-bromopyridine, chlorobenzene, 4-chlorotoluene, and fluorobenzene. In some embodiments, the heterocycle may be a heterocyclic aliphatic compound. In some such cases, the heterocyclic aliphatic compound may be pyrrolidine.

[0009] In some embodiments, the additive may include an amine. In some cases, the amine may be an amine selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1,2-ethylenediamine, aniline, aniline derivatives, N-ethyldiisopropylamine, tert-butylamine, guanidine, and combinations thereof. In some embodiments, the amine may include a fluoroamine. In one example, the fluoroamine is 4-trifluoromethylaniline. In certain realizations, the additive may include an amino acid. In some cases, the amino acid may be an amino acid selected from the group consisting of histidine and alanine.

[0010] In some embodiments, the additive may include an organophosphorus compound. In some such embodiments, the organophosphorus compound may include a phosphazene. In these or other embodiments, the additive may include an oxidizing agent. In some embodiments, the oxidizing agent may include an oxidizing agent selected from the group consisting of hydrogen peroxide, sodium hypochlorite, tetramethylammonium hydroxide, and combinations thereof. In these or other embodiments, the additive may include a bifluoride source. In some cases, the bifluoride source includes a bifluoride source selected from the group consisting of ammonium fluoride, hydrogen fluoride, buffer oxide etching mixture, pyridine hydrogen fluoride, and combinations thereof. In various embodiments, the bifluoride source reacts before or after delivery to the reaction chamber to produce HF2 - It may form

[0011] In some embodiments, the additive may include an aldehyde. In some embodiments, the aldehyde may include an aldehyde selected from the group consisting of acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other embodiments, the additive may include a carbene. In these or other embodiments, the additive may include an organic acid. In some embodiments, the organic acid may include an organic acid selected from the group consisting of formic acid, acetic acid, and combinations thereof.

[0012] In some embodiments, a specific halogen or combination of halogen sources may be used. For example, in some embodiments, the halogen source is selected from the group consisting of hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), fluorine (F2), chlorine (Cl2), bromine (Br2), chlorine trifluoride (ClF3), nitrogen trifluoride (NF3), nitrogen trichloride (NCl3), nitrogen tribromide (NBr3), and combinations thereof. In some embodiments, the halogen source is an organic halide. In some such cases, the organic halide may be selected from the group consisting of fluoroform (CHF3), chloroform (CHCl3), bromoform (CHBr3), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), carbon tetrabromide (CBr4), perfluorobutene (C4F8), perchlorobutene (C4Cl8), and combinations thereof. In some embodiments, the halogen source is a silicon halide. In some such embodiments, the silicon halide is selected from the group consisting of silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), silicon tetrabromide (SiBr4), and SiX6-containing compounds (where X is a halogen), and combinations thereof. In some embodiments, the halogen source is a metal halide. In some such cases, the metal halide is selected from the group consisting of 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).

[0013] In various embodiments, the composition of the gas mixture may be controlled. For example, the ratio of two or more components in the gas mixture may be controlled. In some embodiments, the additive is about 0.1 to 5% (by weight) of the total amount of the additive and the organic solvent and / or water. In these or other embodiments, the volume ratio of the halogen source to the additive may be 10 or less.

[0014] The methods described herein may be used to etch specific materials, and in some cases, the etching is carried out selectively. For example, in some embodiments, the target material is an oxide, and the substrate further comprises a second material different from the target material, and (c) comprises selectively etching the target material with respect to the second material. In some embodiments, the target material is silicon oxide, and the second material is silicon nitride. In some embodiments, the target material is silicon oxide, and the second material is silicon (Si) or silicon germanium (SiGe).

[0015] Further embodiments of the embodiments described herein provide an apparatus for etching a substrate, the apparatus comprising: (a) a reaction chamber configured to withstand a pressure of about 0.2 to 10 Torr in the reaction chamber; (b) a substrate support configured to support the substrate during etching; (c) an inlet for introducing a gas mixture, which is the vapor phase, into the reaction chamber; (d) an outlet for removing chemical species of the vapor phase from the reaction chamber; and (e) a controller configured to implement any of the methods described herein.

[0016] These and other embodiments are further described below with reference to the drawings. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 is a flowchart illustrating a method for etching a semiconductor substrate according to a specific embodiment.

[0018] [Figure 2] Figure 2 is a flowchart illustrating a periodic method for etching a semiconductor substrate according to a specific embodiment.

[0019] [Figure 3A] Figure 3A shows a semiconductor substrate being processed according to the method described in Figure 2. [Figure 3B]Figure 3B shows a semiconductor substrate being processed according to the method described in Figure 2. [Figure 3C] Figure 3C shows a semiconductor substrate being processed according to the method described in Figure 2.

[0020] [Figure 4] Figure 4 shows how the temperature can be changed over time to realize the method in Figure 2.

[0021] [Figure 5] Figure 5 shows an exemplary cross-sectional side view of an apparatus according to the disclosed embodiment.

[0022] [Figure 6] Figure 6 shows a top view of a substrate heater with multiple LEDs.

[0023] [Figure 7] Figure 7 shows a top view of another substrate heater with multiple LEDs.

[0024] [Figure 8] Figure 8 shows the pedestal from Figure 5, along with additional features in various embodiments.

[0025] [Figure 9] Figure 9 shows the substrate support of Figures 5 and 8 according to the disclosed embodiment.

[0026] [Figure 10] Figure 10 shows a plan view of an exemplary first faceplate.

[0027] [Figure 11] Figure 11 shows a plan view of an exemplary second faceplate.

[0028] [Figure 12] Figure 12 shows graphs of four different active cooling experiments.

[0029] [Figure 13] Figure 13 provides an exemplary temperature control sequence.

[0030] [Figure 14] Figure 14 shows a first technique for heat treatment according to the disclosed embodiment.

[0031] [Figure 15] Figure 15 shows a second technique for heat treatment according to the disclosed embodiment.

[0032] [Figure 16] Figure 16 shows a third technique for heat treatment according to the disclosed embodiment.

[0033] [Figure 17] Figure 17 shows graphs of silicon absorption at various wavelengths and temperatures.

[0034] [Figure 18] Figure 18 shows the pedestal from Figure 8, along with additional features in various embodiments. [Modes for carrying out the invention]

[0035] The following description contains numerous specific details to provide a complete understanding of the presented embodiments. The disclosed embodiments may be carried out without some or all of these specific details. In other cases, well-known process operations are not necessarily described in detail so as not to unnecessarily obscure the disclosed embodiments. The disclosed embodiments will be described in relation to specific embodiments, but it will be understood that this is not intended to limit the disclosed embodiments.

[0036] In various embodiments herein, a semiconductor substrate is etched using a mixture of vapor-phase reactants comprising (1) a halogen source such as hydrogen fluoride, (2) an organic solvent and / or water, (3) an additive, and (4) a carrier gas. In this disclosure, the terms “vapor phase” and “gas phase” are used interchangeably. As will be further described below, the additive may have specific properties or a specific composition. The substrate can be etched at low pressure using thermal energy, for example, in a vacuum reaction chamber. In such a case, the substrate is not exposed to plasma during the etching reaction. The substrate may be etched in a selective manner such that one or more materials are targeted for removal, while other materials are etched to a lesser extent. One advantage of the disclosed technique is that it achieves a high degree of selectivity during etching. Another advantage of the disclosed technique is that it provides extremely precise control of the etching rate and etching removal amount, particularly compared to other thermally induced etching processes.

[0037] The techniques described herein may be used to etch various substrate materials in several different situations. Often, the substrate contains two or more different materials exposed on the substrate surface. In a selective etching process, one of these materials may be the target to be removed relative to another of these materials. In some realizations, the substrate contains a first material and a second material, and the first material is selectively etched relative to the second material. In other cases, the substrate may contain only a single exposed material, so the etching does not need to be selective. In yet another case, the substrate may contain multiple different materials, all of which are removed without the need for selectivity. The first material and / or the second material on the substrate may 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.), carbonoxides (e.g., silicon carbonate, etc.), and so on. 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. Typically, a high-k dielectric material is a dielectric material having a higher dielectric constant compared to silicon dioxide, and a low-k dielectric material is a dielectric material having a lower dielectric constant compared to silicon dioxide. Silicon dioxide has a dielectric constant of 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 dioxide, fluorine-doped silicon dioxide, and spin-on organic polymer dielectric materials, such as polyimide, polynorbene, and benzocyclobutene. 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 may be provided in various structures, as required for a particular application.The techniques described herein are widely applicable to many different applications. A further explanation of the etching selectivity of a first material (e.g., silicon dioxide) over a second material (e.g., silicon nitride) is given below.

[0038] In a particular embodiment, the method described herein may be used in connection with trimming silicon fins. Figures 3A to 3C, further described below, illustrate such embodiments. In another particular embodiment, the method described herein may be used in connection with removing native oxides on gate-all-around structures. Many other applications are possible.

[0039] One advantage of the disclosed technology is that it enables extremely precise control of the etching rate. Such etching rate control is significantly improved compared to other thermal (e.g., non-plasma) etching techniques. Another advantage of the disclosed technology is that it achieves a very high degree of etching selectivity. For example, oxide materials can be etched with a higher degree of selectivity compared to nitride materials. Other materials can be etched in a similarly selective manner.

[0040] As described above, the substrate is etched using a specific set of chemicals. These 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 supplied to a reaction chamber and exposed to the substrate while in the vapor phase. Appropriate hardware may be provided to ensure that the reactants are properly vaporized before and during delivery to the reaction chamber, as will be further described below. Two or more of the reactants may be mixed before delivery to the reaction chamber. In other embodiments, each of the reactants may be delivered to the reaction chamber individually, for example, on separate lines or at separate times.

[0041] Halogen source The halogen source may be any halogen-containing compound present in the vapor phase at the processing temperature (for example, X-containing, where X is fluorine (F), chlorine (Cl), bromine (Br), or iodine (I)). 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 realizations, the halogen source is an organic halide, examples of which include fluoroform (CHF3), chloroform (CHCl3), bromoform (CHBr3), carbon tetrafluoride (CF4), carbon tetrachloride (CCl4), carbon tetrabromide (CBr4), perfluorobutene (C4F8), and perchlorobutene (C4Cl8). In some realizations, the halogen source is a silicon halide, such as silicon tetrafluoride (SiF4), silicon tetrachloride (SiCl4), silicon tetrabromide (SiBr4), and SiX6-containing compounds such as H2SiX6. In some realizations, the halogen source is a metal halide, such as 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.

[0042] In the following description, various examples include HF as the halogen source. However, any suitable halogen source may be used. The volume and mass percentages listed for HF can be used for other halogen sources. In some embodiments, two or more halogen sources may be used.

[0043] Organic solvents Alcoholic beverages: In certain embodiments, the organic solvent may be an alcohol. The alcohol can be an alcohol having the chemical formula of X-C(R) n (OH)-Y, n is 1, each X and Y can be independently selected from hydrogen, -[C(R 1 )2] m -C(R 2 )3, or OH, and each R 1 and R 2 can be 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 can be independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0044] In some embodiments, each R, R 1 , and R 2This 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 alcohol may be further substituted with one or more substituents such as alkoxy, amide, amine, thioether, thiol, acyloxy, silyl, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0045] In other embodiments, at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3, or if R is hydrogen and m is 1, then the alcohol can be a C3 alcohol. For example, if at least one R 1 and one R 2 If R is absent, the C3 alcohol may be a C3 alkenol (e.g., allyl alcohol). In other examples, R and one R 2 If the C3 alcohols can form a ring together (for example, a cyclic aliphatic ring), the C3 alcohol may be cyclopropanol or 2-cyclopropenol.

[0046] In other embodiments, at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3, or if R is hydrogen and m is 2, then the alcohol can be a C4 alcohol. For example, if at least one R 1 and one R 2 If R is absent, the C4 alcohol may be a C4 alkenol (e.g., 2-buten-1-ol or 3-buten-1-ol). In other examples, R and one R 2 If the elements can form a ring together (e.g., a cyclic aliphatic), then the C4 alcohol may be a C4 cyclic alcohol (cyclobutanol or cyclopropylmethanol). In yet another example, if neither X nor Y is an OH group, then the C4 alcohol may be a C4 branched alcohol (e.g., 2-butanol, isobutanol, or tert-butanol).

[0047] In some cases, X = OH and Y = -[C(R 1 )2] m -C(R 2 )3 If the alcohol is a diol, then the alcohol may be a diol. Otherwise, at least one X or Y is -[C(R 1 )2] m -C(R 2 )3, and at least one R 1 Is OH or one R 2 An alcohol can be a diol if R is an OH group or if R=OH. Exemplary diols include, but are not limited to, 1,4-butanediol and propylene-1,3-diol.

[0048] In other cases, if X=Y=OH, the alcohol can be a triol. In yet other cases, if X=R=OH, the alcohol can be a triol. In some cases, at least one of X or Y is -[C(R 1 )2] m -C(R 2 )3, and one R 1and at least one R 2 However, if it is OH, the alcohol can be a triol. In other cases, R=OH, and X=-[C(R 1 )2] m -C(R 2 )3, and one R 1 and at least one R 2 If the OH group is present, the alcohol may be a triol. Exemplary triols include, but are not limited to, glycerol or its glycerol derivatives.

[0049] In certain embodiments, if R = cycloheteraliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, the alcohol may be a heterocyclyl alcohol (e.g., a heterocyclyl substituted with more hydroxyls of optional substitution, e.g., 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 However, if the alcohol is a cycloheteraliphatic, heterocyclyl, heteroaryl, alkyl-heterocyclyl, alkenyl-heterocyclyl, alkynyl-heterocyclyl, heteroalkyl-heterocyclyl, heteroalkenyl-heterocyclyl, or heteroalkynyl-heterocyclyl, then the alcohol may be a heterocyclyl alcohol.

[0050] 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.

[0051] Laboratory solvents: In these or other cases, the organic solvent may include laboratory solvents, such as acetonitrile, dichloromethane, carbon tetrachloride, or a combination thereof.

[0052] Ketones: In some embodiments, the organic solvent may be a ketone.

[0053] Organic solvents are also X-[C(O)] n It can be a ketone having the chemical formula -Y, n is an integer between 1 and 2. Each X and Y is -C(R 1 )3, -R 2 , or -[C(R 3 )2] m -C(O)-R 4 It can be selected independently from each R 1 , R 2 , R 3 , and R 4 This can be independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. R 3 and R 4 Each of the atoms to which X and Y are bonded can optionally form a cyclic aliphatic or cyclic heteroaliphatic structure, m is an integer between 0 and 10.

[0054] Several embodiments, each R 1 , R 2 , R 3 , and R 4 These are, 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 aldehydes (-C(O)H), oxo (=O), alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof. An example of a ketone is acetone.

[0055] In some embodiments, the organic solvent can be a cyclic ketone if X and Y, together with the atoms to which they are bonded, form a cyclic aliphatic or cyclic heteroaliphatic molecule. Exemplary cyclic ketones include cyclohexanone, cyclopentanone, and the like.

[0056] In other embodiments, at least one of X or Y is -[C(R3 )2] m -C(O)-R 4 In this case, the organic solvent may be a diketone. Exemplary diketones include diacetyl, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, acetylacetone, acetonylacetone, and their halogenated forms, such as hexafluoroacetylacetone.

[0057] In a further embodiment, at least one of X or Y is -[C(R 3 )2] m -C(O)-R 4 If X and Y, together with the atoms to which they are each bonded, form a cyclic aliphatic or cyclic heteroaliphatic molecule, the organic solvent can be a cyclic diketone. Exemplary cyclic diketones include dimedone and 1,3-cyclohexanedione.

[0058] In some cases, if X = -CH3, then the organic solvent is Y = -C(R 1 )3, can be set to at least one R 1 C 2-10 These are hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl propyl ketone, methyl butyl ketone, hydroxyacetone, and the like.

[0059] In some cases, if X = -CH3, then the organic solvent is Y = -R 2 , can have, and at least one R 2 C2 alkenyl, C 3-10 These materials may be aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. Exemplary materials may include methyl vinyl ketone, methyl propyl ketone, methyl butyl ketone, and the like.

[0060] In other cases, if at least one of X or Y is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic, the organic solvent can be an aromatic ketone. Exemplary materials include acetophenone, benzophenone, benzylacetone, 1,3-diphenylacetone, and cyclopentylphenyl ketone.

[0061] In certain embodiments, the organic solvent may be selected from acetone and acetophenone. Similarly, one or more additional ketones and / or other organic solvents described herein may be provided.

[0062] Alkan: In some embodiments, the organic solvent may be an alkane. In certain embodiments, the alkane is a compound with the general chemical formula C n H 2n+2 The alkane may be acyclic branched or unbranched hydrocarbon having ,. Exemplary cyclic 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.

[0063] Aromatic solvents: In some embodiments, the organic solvent may be an aromatic solvent. As used herein, “aromatic” means a cyclic conjugated group or moiety of 5 to 15 ring atoms, having a single ring (e.g., phenyl) or a plurality of fused rings (e.g., naphthyl, indolyl, or pyrazolopyridinyl) in which at least one ring is aromatic, unless otherwise specified. That is, at least one ring, and optionally a plurality of fused rings, have a continuous, delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Hückel's rule (4n+2). Bonding to the parent structure is typically via the aromatic moiety of the fused ring system. In some cases, the aromatic solvent may be selected from toluene and benzene.

[0064] ether: In some embodiments, the organic solvent may be an ether having the chemical formula of X-O-Y, or X-O-[C(R)2] n -O-Y, 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, and can 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, p is an integer from 1 to 10, X and Y, together with the atoms to which each is attached, can optionally form a cyclic heteroaliphatic group.

[0065] In some embodiments, each R, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6This 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, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0066] In some embodiments, when X and Y, together with the atoms to which each is attached, form a cyclic heteroaliphatic group, the organic solvent is a cyclic ether such as an acetal, dioxane, or dioxolane. In some embodiments, when n = 1 and each R = H, X and Y, when introduced together, form a 6-membered, 7-membered, 8-membered, 9-membered, or 10-membered ring. Exemplary ethers include, but are not limited to, 1,3-dioxolane or derivatives thereof. In other embodiments, when n = 2 and R = H, X and Y form a 7-membered, 8-membered, 9-membered, or 10-membered ring. Exemplary ethers include, but are not limited to, 1,4-dioxane or derivatives 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.

[0067] In other embodiments, when at least one of X or Y is aromatic, the organic solvent can be an aromatic ether. Exemplary aromatic ethers include anisole, diphenyl ether, and the like.

[0068] In some embodiments, when at least one of X or Y is cycloaliphatic, the organic solvent can be a cycloalkyl ether. Exemplary cycloalkyl ethers include cyclopentylmethyl ether, cyclohexylmethyl ether, and the like.

[0069] In other embodiments, when at least one of X or Y is -[C(R 4 )2-O] p -C(R 6)3. If so, the organic solvent can be a glycol ether. Exemplary glycol ethers include diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, poly(ethylene glycol) dimethyl ether, etc., and include monoethers and diethers of ethylene glycol with methyl, ethyl, propyl, and butyl, etc.

[0070] Nitriles: In some cases, the organic solvent is a nitrile having the chemical formula R-C≡N, where R is aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic.

[0071] In certain embodiments, R can optionally be substituted with a hydroxyl group (for example, in one example, R can be CH3-CH(OH)-CH2-, and the organic solvent is CH3-CH(OH)-CH2-CN).

[0072] An example of the nitrile is the aforementioned acetonitrile.

[0073] In some embodiments, the organic solvent may include two or more organic solvents or two or more types of organic solvents described herein. In some embodiments, water may be supplied instead of or in addition to the organic solvent.

[0074] Carrier gas The carrier gas can 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.

[0075] Additive The additive may be selected from several different types of additives. For example, the additive may be a heterocyclic compound, a heterocyclic aromatic compound, a halogen-substituted heterocyclic aromatic compound, a heterocyclic aliphatic compound, an amine, a fluoroamine, an amino acid, an organophosphorus compound, an oxidizing agent, a bifluoride source, an ammonia, an aldehyde, a carbene, or an organic acid. In some cases, two or more additives 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. - This is an example of a Lewis acid that forms a reaction. In some cases, the additive may belong to two or more of the categories listed above. In various embodiments, the additive serves the purpose of accelerating the reaction rate and improving reaction selectivity.

[0076] Heterocyclic aromatic compounds: In certain embodiments, the additive is a heterocyclic aromatic compound. The term “aromatic” is defined above. Unless otherwise specified, a heterocyclic aromatic compound is an aromatic compound containing a five-membered, six-membered, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Examples of heterocyclic aromatic compounds that may be used include, but are not limited to, picoline, pyridine, pyrrole, imidazole, thiophene, N-methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolinic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, and azulene. In some cases, the heterocyclic aromatic compound may be methylated. In some cases, the heterocyclic aromatic compound may follow Hückel's 4n+2 rule. In some cases, the additive is a halogen-substituted aromatic compound. Halogen-substituted aromatic compounds are aromatic compounds that contain 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, and fluorobenzene.

[0077] Heterocyclic aliphatic compounds: In some embodiments, the additive is a heterocyclic aliphatic compound. As used herein, “aliphatic” means a compound with at least one carbon atom to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 This refers to hydrocarbon groups having ), including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), and their cyclic versions, and further including linear and branched configurations, as well as total stereoisomers and positional isomers. Heterocyclic aliphatic compounds are aliphatic compounds containing a 5-membered, 6-membered, or 7-membered ring, unless otherwise specified, containing one, two, three, or four noncarbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). Exemplary heterocyclic aliphatic compounds include pyrrolidine and piperidine.

[0078] Amine: In some embodiments, the additive is NR 1 R 2 R 3 It is an amine having the chemical formula, R 1 , R 2 , and R 3 Each of these is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof. R 1 and R 2 Each atom can optionally form a cyclic heteroaliphatic with the atoms to which it is bonded. R 1 , R 2 , and R 3 Each atom can optionally form a cyclic heteroaliphatic group with the atoms to which it is bonded.

[0079] Several embodiments, each R 1 , R2 , and R 3 This 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 amine may be further substituted with one or more substituents such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0080] In some embodiments, R 1 , R 2 , and R 3 If at least one of the elements is aliphatic, haloaliphatic, haloheteroaliphatic, or heteroaliphatic, the additive is an alkylamine. The alkylamine may include dialkylamines, trialkylamines, and their derivatives. Exemplary alkylamines include dimethylisopropylamine, N-ethyldiisopropylamine, trimethylamine, dimethylamine, methylamine, triethylamine, and t-butylamine.

[0081] In other embodiments, R 1 , R 2 , and R 3 If at least one of them contains hydroxyl, the additive is an alcoholamine. For example, R 1 , R 2 , and R 3 At least one of these is an aliphatic group substituted with one or more hydroxyls. Exemplary alcoholamines include 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-(dipropylamino)ethanol, 2-(dibutylamino)ethanol, N-ethyldiethanolamine, N-tertbutyldiethanolamine, and the like.

[0082] In some embodiments, R 1 and R 2 However, if each atom, together with the atoms to which it is bonded, forms a cyclic heteroaliphatic, the additive may be a cyclic amine. Exemplary cyclic amines include piperidine, N-alkylpiperidine (e.g., N-methylpiperidine, N-propylpiperidine, etc.), pyrrolidine, N-alkylpyrrolidine (e.g., N-methylpyrrolidine, N-propylpyrrolidine, etc.), morpholine, N-alkylmorpholine (e.g., N-methylmorpholine, N-propylmorpholine, etc.), piperazine, N-alkylpiperazine, N,N-dialkylpiperazine (e.g., 1,4-dimethylpiperazine), and the like.

[0083] In other embodiments, R 1 , R 2 , and R 3 If at least one of them contains an aromatic compound, the additive is an aromatic amine. In some embodiments, R 1 , R 2 , and R 3 At least one of them is aromatic, aliphatic-aromatic, or heteroaliphatic-aromatic. In other embodiments, R 1 and R 2 Both contain aromatic compounds. In yet another embodiment, R 1 and R 2 , and optionally R 3These are cycloheteraliphatic atoms, each of which is aromatic along with the atom to which it is bonded. Exemplary aromatic amines include aniline, histamine, pyrrole, pyridine, imidazole, pyrimidine, and their derivatives.

[0084] In some embodiments, the additive may include an amine selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1,2-ethylenediamine, aniline (and aniline derivatives such as N,N-dimethylaniline), N-ethyldiisopropylamine, tert-butylamine, and combinations thereof.

[0085] In some embodiments, the additive may include a fluoroamine, which is an amine having one or more fluorinated substituents. Exemplary fluoroamines that may be used include, but are not limited to, 4-trifluoromethylaniline.

[0086] In some embodiments, the additive is of the chemical formula, R 1 NC (NR) 2 )-NR 3 It may be a nitrogen analog of carbonic acid having ,. Exemplary additives may include, but are not limited to, guanidine or its derivatives.

[0087] In some embodiments, the additive may be a relatively low molecular weight amine, for example, having a molecular weight of less than 200 g / mol or less than 100 g / mol in certain embodiments. In some embodiments, high molecular weight amines may be used, including amines having long-chain compounds with aromatic rings and / or heterocyclic compounds.

[0088] amino acid: In some embodiments, the additive may include an amino acid. The amino acid may have the chemical formula R-CH(NR'2)-COOH. Each R and R’ is independently hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0089] Exemplary amino acids that may be used include, but are not limited to, histidine, alanine, and derivatives thereof.

[0090] Organic phosphorus compounds: In some embodiments, the additive may include an organic phosphorus compound. The organic phosphorus compound may be a phosphate ester, phosphoric amide, phosphonic acid, phosphinic acid, phosphonate, phosphinate, phosphine oxide, phosphine imide, or phosphonium salt. Exemplary organic phosphorus compounds include phosphoric acid and trialkyl phosphates. In some cases, the organic phosphorus compound is a phosphazene. A phosphazene is an organic phosphorus compound containing phosphorus(V) with a double bond between P and N. A phosphazene may have the chemical formula 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 may have the chemical formula n (X is a halide, alkoxide, or amide). Other types of phosphazenes may be used as desired.

[0091] Oxidizing agents: In some embodiments, the additive includes an oxidizing agent. As used herein, an oxidizing agent is a material having the ability to oxidize another substance (e.g., accept electrons from another substance). Examples of oxidizing agents that may be used may include, but are not limited to, hydrogen peroxide, sodium hypochlorite, and tetramethylammonium hydroxide.

[0092] Bifluoride source: In some embodiments, the additive includes a bifluoride source. The bifluoride source is bifluoride (HF2- The material contains or produces ) . Examples of bifluoride sources that may be used include, but are not limited to, ammonium fluoride, aqueous HF solutions, gaseous HF, buffer oxide etching mixtures (e.g., a mixture of HF and a buffer such as ammonium fluoride), and pyridine hydrogen fluoride. In some embodiments, the bifluoride source (and / or one or more of the other additives listed herein) reacts before or after being delivered to the reaction chamber to produce HF2 - It is possible to form this.

[0093] aldehyde: In some embodiments, the additive includes an aldehyde having the chemical formula X-[C(O)]-H, X is hydrogen, -R 1 , -C(R 2 )3, or -[C(R 3 )2] m -C(O)H can be selected from, each R 1 , R 2 , and R 3 m is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, and m is an integer between 0 and 10.

[0094] Several embodiments, each R 1 , R 2 , and R 3These are, 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, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof.

[0095] In some embodiments, X is aromatic, and the additive may be an aromatic aldehyde. Exemplary aromatic aldehydes include benzaldehyde, 1-naphthaldehyde, phthalaldehyde, and the like.

[0096] In other embodiments, if X = aliphatic, the additive may be an aliphatic aldehyde. Exemplary aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isovalerylaldehyde, and the like.

[0097] In yet another embodiment, X = -[C(R 3 )2]m The additive may be a dialdehyde if it is -C(O)H and m is between 0 and 10, or if X is an aliphatic or heteroaliphatic compound substituted with -C(O)H. Exemplary dialdehydes include glyoxal, phthalaldehyde, glutaraldehyde, malondialdehyde, succinaldehyde, and the like.

[0098] In some embodiments, the aldehyde used as an additive may be selected from the group consisting of acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde. In these or other cases, the aldehyde used as an additive may be selected from the aldehydes discussed in this section and the aldehydes discussed in the section on organic solvents.

[0099] Carven: In some embodiments, the additive includes a carbene. The carbene may have the chemical formula X-(C:)-Y. Each of X and Y is 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, can be selected independently from R 1 and R 2 Each of these is independently selected from hydrogen, hydroxyl, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof, where m is an integer from 0 to 10. R 1 and R 2 Each atom can optionally form a cyclic heteroaliphatic group with the atom to which it is bonded. X and Y, together with the atoms to which they are bonded, can optionally form a cyclic aliphatic group or a cyclic heteroaliphatic group.

[0100] Furthermore, additives have a chemical formula, R 1 -C + (R) New R 2 It can be a carbenium cation having R, R 1 , and R 2 Each of these is independently selected from hydrogen, aliphatic, haloaliphatic, haloheteroaliphatic, heteroaliphatic, aromatic, aliphatic-aromatic, heteroaliphatic-aromatic, or any combination thereof.

[0101] Several operating mechanisms, each R, R 1 , and R 2This 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 carbene may be further substituted with one or more substituents such as alkoxy, amide, amine, hydroxyl, thioether, thiol, acyloxy, silyl, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized 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 these can be selected independently.

[0102] In some embodiments, the additive may be a halocarbene, where at least one of X or Y is a halo. Exemplary and non-limiting halocarbenes include dihalocarbenes such as dichlorocarbene and difluorocarbene.

[0103] In some embodiments, both X and Y are -NR 1 R 2 In that case, the additive may be diaminocarbene. For example, R 1 and R 2Each of these is independently aliphatic. Exemplary diaminocarbenes include bis(diisopropylamino)carbene, etc.

[0104] In other embodiments, at least one of X or Y is -NR 1 R 2 and R in X or Y 1 or R 2 However, if each of these forms a cyclic heteroaliphatic group with the nitrogen atom to which it is bonded, the additive can be a cyclic diaminocarbene. Exemplary cyclic diaminocarbenes include bis(N-piperidyl)carbene and bis(N-pyrrolidinyl)carbene.

[0105] For example, X=Y=-NR 1 R 2 , and R from X 1 Base and R from Y 2 If the groups, together with the nitrogen atom to which each of them is bonded, form a cycloheteraliphatic group, the additive is an N-heterocyclic carbene. Exemplary N-heterocyclic carbenes include imidazole-2-ylidene (e.g., 1,3-dimesitylimidazole-2-ylidene, 1,3-dimesityl-4,5-dichloroimidazole-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene, 1,3-di-tert-butylimidazole-2-ylidene, etc.), imidazolidine-2-ylidene (e.g., 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene), triazol-5-ylidene (e.g., 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene), etc.

[0106] In some embodiments, for example, X = -NR 1 R 2 , and Y=-SR 2 And R from X 1 Base and R from Y 2If the groups, together with the nitrogen atoms to which each of them is bonded, form a cyclic heteroaliphatic group, the additive is an acyclic thioalkylaminocarbene. Exemplary cyclic thioalkylaminocarbenes include thiazole-2-ylidene (e.g., 3-(2,6-diisopropylphenyl)thiazole-2-ylidene).

[0107] In some embodiments, X = -NR 1 R 2 Y = -C(R 2 )3, and R from X 1 Base and R from Y 2 The additive is a cyclic alkylaminocarbene when the groups, together with the atoms to which each of them is bonded, form a cyclic heteroaliphatic group. Exemplary cyclic alkylaminocarbenes include pyrrolidine-2-ylidene (e.g., 1,3,3,5,5-pentamethyl-pyrrolidine-2-ylidene) and piperidine-2-ylidene (e.g., 1,3,3,6,6-pentamethyl-piperidine-2-ylidene).

[0108] Further exemplary carbenes and their derivatives include compounds having a thiazole-2-ylidene moiety, a dihydroimidazole-2-ylidene moiety, an imidazole-2-ylidene moiety, a triazole-5-ylidene moiety, or a cyclopropenylidene moiety. Further other carbenes and carbene analogs include aminothiocarbene compounds, aminooxycarbene compounds, diaminocarbene compounds, heteroaminocarbene compounds, 1,3-dithioliumcarbene compounds, mesoionic carbene compounds (e.g., imidazoline-4-ylidene compounds, 1,2,3-triazolylidene compounds, pyrazolinylidene compounds, tetrazole-5-ylidene compounds, isoxazole-4-ylidene compounds, thiazole-5-ylidene compounds, etc.), cyclic alkylaminocarbene compounds, boronylidene compounds, silylene compounds, stannylene compounds, nitrene compounds, phosphinidene compounds, foilcarbene compounds, etc. Further exemplary carbenes include dimethylimidazole-2-ylidene, 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole-2-ylidene, (phosphanyl)(trifluoromethyl)carbene, bis(diisopropylamino)carbene, bis(diisopropylamino)cyclopropenylidene, 1,3-dimesityl-4,5-dichloroimidazole-2-ylidene, and 1,3-diadamantylimidazole This includes -2-ylidene, 1,3,4,5-tetramethylimidazole-2-ylidene, 1,3-dimethitylimidazole-2-ylidene, 1,3-dimethitylimidazole-2-ylidene, 1,3,5-triphenyltriazol-5-ylidene, bis(diisopropylamino)cyclopropenylidene, bis(9-antryl)carbene, norbornene-7-ylidene, dihydroimidazole-2-ylidene, methylidenecarbene, etc.

[0109] Organic acids: In some embodiments, the additive includes an organic acid. The organic acid may have the chemical 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, cyclic aliphatic, aryl, aldehyde, ketone, ester, carboxylic acid, acyl, halide acyl, cyano, halogen, sulfonate, nitro, nitroso, quaternary amine, pyridinyl (or pyridinyl in which the nitrogen atom is functionalized with an aliphatic or aryl group), alkyl halide, or any combination thereof. In certain realizations, the organic acid may be selected from formic acid and acetic acid.

[0110] Replace with: Any of the exemplary materials described herein include unsubstituted and / or substituted forms of the compound. Non-limiting examples of substituents include one, two, three, four, or more substituents independently selected from the following groups: (1) C 1-6 Alkoxy (for example, -OR, where R is C) 1-6 (2) C 1-6 Alkyl sulfinyl (for example, -S(O)-R, where R is C) 1-6 It is alkyl; (3)C 1-6Alkyl sulfonyl (for example, -SO2-R, where R is C) 1-6 (4) Alkyl; (e.g., -C(O)NR 1 R 2 , or -NHCOR 1 , and R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, each, together with the nitrogen atom to which it is bonded, forms a heterocyclyl group as defined herein; (5) aryl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aliloyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 (12) Cycloalkyl; (13) Halo; (14) Heterocyclyl (e.g., as defined herein, e.g., a five-membered, six-membered, or seven-membered ring containing one, two, three, or four noncarbon heteroatoms); (15) Heterocyclyloxy (e.g., -OR, where R is a heterocyclyl as defined herein); (16) Heterocyclyl (e.g., -C(O)-R, where R is a heterocyclyl as defined herein); (17) Hydroxyl (e.g., -OH); (18) N-Protected Amino; (19) Nitro (e.g., -NO2); (10) Oxo (e.g., =O); (11) C 1-6 Thiokalkoxy (for example, -SR, where R is C) 1-6 (21) Alkyl; (22) Thiol (e.g., -SH); (23)-CO2R 1 , and R 1 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C)1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (23)-C(O)NR 1 R 2 , and R 1 and R 2 Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (24)-SO2R 1 , and R 1 (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (25)-SO2NR 1 R 2 , and R 1 and R 2 Each of them is (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (26)-NR is independently selected from the group consisting of (1) aryl; and (26)-NR 1 R 2 , and R 1 and R 2 Each of these is (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 Alkenil, (e)C 2-6 Alkinyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18Aryl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (It is an aryl compound), (h)C 3-8 Cycloalkyl, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 3-8 Independently selected from the group consisting of (cycloalkyl groups), in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl or sulfonyl group.

[0111] In certain embodiments, the additive functions as a proton acceptor, and HF2 - The formation of may be promoted. In some such cases, HF2 - This may involve actively etching one or more materials on the substrate, such as oxide materials or other materials.

[0112] etching The chemical species of the vapor phase delivered to the reaction chamber may be collectively referred to as the gas mixture. The non-inactive chemical species delivered to the reaction chamber (e.g., reactants other than the carrier gas) may be collectively referred to as the reaction mixture. The gas mixture includes the reaction mixture and the carrier gas. In some cases, the reaction mixture and / or gas mixture may have a specific composition. For example, hydrogen fluoride or other halogen sources may be provided in the reaction 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 sources may be provided in the gas mixture at a concentration of about 0.5–20% by volume. Organic solvents and / or water may be provided in the reaction mixture at a concentration of about 10–100% by volume, or about 10–99% by volume. In these or other cases, organic solvents and / or water may be provided in the gas mixture at a concentration of about 0–10% by volume. Additives may be provided in the reaction 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, as well as the organic solvent and / or water, are mixed such that the additive constitutes about 0.1–5% by weight of the mixture of the additive and the organic solvent and / or water. The reaction mixture may be characterized by the additive being about 0.1–5% by weight of the total amount of the additive and the organic solvent and / or water, regardless of the order of mixing.

[0114] In the same or alternative embodiments, the reaction mixture may be characterized by the volume ratio of the halogen source to the additive. As will be further described below, in some embodiments, selectivity can be controlled by the volume ratio of the halogen source to the additive, and selectivity increases as the amount of additive increases (and therefore as the ratio decreases). In some embodiments, the ratio of halogen source to additive is 10 or less. In some embodiments, the ratio of halogen to source additive is greater than 10.

[0115] According to various embodiments, the reaction mixture may contain a halogen source, an alcohol, and an amine, with the amine being 0.1 to 5% by weight of the total amount of the alcohol and amine. In some embodiments, the volume ratio of the halogen source to the amine is 10 or less. In other embodiments, the volume ratio of the halogen source to the 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 described above, in various implementations, etching may be selective to certain materials on the substrate compared to other materials. In other implementations, etching may be inselective to multiple materials on the substrate.

[0117] In some embodiments, oxides are selectively etched against nitrides and one or more epitaxial materials, such as Si and SiGe. The etching selectivity of the reaction mixture for silicon oxide can be controlled by the amount of additives in the mixture. For example, very high etching selectivity (at least 50:1) of silicon oxide for silicon nitride is achieved by reaction mixtures where the halogen source:additive ratio (e.g., HF:pyridine) is 10 or less. Etching selectivity decreases with increasing ratio, and consequently, no selectivity is observed in the absence of additives. Similar effects may be observed for the etching selectivity of silicon oxide for Si and SiGe.

[0118] In some embodiments, low-k materials are selectively etched against barrier materials. For example, carbon-doped silicon oxide materials may be selectively etched against barrier materials such as titanium nitride layers.

[0119] Examples of target materials, second materials, and etching chemicals for achieving selective or non-selective etching of a target material with respect to a second material are listed in the table below. The percentages in parentheses indicate the approximate etching rate of the target material with respect to the second material. [Table 1]

[0120] Figure 1 shows a flowchart of a method for etching a substrate according to various embodiments described herein. The method begins with operation 101, in which the substrate is provided into a reaction chamber. The substrate contains one or more materials on which 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 the composition and other properties as described herein. Similarly, one or more processing variables, such as pressure, temperature, absolute flow rate and relative flow rate, may be controlled as described herein. In operation 105, the substrate is exposed to the gas mixture, and as a result of such exposure, one or more of the materials on the substrate are etched. These operations may overlap in time.

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

[0122] In some embodiments, one or more processing variables may be controlled during etching. For example, the pressure in the reaction chamber may be controlled to about 10 Torr or less, for example, to about 0.2 to 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 placed 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 to a temperature of, for example, about 20 to 500°C during etching. In some embodiments, the temperature of one or more of these elements may be repeated between two or more different temperatures. An example will be discussed further below in relation to Figures 2 to 4. In some embodiments, the duration of exposure of the substrate to the gas mixture may be controlled. For example, this duration may be about 0 to 10 minutes. In some cases, the duration of exposure to the gas mixture may control the degree to which the material on the substrate is etched. In other cases, the etching process may be self-limiting, and as a result, extending the exposure duration does not lead to further etching of the target material. One such example is discussed in relation to Figures 2-4.

[0123] Figure 2 is a flowchart illustrating a periodic etching method that may be used in some embodiments. Figures 3A–3C show partially fabricated semiconductor substrates undergoing the processing method of Figure 2. Figure 4 shows how the temperature can be controlled during the method of Figure 2 in a particular embodiment. For clarity, these figures will be discussed later with reference to one another.

[0124] The method in Figure 2 begins with operation 201, where a substrate 301 is provided to the reaction chamber. As described above, the substrate may have one or more materials on it. One or more of these materials may be targeted for removal compared to other materials present on the substrate. In the particular example shown in Figure 3A, the substrate 301 includes silicon fins 302, as well as an exposed spacer layer (not shown) containing a spacer material such as SiN, SiCN, SiCO, or SiCON. In this example, it is desired to trim the fins so that they become 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 contains one or more chemical species that will function to modify one or more materials present on the substrate surface 301. In some cases, the modification form involves the formation of an oxide material. In these or other cases, the modification involves fluorination of the exposed material, adsorption of organic molecules on the exposed material, etc. Various surface modification forms are available. In relation to the embodiments shown in Figures 3A to 3C, the first reactant or first gas mixture contains an oxidizing species (e.g., O2 or other oxidizing species) that will function to modify the silicon fins 302 to form silicon oxide 303, as will be described later. In many embodiments, the first reactant or first gas mixture may selectively modify one or more of the materials on the substrate 301 compared to other materials on the substrate 301. For example, in relation to Figures 3A to 3C, the oxygen supplied to the reaction chamber selectively modifies the silicon fins 302, resulting in virtually no modification (or no modification at all) occurring on other materials such as spacer materials.

[0126] In step 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 substrate surface 301. In the embodiments shown in Figures 3A to 3C, as a result of exposure to the first reactant or the first gas mixture, the exposed surface of the silicon fin 302 is modified to form a thin layer of silicon oxide 303, as shown in Figure 3B.

[0127] In operation 207, a second gas mixture is supplied to the reaction chamber. The second gas mixture may have the composition and properties 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, and the modified material formed in operation 205 (e.g., silicon oxide 303 in Figure 3B) is etched away. If the substrate 301 contains multiple exposed materials, the modified material formed in operation 205 can be selectively etched away compared to other materials such as spacer material. At this point, a portion of the material targeted for removal has been modified and is then removed from the substrate 301. In relation to Figures 3A-3C, this means that the silicon fin 302 is now smaller / narrower than before, as shown in Figure 3C.

[0129] Next, in operation 211, it is determined whether the etching process is sufficiently complete (for example, whether a sufficient amount of material has been removed from the substrate 301). This determination may be based on many factors, including time, etching rate, and the thickness of the material being removed. If it is determined that a sufficient amount of material has been removed from the substrate 301, the method is complete. Otherwise, the method is repeated, starting from operation 203. The surface modification and etching steps are repeated alternately until it is determined that a sufficient amount of material has been removed from the substrate 301.

[0130] Figure 4 illustrates how the temperature inside the reaction chamber may be controlled over time when performing the iterative etching techniques described in Figures 2 and 3A-3C. Although Figure 4 is described in relation to Figures 2 and 3A-3C, the embodiments are not limited in this way, and it should be understood that the temperature control described in Figure 4 may be used in many different situations, including those utilizing other structures and / or other materials.

[0131] The temperature may be controlled by controlling the temperatures of, for example, the substrate support, showerhead, reaction chamber walls, and process gas, using multiple techniques that may be combined as desired. The process sequence in Figure 4 begins at time t0. At this time, the substrate is introduced into the reaction chamber as described in operation 201 in Figure 2. The substrate contains one or more materials that will be removed or etched. For example, in the example in Figures 3A-3C, the substrate 301 contains silicon fins 302 that will be trimmed as shown in Figure 3A. At time t0, the temperature is at the initial starting temperature, T0. Between times t0 and t1, as shown in Figure 4, the temperature increases from T0 to T2. Since the temperature is increasing gradually, this period may be called the gradual increase period. Between times t1 and t2, the temperature is maintained at T2. This period may be called the modification period. During the modification period, the substrate is exposed to a first reactant or a first gas mixture, as described in operations 203 and 205 of Figure 2, thereby modifying one or more materials on the substrate. In some cases, the first reactant or the first gas mixture may begin to flow into the reaction chamber at or immediately thereafter at time t1, while in other cases, the first reactant or the first gas mixture may begin to flow into the reaction chamber at a time between t0 and t1. In the examples of Figures 3A to 3C, during the modification period, the exposed portion of the silicon fin 302 is converted to silicon oxide 303, as shown in Figure 3B.

[0132] Returning to Figure 4, between t2 and t3, the temperature decreases from T2 to T1. As shown in the figure, T1 may be greater than T0. In other cases, T1 may be less than or equal to T0. The period between times t2 and t3 may be called the cooling period because the temperature is decreasing. Between times t3 and t4, the temperature is maintained at T1. This period may be called the vapor etching period. During the vapor etching period, the substrate is exposed to the second gas mixture, as described in operations 207 and 209 in Figure 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 immediately thereafter at time t3, while in other cases, the second gas mixture may begin to flow into the reaction chamber at a time between t2 and t3. In relation to Figures 3A to 3C, silicon dioxide 303 may be partially or completely removed during the vapor etching period. After the vapor etching period, the substrate 301 may be in the state shown in Figure 3C. By time t3, at least a portion of the material that was the target to be removed (e.g., the silicon fins 302 in Figures 3A-3C) has been removed. However, additional etching may be desired. Thus, at time t4, it is determined whether the etching is sufficiently complete, as described in operation 211 in Figure 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 Figure 4). If the etching is not yet sufficiently complete, the method may return to the initial stage, as indicated by arrow 400. At this point, the temperature is raised to T2 in a second gradual increase period, followed by a second modification period, a second cooling period, and a second vapor etching period. The gradual increase period, modification period, cooling period, and vapor etching period may be repeated as desired until the etching is sufficiently complete.

[0133] As shown in Figure 4, when periodic etching techniques are used, the temperature may repeat between two or more different settings. In some embodiments, the temperature during the modification period (e.g., T2) may be approximately 100–500°C, while the temperature during the vapor etching period (e.g., T1) may be approximately 20–200°C. In various implementations, the substrate is not exposed to plasma during any of the periods described in Figure 4. In such embodiments, both the reactions occurring during the modification period and the reactions occurring during the vapor etching period are induced by thermal energy.

[0134] The etching operations described in Figures 2 to 4 may be carried out in a self-limiting manner. For example, a second gas mixture supplied during the vapor etching period may selectively etch the reformed material formed during the reforming period. Once the reformed material is consumed, the etching rate may decrease significantly or even stop as a result of the selective nature of the etching process. Thus, the etching process may be considered self-limiting in certain embodiments. Furthermore, 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 spacer material or other materials that are not the etching target. In some cases, the material targeted for removal may be etched with a selectivity of at least about 2:1 with respect to other materials on the substrate, such as spacer material. As used herein, an etching process having a selectivity of at least about 2:1 is considered selective. In some embodiments, the selectivity may be at least about 1000:1.

[0135] Additional definitions This section presents additional definitions that may be used herein. Some of the materials described in this section may overlap with materials presented elsewhere in this specification.

[0136] In this specification, the terms “acyl” and “alkanoyl” are used interchangeably and refer to a linear, branched, or cyclic configuration of a group of 1, 2, 3, 4, 5, 6, 7, 8, or more carbon atoms, which can be saturated, unsaturated, aromatic, or a combination thereof, or in which hydrogen is bonded to the parent molecule group via a carbonyl group, as defined herein. Examples of such groups include formyl, acetyl, propionyl, isobutyryl, and butanoyl. 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" refers to the -C(O)H group.

[0139] "Aliphatic" refers to a molecule with at least one carbon atom to 50 carbon atoms (C) 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10 The term refers to hydrocarbon groups having ), including alkanes (or alkyls), alkenes (or alkenyls), alkynes (or alkynyls), and cyclic versions thereof, and further including linear and branched configurations, as well as total stereoisomers and positional isomers.

[0140] "Alkyl-aryl," "alkenyl-aryl," and "alkynyl-aryl" mean aryl groups as defined herein, which are bonded to or can be bonded (or attached to or can be attached) to a parent molecule group by an alkyl, alkenyl, or alkynyl group as defined herein. Alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted or unsubstituted. For example, alkyl-aryl, alkenyl-aryl, and / or alkynyl-aryl groups may be substituted by one or more substituents for alkyl, alkenyl, alkynyl, and / or aryl as described herein. Exemplary unsubstituted alkyl-aryl groups have 7 to 16 carbon atoms (C 7-16 Alkyl-aryl groups, and also 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 It is an aryl group. An example of an unsubstituted alkenyl-aryl group is one having 7 to 16 carbon atoms (C 7-16 Alkenyl-aryl compounds, and also those having an alkenyl group with 2 to 6 carbon atoms and an aryl group with 4 to 18 carbon atoms (i.e., C 2-6 Alkenil-C 4-18 It is an aryl group. An example of an unsubstituted alkynyl-aryl group is one having 7 to 16 carbon atoms (C 7-16 Alkynyl-aryl) and also having an alkynyl group having 2 to 6 carbon atoms and an aryl group having 4 to 18 carbon atoms (i.e., C 2-6 Alkinyl-C 4-18In 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" is a group of at least two carbon atoms to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10 Alkenyl groups are defined as unsaturated monovalent hydrocarbons having at least one carbon-carbon double bond, which can be derived by removing one hydrogen atom from one carbon atom of the parent alkene. Alkenyl groups can be branched, linear, cyclic (e.g., cycloalkenyl), cis, or trans (e.g., E or Z). Exemplary alkenyls are those having one or more double bonds, optionally substituted with C 2-24 The group contains alkyl groups. The alkenyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogen atoms to form a suitable bond to the parent molecule group or a suitable bond between the parent molecule group and another substituent. The alkenyl group can also be substituted or unsubstituted. For example, the alkenyl group can be substituted with one or more substituents, as described herein for alkyl groups.

[0142] "Alkyl-heteroaryl" means a heteroaryl group as defined herein bonded to a parent molecule 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" mean heterocyclyl groups as defined herein, which are bonded to or can be bonded (or attached to or can be attached) to a parent molecule population by an alkyl, alkenyl, or alkynyl group as defined herein. Alkyl-heterocyclyl groups, alkenyl-heterocyclyl groups, and / or alkynyl-heterocyclyl groups may be substituted or unsubstituted. For example, alkyl-heterocyclyl, alkenyl-heterocyclyl, and / or alkynyl-heterocyclyl groups may be substituted by one or more substituents as described herein with respect to alkyl, alkenyl, alkynyl, and / or heterocyclyl. Exemplary unsubstituted alkyl-heterocyclyl groups have 2 to 16 carbon atoms (C 2-16 Alkyl-heterocyclyl) and also 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 It is a heterocyclyl. An example of an unsubstituted alkenyl-heterocyclyl group is one having 3 to 16 carbon atoms (C 3-16 Alkenyl-heterocyclyl) and 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 Alkenil-C 1-18 It is a heterocyclyl group. An example of an unsubstituted alkynyl-heterocyclyl group is one having 3 to 16 carbon atoms (C 3-16 Alkynyl-heterocyclyl) and also 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 Alkinyl-C 1-18(heterocyclyl). In 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. Alkoxy groups may be substituted or unsubstituted. For example, an alkoxy group may be substituted with one or more substituents, as described herein for alkyls. 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 Contains an alkoxy group.

[0145] "Alkyl" refers to a group of at least one carbon atom to 50 carbon atoms (C 1-50 ), for example, 1 to 25 carbon atoms (C 1-25 ) or 1 to 10 carbon atoms (C 1-10Alkyl groups are saturated monovalent hydrocarbons having 1 to 24 carbon atoms, and saturated monovalent hydrocarbons can be derived by removing one hydrogen atom from one carbon atom of a parent compound (e.g., an alkane). Alkyl groups can be branched, linear, or cyclic (e.g., cycloalkyl). Exemplary alkyl groups 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, and tetracosyl. Alkyl groups can also be substituted or unsubstituted. Alkyl groups can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecule group or a suitable bond between the parent molecule group and another substituent. For example, an alkyl group can be substituted with one, two, or three substituents independently selected from the following groups, or, in the case of an alkyl group having two or more carbon atoms, with four substituents: (1) C 1-6 Alkoxy (for example, -OR, where R is C) 1-6 (2) C 1-6 Alkyl sulfinyl (for example, -S(O)-R, where R is C) 1-6 It is alkyl; (3)C 1-6 Alkyl sulfonyl (for example, -SO2-R, where R is C) 1-6 (4) Alkyl; (e.g., -C(O)NR 1 R 2 , or -NHCOR 1 , and here, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2However, each, together with the nitrogen atom to which it is bonded, forms a heterocyclyl group as defined herein; (5) aryl; (6) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl); (7) aliloyl (e.g., -C(O)-R, where R is aryl); (8) azide (e.g., -N3); (9) cyano (e.g., -CN); (10) aldehyde (e.g., -C(O)H); (11) C 3-8 (12) Cycloalkyl; (13) Halo; (14) Heterocyclyl (e.g., as defined herein, e.g., a five-membered, six-membered, or seven-membered ring containing one, two, three, or four noncarbon heteroatoms); (15) Heterocyclyloxy (e.g., -OR, where R is a heterocyclyl as defined herein); (16) Heterocyclyl (e.g., -C(O)-R, where R is a heterocyclyl as defined herein); (17) Hydroxyl (e.g., -OH); (18) N-Protected Amino; (19) Nitro (e.g., -NO2); (10) Oxo (e.g., =O); (11) C 1-6 Thioalkoxy (e.g., -SR, where R is alkyl); (21) Thiol (e.g., -SH); (22)-CO2R 1 , and R 1 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (23)-C(O)NR 1 R 2 , and R 1 and R 2 Each of them independently consists of (a) hydrogen and (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18Selected from the group consisting of (aryls); (24)-SO2R 1 , and R 1 (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (25)-SO2NR 1 R 2 , and R 1 and R 2 Each of them is (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (26)-NR is independently selected from the group consisting of (1) aryl; and (26)-NR 1 R 2 , and R 1 and R 2 Each of these is (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 Alkenil, (e)C 2-6 Alkinyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (It is an aryl compound), (h)C 3-8 Cycloalkyl, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 3-8A group independently selected from the group consisting of (cycloalkyl groups), and in one embodiment, no two groups are bonded 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 groups). In some embodiments, the unsubstituted alkyl group is C 1-3 , C 1-6 , C 1-12 , C 1-16 , C 1-18 , C 1-20 , or C 1-24 It is an alkyl group.

[0146] "Alkylsulfinyl" means an alkyl group bonded to a parent molecule group via an -S(O)- group, as defined herein. In some embodiments, the unsubstituted alkylsulfinyl group is C 1-6 or C 1-12 It is an alkylsulfinyl group. In other embodiments, the alkylsulfinyl group is -S(O)-R, where R is an alkyl group as defined herein.

[0147] "Alkylsulfonyl" means an alkyl group bonded to a parent molecule group via a -SO2- group, as defined herein. In some embodiments, the unsubstituted alkylsulfonyl group is C 1-6 or C 1-12 It is an alkylsulfonyl group. In other embodiments, the alkylsulfonyl group is -SO2-R, where R is an optionally substituted alkyl (e.g., an optionally substituted C as described herein). 1-12 (This includes alkyl, haloalkyl, or perfluoroalkyl compounds.)

[0148] "Alkynyl" is a compound containing at least two carbon atoms to 50 carbon atoms (C 2-50 ), for example, 2 to 25 carbon atoms (C 2-25 ) or 2 to 10 carbon atoms (C 2-10Alkynnyl groups are defined as unsaturated monovalent hydrocarbons having at least one carbon-carbon triple bond, which can be derived by removing one hydrogen atom from one carbon atom of the parent alkyne. Alkynnyl groups can be branched, linear, or cyclic (e.g., cycloalkynyl). Exemplary alkynyls are those having one or more triple bonds, optionally substituted with C 2-24 The alkyl group is included. The alkynyl group can be cyclic or acyclic, as exemplified by ethynyl, 1-propynyl, and the like. The alkynyl group can be monovalent or polyvalent (e.g., divalent) by removing one or more hydrogens to form a suitable bond to the parent molecule group or a suitable bond between the parent molecule group and another substituent. The alkynyl group can also be substituted or unsubstituted. For example, the alkynyl group can be substituted with one or more substituents, as described herein for alkyl groups.

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

[0150] "Amine" is -NR 1 R 2 , meaning, here, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, together with the nitrogen atom to which each is bonded, they 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 L is an alkyl group as defined herein, and R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, together with the nitrogen atom to which each is bonded, they form a heterocyclyl group as defined herein. In other embodiments, the aminoalkyl group is -LC(NR 1 R 2 )(R 3 )-R 4 L is a covalent bond or an alkyl group as defined herein; R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, together with the nitrogen atom to which each is bonded, they form a heterocyclyl group as defined herein; R 3 and R 4 Each of them is independently H or alkyl as defined herein.

[0152] Unless otherwise specified, "aromatic" refers to 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. That is, at least one ring, and optionally multiple fused rings, have a continuous, delocalized π-electron system. Typically, the number of out-of-plane π-electrons corresponds to Hückel's rule (4n+2). Bonding to the parent structure is typically via the aromatic moiety of the fused ring system.

[0153] "Aryl" is a group of at least 5 to 15 carbon atoms (C 5-15 ), for example, 5 to 10 carbon atoms (C 5-10 ) means an aromatic carbocyclic group having a single ring or multiple fused rings, wherein the fused ring may or may not be aromatic if the bonding site to the remaining position of the compound disclosed herein is via an atom of the aromatic carbocyclic group. The aryl group may be substituted with one or more groups other than hydrogen, e.g., aliphatic, heteroaliphatic, aromatic, other functional groups, or any combination thereof. Exemplary aryl groups include, but are not limited to, benzyl, naphthalene, phenyl, biphenyl, and phenoxybenzene. The term aryl also includes heteroaryls, which are defined as groups containing an aromatic group in which at least one heteroatom is incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Similarly, the term nonheteroaryl, 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 one, two, three, four, or five substituents independently selected from the group consisting of: (1) C 1-6 Alkanoyl (for example, -C(O)-R, where R is C) 1-6 (2) C 1-6 Alkyl; (3)C 1-6 Alkoxy (for example, -OR, where R is C) 1-6 It is alkyl; (4)C 1-6Alkoxy-C 1-6 Alkyl (for example, -LOR, where each of L and R is independently C) 1-6 It is alkyl; (5)C 1-6 Alkyl sulfinyl (for example, -S(O)-R, where R is C) 1-6 It is alkyl; (6)C 1-6 Alkylsulfinyl- 1-6 Alkyl (e.g., -LS(O)-R), where each of L and R is independently C 1-6 It is alkyl; (7)C 1-6 Alkyl sulfonyl (for example, -SO2-R, where R is C) 1-6 It is alkyl; (8)C 1-6 Alkylsulfonyl-C 1-6 Alkyl (for example, -L-SO2-R, where L and R are independently C) 1-6 (9) alkyl; (10) aryl; (10) amine (e.g., -NR) 1 R 2 , and here, R 1 and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, together with the nitrogen atom to which each is bonded, they 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 And, L 1 C 1-6 It is alkyl; L2 is covalent or C 1-6 It is alkyl; R 1 and R 2Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, together with the nitrogen atom to which each is bonded, they form a heterocyclyl group as defined herein; R 3 and R 4 Each of these is independently H or C 1-6 (12) Alkyl; (13) C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (14) Aryl (e.g., -C(O)-R, where R is aryl); (15) Azide (e.g., -N3); (16) Cyano (e.g., -CN); (17) C 1-6 Azidoalkyl (for example, -L-N3, where L is C) 1-6 (18) Aldehydes (e.g., -C(O)H); (19) Aldehydes -C 1-6 Alkyl (for example, -LC(O)H, where L is C) 1-6 It is alkyl; (20)C 3-8 Cycloalkyl; (21)C 1-6 Alkyl-C 3-8 Cycloalkyl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 3-8 (22) Halo; (23) C 1-6 Haloalkyl (e.g., -L) 1 -X, or -L 2 -C(X)(R 1 )-R 2 , and L 1 C 1-6 Alkyl; L 2 is a covalent bond or C 1-6 It is alkyl; X is fluoro, bromo, chloro, or iodine; R 1 and R 2 Each of these is independently H or C 1-6(1) alkyl; (24) heterocyclyl (e.g., as defined herein, e.g., a five-membered, six-membered, or seven-membered ring containing one, two, three, or four noncarbon heteroatoms); (25) heterocyclyloxy (e.g., -OR, where R is a heterocyclyl as defined herein); (26) heterocycliroyl (e.g., -C(O)-R, where R is a heterocyclyl as defined herein); (27) hydroxyl (-OH); (28) C 1-6 Hydroxyalkyl (e.g., -L) 1 -OH, or -L 2 -C(OH)(R 1 )-R 2 , and L 1 C 1-6 Alkyl; L 2 is covalent or alkyl; R 1 and R 2 Each of these independently has an 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 , and L 1 C 1-6 Alkyl; L 2 is covalent or alkyl; R 1 and R 2 Each of these independently has an H or C as defined herein. 1-6 (31) Alkyl; (32) N-protected amino-C 1-6 Alkyl; (33) Oxo (e.g., =O); (34) C 1-6 Thiokalkoxy (for example, -SR, where R is C) 1-6 Alkyl; (35) Thio-C 1-6 Alkoxy-C 1-6 Alkyl (for example, -LSR, where each of L and R is independently C) 1-6 Alkyl; (36)-(CH2) r CO2R1 , where r is an integer from 0 to 4, R 1 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (37)-(CH2) r CONR 1 R 2 , where r is an integer from 0 to 4, and each R 1 and R 2 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (38)-(CH2) are independently selected from the group consisting of aryls; r SO2R 1 , where r is an integer from 0 to 4, R 1 (a)C 1-6 Alkyl, (b)C 4-18 Aryl, and (c)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 Selected from the group consisting of (aryls); (39)-(CH2) r SO2NR 1 R 2 , where r is an integer from 0 to 4, and each R 1 and R 2 (a) hydrogen, (b) C 1-6 Alkyl, (c)C 4-18 Aryl, and (d)C 1-6 Alkyl-C 4-18 Arial (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18Independently selected from the group consisting of (aryls); (40)-(CH2) r NR 1 R 2 , where r is an integer from 0 to 4, R 1 and R 2 Each of these is (a) hydrogen, (b) N-protecting group, (c) C 1-6 Alkyl, (d)C 2-6 Alkenil, (e)C 2-6 Alkinyl, (f)C 4-18 Aryl, (g)C 1-6 Alkyl-C 4-18 Aryl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 4-18 (It is an aryl compound), (h)C 3-8 Cycloalkyl, and (i)C 1-6 Alkyl-C 3-8 Cycloalkyl (for example, -LR, where L is C) 1-6 It is alkyl, and R is C 3-8 (41) Thiols (e.g., -SH), (42) Perfluoroalkyls (e.g., -(CF2)) are independently selected from the group consisting of (41) cycloalkyls, and in one embodiment, no two groups are bonded to the nitrogen atom via a carbonyl or sulfonyl group; (42) thiols (e.g., -SH), (43) perfluoroalkyls (e.g., -(CF2)) n (CF3, where n is an integer from 0 to 10), (43) Perfluoroalkoxy (e.g., -O-(CF2) n (44) aryloxy (e.g., -OR, where n is an integer from 0 to 10), (45) cycloalkoxy (e.g., -OR, where R is a cycloalkyl), (46) cycloalkylalkoxy (e.g., -OLR, where L is alkyl and R is a cycloalkyl), (47) arylalkoxy (e.g., -OLR, where L is alkyl and R is aryl). In certain embodiments, the unsubstituted aryl group is C 4-18 , C 4-14 , C 4-12 , C 4-10 , C 6-18 , C 6-14 , C 6-12 , or C6-10 It is an aryl group.

[0154] "Arylalkoxy" means an alkyl-aryl group bonded to a parent molecule group via an oxygen atom, as defined herein. 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" means -OR, where R is an optionally substituted aryl group as described herein. In some embodiments, the unsubstituted aryloxy group is C 4-18 or C 6-18 It is an aryloxy group.

[0156] "Aliroyl" refers to an aryl group bonded to the parent molecule group via a carbonyl group. In some embodiments, the unsubstituted aryl group is C 7-11 Aliroyl group or C 5-19 It is an aryl group. In other embodiments, the aryl group is -C(O)-R, where R is an aryl group as defined herein.

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

[0158] "Azidoalkyl" means an azide group bonded to a parent molecule group via an alkyl group, as defined herein. In some embodiments, the azidoalkyl is -L-N3, where L is an alkyl group as defined herein. "Azo" means an -N=N- group.

[0159] "Carbene" refers to a derivative of the same molecule having H2C: and a carbon atom, i.e., (C:), with two non-bonding electrons. In some embodiments, the carbene is R 1 R 2 (C:), and R 1 and R 2Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 However, each atom, together with the atom to which it is bonded, forms a cyclic aliphatic group as defined herein.

[0160] "Carbenium cation" is H3C + , and carbon having a formal charge of +1, i.e., C + It is a derivative having the same. In some embodiments, the carbenium cation is R 1 -C + (R) New R 2 , and R, R 1 , and R 2 Each of these is independently selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein, or R 1 and R 2 , and optionally, R, together with the atoms to which each is bonded, forms a cyclic aliphatic group as defined herein.

[0161] "Carbonyl" refers to a -C(O)- group, which can be represented as >C=O.

[0162] "Carboxyl" refers to the -CO2H group, or its anion.

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

[0164] "Cyclic aliphatic" means a cyclic aliphatic group as defined herein.

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

[0166] "Cycloalkylalkoxy" means an alkyl-cycloalkyl group bonded to a parent molecule group via an oxygen atom, as defined herein. 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] Unless otherwise specified, "cycloalkyl" means a monovalent, saturated or unsaturated, non-aromatic cyclic hydrocarbon group having 3 to 8 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and bicyclo[2.2.1heptyl]. Cycloalkyl groups can also be substituted or unsubstituted. For example, a cycloalkyl group can be substituted with one or more groups, including the groups described herein for alkyl groups.

[0168] "Cycloheteraliphatic" means a cyclic heteroaliphatic group as defined herein.

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

[0171] "Haloaliphatic" means an aliphatic group as defined herein, in which one or more hydrogen atoms, for example, 1 to 10 hydrogen atoms, are independently substituted with halogen atoms such as fluoro, bromo, chloro, or iodine.

[0172] "Haloalkyl" means an alkyl group as defined herein, in which one or more hydrogen atoms, e.g., 1 to 10 hydrogen atoms, are independently substituted with halogen atoms such as fluoro, bromo, chloro, or iodine. In independent embodiments, the haloalkyl group can be a -CX3 group, where each X can be independently selected from fluoro, bromo, chloro, or iodine. In some embodiments, the "haloalkyl group" is -LX, where L is an alkyl group as defined herein, and X is fluoro, bromo, chloro, or iodine. 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 iodine; R 1 and R 2 Each of them is independently H or alkyl as defined herein.

[0173] "Haloheteroaliphatic" means a heteroaliphatic as defined herein, in which one or more hydrogen atoms, for example, 1 to 10 hydrogen atoms, are independently substituted with halogen atoms such as fluoro, bromo, chloro, or iodine.

[0174] "Heteroaliphatic" means an aliphatic group as defined herein, comprising at least one heteroatom to 20 heteroatoms, for example, 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 their oxidized forms within the group.

[0175] "Heteroalkyl," "heteroalkenyl," and "heteroalkynyl" each refer to an alkyl group, alkenyl group, or alkynyl group (which may be branched, linear, or cyclic) as defined herein, containing at least one heteroatom to 20 heteroatoms, for example, 1 to 15 heteroatoms or 1 to 5 heteroatoms, respectively, which may be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms.

[0176] "Heteroalkyl-aryl," "heteroalkenyl-aryl," and "heteroalkynyl-aryl" mean aryl groups as defined herein that are bonded to or can be bonded to the compounds disclosed herein, the aryl groups being bonded to or to via heteroalkyl, heteroalkenyl, or heteroalkynyl groups 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 heteroalkynyl-aryl group is -LR, where L is a heteroalkynyl group as defined herein and R is an aryl group as defined herein.

[0177] "Heteroalkyl-heteroaryl," "heteroalkenyl-heteroaryl," and "heteroalkynyl-heteroaryl" mean heteroaryl groups as defined herein that are bonded to or can be bonded to the compounds disclosed herein, the heteroaryl groups being bonded to or to via heteroalkyl groups, heteroalkenyl groups, or heteroalkynyl groups 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 heteroalkynyl-heteroaryl group is -LR, where L is a heteroalkynyl group as defined herein and R is a heteroaryl group as defined herein.

[0178] "Hyperaryl" means an aryl group containing at least one to six heteroatoms, e.g., one to four heteroatoms, which can be selected from, but are not limited to, oxygen, nitrogen, sulfur, silicon, boron, selenium, phosphorus, and their oxidized forms within the ring. Such a heteroaryl group may have a single ring or multiple fused rings, the fused rings may or may not be aromatic if the bonding site is through an atom of the aromatic heteroaryl group, and / or may or may not contain heteroatoms. The heteroaryl group may be substituted with one or more groups other than hydrogen, e.g., 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., they contain 4n+2 π electrons in a monocyclic or polycyclic system.

[0179] "Heteroatom" means an atom other than carbon, such as oxygen, nitrogen, sulfur, silicon, boron, selenium, or phosphorus. In certain disclosed embodiments, such as when not permitted due to valency restrictions, heteroatoms do not include halogen atoms.

[0180] Unless otherwise specified, "heterocyclyl" means a five-membered, six-membered, or seven-membered ring containing one, two, three, or four non-carbon heteroatoms (e.g., independently selected from the group consisting of nitrogen, oxygen, phosphorus, sulfur, or halo). A five-membered ring has 0 to 2 double bonds, while six-membered and seven-membered rings have 0 to 3 double bonds. The term "heterocyclyl" also includes bicyclic, tricyclic, and tetracyclic groups in which any of the above heterocyclic rings is condensed to one, two, or three rings independently selected from the group consisting of aryl rings, cyclohexane rings, cyclohexene rings, cyclopentane rings, cyclopentene rings, and other monocyclic heterocyclic rings, such as indolyl, quinolyl, isoquinolyl, tetrahydroquinolyl, benzofuryl, benzothienyl, etc. Heterocyclic compounds include thyranyl, thietanyl, tetrahydrothienyl, thianyl, thiepanyl, azilidinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, pyridyl, homopiperidinyl, pyrazinyl, piperazinyl, pyrimidinyl, pyridadinyl, oxazolyl, oxazolidinyl, oxazolidonyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiomorpholinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, indolyl, quinolinyl, isoquinoli This includes yl, benzimidazolyl, benzothiazolyl, benzoxazolyl, furyl, thienyl, thiazolidinyl, isothiazolyl, isoindazoyl, triazolyl, tetrazolyl, oxadiazolyl, uricil, thiadiazolyl, pyrimidyl, tetrahydrofuranil, dihydrofuranil, dihydrothienyl, dihydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, pyranil, dihydropyranil, tetrahydropyranil, dithiazolyl, dioxanil, dioxynyl, dithianil, trithianil, oxazinyl, thiadinyl, oxothiolanil, triazinyl, benzofuranil, benzothienyl, etc.

[0181] "Heterocyclyloxy" means a heterocyclyl group bonded to a parent molecule group via an oxygen atom, as defined herein. In some embodiments, the heterocyclyloxy group is -OR, where R is a heterocyclyl group as defined herein.

[0182] "Heterocyclyl" means a heterocyclyl group, as defined herein, bonded to a parent molecule group via a carbonyl group. In some embodiments, the heterocyclyl group is -C(O)-R, where R is a heterocyclyl group as defined herein.

[0183] "Hydroxyl" means -OH.

[0184] "Hydroxyalkyl" means an alkyl group as defined herein, substituted with one to three hydroxyl groups, provided that only one hydroxyl group may be bonded to a single carbon atom of the alkyl group, and is exemplified by hydroxymethyl, dihydroxypropyl, etc. 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, and R 1 and R 2 Each of them is independently H or alkyl as defined herein.

[0185] "Ketone" means -C(O)R, where R is selected from aliphatic, heteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0186] "Nitro" refers to the -NO2 group.

[0187] "Nitroalkyl" means an alkyl group as defined herein, substituted with one to three nitro groups. In some embodiments, the nitroalkyl group is -L-NO, where L is an alkyl group as defined herein. In other embodiments, the nitroalkyl group is -LC(NO)(R 1 )-R 2 , where L is a covalent bond or an alkyl group as defined herein, and R 1 and R 2 Each of them is independently H or alkyl as defined herein.

[0188] "Oxo" means =O group.

[0189] "Oxy" means -O-.

[0190] "Perfluoroalkyl" means an alkyl group as defined herein, in which each hydrogen atom is replaced by a fluorine atom. Exemplary perfluoroalkyl groups include trifluoromethyl, pentafluoroethyl, and the like. In some embodiments, the perfluoroalkyl group is -(CF2) n CF3, where n is an integer between 0 and 10.

[0191] "Perfluoroalkoxy" means an alkoxy group as defined herein, in which each hydrogen atom is replaced by a fluorine atom. In some embodiments, the perfluoroalkoxy group is -OR, where R is a perfluoroalkyl group as defined herein.

[0192] "Salt" means the ionic form of a compound or structure (e.g., any chemical formula, compound, or composition described herein) that contains a cationic or anionic compound and forms an electrically neutral compound or structure. Salts are well known in the art. For example, non-toxic salts are described in "Pharmaceutical salts," J. Pharm. Sci. January 1977; 66(1):1-19 by Berge SM et al., and "Handbook of Pharmaceutical Salts: Properties, Selection, and Use," Wiley-VCH, April 2011 (2nd rev. ed., eds. PHStahl and CG Wermuth). Salts can be prepared in situ or separately during the final separation and purification of the compounds of the present invention by reacting a free base with a suitable organic acid (to produce an anionic salt) or by reacting an acidic group with a suitable metal or organic salt (to produce a cationic salt).Typical anionic salts include acetate, adipine, alginate, ascorbate, aspartate, benzenesulfonate, benzoate, bicarbonate, bisulfate, hydrogen tartrate, borate, bromide, butyrate, camphorate, camphor sulfonate, chloride, citrate, cyclopentanepropionate, digluconate, hydrochloride, diphosphate, dodecyl sulfate, edetate, ethanesulfonate, fumarate, glucoheptone, gluconate, glutamate, glycerophosphate, hemisulfate, heptone, hexanoate, hydrobromide, hydrochloride, hydroiodide, hydroxyethanesulfonate, hydroxynaphthoate, iodide, lactate, and lactobion. This includes salts, laurates, lauryl sulfates, malates, maleates, malons, mandelates or esters, mesylates, methanesulfons, methyl bromides, methylnitrates, methyl sulfates, mucates, 2-naphthalenesulfons, nicotinates, nitrates, oleates, oxalates, palmitates, pamoates, pectins, persulfates, 3-phenylpropionates, phosphates, picrinates, pivalates, polygalacturonic acid, propions, salicylates, stearates, basic acetates, succinates, sulfates, tannates, tartrates, theophyllines, thiocyans, triethyl iodide, toluenesulfons, undecanoates, and valerates. Typical cationic salts include metal salts, such as alkali or alkaline earth salts, such as barium, calcium (e.g., calcium EDTA), lithium, magnesium, potassium, and sodium; other metal salts, such as aluminum, bismuth, iron, and zinc; and non-toxic ammonium, quaternary ammonium, and amine cations, such as ammonium, tetramethylammonium, tetraethylammonium, methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, and pyridinium, but not limited to these. Other cationic salts include organic salts, such as chloroprocaine, choline, dibenzylethylenediamine, diethanolamine, ethylenediamine, methylglucamine, and procaine.Furthermore, other salts include ammonium, sulfonium, sulfoxonium, phosphonium, iminium, imidazolium, benzimidazolium, amidinium, guanidinium, phosphadinium, phosphazenium, pyridinium, and other cationic groups described herein (for example, optionally substituted isoxazolium, optionally substituted oxazolium, optionally substituted thiazolium, optionally substituted pyrorium, optionally substituted furanium, optionally substituted thiophenium, optionally substituted imidazolium, optionally substituted pyrazorium, optionally substituted isothiazorium, optionally substituted triazorium, optionally substituted tetrazolium, optionally substituted flurzanium, optionally substituted pyridinium, optionally substituted pyrimidinium, optionally substituted pyrazinium, optionally substituted triazinium, optionally substituted tetrazinium, optionally substituted pyridazinium, optionally substituted oxazinium, optionally substituted pyrrolidinium, optionally substituted pyrazolidinium, optionally substituted imidazolinium, optionally substituted isoxazolidinium, optionally substituted oxazolidinium, optionally substituted piperadinium, optionally substituted piperidinium, optionally substituted morpholinium, optionally substituted azepanium, optionally substituted azepinium, optionally substituted (Indorium, optionally substituted isoindorium, optionally substituted indridinium, optionally substituted indazolium, optionally substituted benzimidazolium, optionally substituted isoquinolinium, optionally substituted quinolidinium, optionally substituted dehydroquinolidinium, optionally substituted quinolinium, optionally substituted isoindrinium, optionally substituted benzimidazolinium, and optionally substituted prium).

[0193] "Sulfo" refers to the -S(O)2OH group.

[0194] "Sulfonyl" or "sulfonate" means an -S(O)2- group, or -SO2R, where R is selected from hydrogen, aliphatic, heteroaliphatic, haloaliphatic, haloheteroaliphatic, aromatic, or any combination thereof, as defined herein.

[0195] "Thioalkoxy" means an alkyl group bonded to a parent molecule group via a sulfur atom, as defined herein. An example of an unsubstituted thioalkoxy group is C 1-6 It contains a thioalkoxy. In some embodiments, the thioalkoxy group is -SR, where R is an alkyl group as defined herein.

[0196] "Thiol" refers to the -SH group.

[0197] Those skilled in the art will recognize that the definitions provided above are not intended to include unacceptable substitution patterns (e.g., methyl being substituted with five different groups). Such unacceptable substitution patterns are readily recognizable to those skilled in the art. Any functional group disclosed herein and / or defined above may be substituted or unsubstituted unless otherwise specified.

[0198] Device The methods described herein can be carried out in any suitable apparatus. The following description provides an example of a suitable apparatus. The apparatus described herein enables rapid and precise control of the substrate temperature during semiconductor processing, and this control includes performing etching using thermal energy instead of or in addition to plasma energy to facilitate modification and removal operations. In certain embodiments, etching that relies primarily on thermal energy rather than plasma to facilitate chemical reactions in modification and removal operations can be considered “thermal etching.” This etching is not limited to ALE (atomic layer etching). This etching is applicable to any etching technique.

[0199] In certain embodiments, thermal etching processes, such as those using one or more thermal cycles, have relatively rapid heating and cooling, as well as relatively precise temperature control. In some cases, these features may be influenced to provide good throughput and / or to reduce non-uniformity and wafer defects.

[0200] Many conventional etching systems lack the ability to adjust and control the substrate temperature at an appropriate speed. For example, some etching systems may be able to heat the substrate to multiple temperatures, but only at a slow speed, or unable to reach the desired temperature range, or unable to maintain the substrate temperature within the desired range for the desired time. Similarly, typical etching systems often cannot cool the substrate sufficiently rapidly to enable high throughput, or to cool the substrate to the desired temperature range. In some applications, it is desirable to reduce the temperature gradual increase time as much as possible, for example, to less than about 120 seconds in some embodiments, but many conventional etching systems cannot heat, cool, or both the substrate in less than that time. In some systems, it may take several minutes to cool and / or heat the substrate, which slows down throughput.

[0201] In various embodiments, the apparatus described herein is designed or configured to rapidly heat and cool a wafer and to precisely control the wafer temperature. In some embodiments, the wafer is rapidly heated, and its temperature is precisely controlled using part of visible light emitted from light-emitting diodes (LEDs) placed in a pedestal beneath the wafer. The visible light may have wavelengths ranging from 400 nanometers (nm) to 800 nm, and varying between these wavelengths. The pedestal may include various features that enable wafer temperature control, such as a transparent window that may have a lens effect to favorably guide or focus the emitted light, a reflective material to favorably guide or focus the emitted light, and a temperature control element that assists in the temperature control of the LEDs, pedestal, and chamber.

[0202] The apparatus may also thermally separate or thermally "levitate" the wafer within the processing chamber, so that only the minimum thermal mass is heated, ideally the minimum thermal mass being only the substrate itself, thereby enabling faster heating and cooling. The wafer may be rapidly cooled using a cooling gas and / or radiant heat transfer to a heat sink such as an upper plate (or other gas distribution element) above the wafer. In some cases, the apparatus may also include temperature control elements within the processing chamber walls, pedestal, and upper plate (or other gas distribution element) to enable further temperature control of the wafer and processing conditions within the chamber, such as preventing undesirable condensation of the processing gas and vapor.

[0203] The apparatus may also be configured to implement various control loops to precisely control wafer and chamber temperatures (for example, using a controller configured to execute instructions for the apparatus to perform these loops). This may include the use of various sensors that determine wafer and chamber temperatures as part of open-loop and feedback control loops. These sensors may include in-wafer support temperature sensors that contact the wafer to measure its temperature, and non-contact sensors such as photodetectors that measure the light output of an LED and pyrometers configured to measure the temperature of various types of wafers. As will be described in more detail below, conventional pyrometers determine the temperature of an object by emitting an infrared or other optical signal to the object and measuring the signal reflected or emitted by the object. However, many silicon wafers cannot be measured with conventional pyrometers because silicon can be optically transparent at various temperatures and under various treatments, for example, when doped or undoped. For example, undoped silicon wafers are transparent to infrared signals at temperatures below 200°C. The novel pyrometers provided herein are capable of measuring multiple types of silicon wafers at various temperatures.

[0204] Figure 5 shows a cross-sectional side view of an exemplary apparatus according to the disclosed embodiment. Using this apparatus, any of the methods described herein may be carried out, for example, using the chemicals described herein. As detailed 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 processing 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.

[0205] The processing chamber 102 includes side walls 112A, an upper section 112B, and a bottom section 112C, which at least partially define the chamber interior 114, which can be considered as a plenum volume. As described herein, in some embodiments, it may be desirable to actively control the temperature of the processing chamber walls 112A, upper section 112B, and bottom section 112C to prevent undesirable condensation on the surface. In some new semiconductor processing operations, vapors such as water and / or alcohol vapor are flowed over a substrate, which adsorbs onto the substrate, but undesirably, it may also adsorb onto the inner surface of the chamber. This can lead to undesirable deposition and etching on the inner surface of the chamber, thereby damaging the chamber surface and potentially causing substrate defects as fine particles detach and reach the substrate. To reduce and prevent undesirable condensation on the inner surface of the chamber, the temperature of the chamber walls, upper section, and bottom section may be maintained at a temperature at which condensation of the chemicals used in the processing operation does not occur.

[0206] This active temperature control of the chamber surface may be achieved using heaters to heat the chamber walls 112A, the top 112B, and the bottom 112C. As shown in Figure 5, a chamber heater 116A is positioned on the chamber wall 112A and configured to heat it, a chamber heater 116B is positioned on the top 112B and configured to heat it, and a chamber heater 116C is positioned on the bottom 112C and configured to heat it. The chamber heaters 116A-116C may be resistive heaters configured to generate heat when an electric current is passed through a resistive element. The chamber heaters 116A-116C may be fluid conduits through which a heat transfer fluid, such as a heating fluid which may contain heated water, can flow. In some cases, the chamber heaters 116A-116C may be a combination of a heating fluid and a resistive heater. Chamber heaters 116A to 116C are configured to generate heat to bring the inner surfaces of the chamber walls 112A, the upper section 112B, and the bottom section 112C to a desired temperature, for example, in the range of about 40°C to about 150°C, and including about 80°C to about 130°C, or about 90°C, or about 120°C. Under some conditions, it has been found that water and alcohol vapors do not condense on surfaces maintained at a temperature of about 90°C or higher.

[0207] The chamber walls 112A, upper section 112B, and bottom section 112C may also be composed of various materials capable of withstanding the chemicals used in the processing technology. These chamber materials may include, for example, aluminum, anodized aluminum, aluminum with polymers such as plastics, metals or metal alloys with yttria coatings, metals or metal alloys with zirconia coatings, and metals or metal alloys with aluminum oxide coatings. In some cases, the coating materials may be blends or layers of various materials, for example, alternating layers of aluminum oxide and yttria, or alternating layers of aluminum oxide and zirconia. These materials are configured to withstand the chemicals used in the processing technology, such as anhydrous HF, water vapor, methanol, isopropyl alcohol, chlorine, fluorine gas, nitrogen gas, hydrogen gas, helium gas, and mixtures thereof.

[0208] The apparatus 100 may be configured to perform the processing operation in a vacuum or near a vacuum, for example, at a pressure of about 0.1 Torr to about 100 Torr, or about 20 Torr to about 200 Torr, or about 0.1 Torr to about 10 Torr. This may include a vacuum pump 184 configured to draw air from inside the chamber 114 to a vacuum having a low pressure, for example, a pressure of about 0.1 Torr to about 100 Torr or other pressure ranges as described herein.

[0209] Here, we discuss various features of the pedestal 104. The pedestal 104 includes a heater 122 (indicated by a dashed rectangle in Figure 5), which has multiple LEDs 124 configured to emit visible light having wavelengths of 400 nm to 800 nm, including 450 nm. The heater LEDs emit this visible light to the back surface of the substrate, and this visible light heats the substrate. Visible light with wavelengths of approximately 400 nm to 800 nm can be rapidly and efficiently heated to ambient temperatures, for example, from approximately 20°C to approximately 600°C, because silicon absorbs light in this range. In contrast, at temperatures up to approximately 400°C, radiative heating, including infrared radiant heating, may not be effective in heating silicon because silicon tends to be transparent to infrared radiation at temperatures below approximately 400°C. In addition, radiant heaters that directly heat the top of the wafer can cause damage or other adverse effects on the top film, as is the case with many conventional semiconductor processes. Conventional "hot plate" heaters, which rely on solid-to-solid heat transfer between a substrate and a heating platen such as a pedestal with a heating coil, have relatively slow heating and cooling rates and can result in uneven heating due to substrate warping and inconsistent contact with the heating platen. For example, it may take several minutes to heat a conventional pedestal to a desired temperature, to raise it from a first temperature to a second higher temperature, and to cool the pedestal to a lower temperature.

[0210] Figure 17 shows a graph of silicon absorption at various wavelengths and temperatures. The x-axis represents the wavelength of light, and the vertical axis represents absorption, with a maximum value of 1.0 (i.e., 100%). The data represents the optical absorption of silicon at various temperatures. As can be seen from the figure, in region 1, the silicon absorption of light from 400 nm to 800 nm remains relatively constant with respect to changes in silicon temperature. However, the silicon absorption of infrared light, i.e., light with wavelengths greater than approximately 1 micrometer, changes with the silicon temperature until the temperature reaches 600°C, indicating inconsistency in silicon absorption. In addition, the absorption range for various wavelengths and temperatures is reduced compared to the visible range. For example, silicon at 270°C has a very low absorption rate of approximately 0.05, or 5%, for infrared emission from approximately 1.8 micrometers to approximately 6 micrometers, followed by an inconsistent rate from approximately 6 micrometers to 10 micrometers. Silicon at 350°C has the next lowest infrared absorption rate, ranging from approximately 10% to 20% from approximately 1.8 micrometers to approximately 5 micrometers. Therefore, using visible light results in consistent absorption that is independent of silicon temperature.

[0211] Multiple LEDs in a heater may be arranged, electrically connected, and electrically controlled in various configurations. Each LED may be configured to emit visible blue light and / or visible white light. In certain embodiments, white light (generated using the wavelength range in the visible portion of the EM spectrum) is used. In some semiconductor processing operations, white light can reduce or prevent undesirable thin-film interference. For example, some substrates have a back film that reflects various light wavelengths in varying amounts, resulting in uneven and inefficient heating. Using white light can reduce this undesirable variation in reflection by averaging out the thin-film interference across the broad visible spectrum provided by the white light. In some cases, depending on the material on the back surface of the substrate, it may be advantageous to use visible non-white light, such as blue light with a wavelength of 450 nm, to provide a single-band or narrow-band wavelength that can result in more efficient, powerful, and direct heating of some substrates that can absorb narrow-band wavelengths better than white light.

[0212] Various types of LEDs may be used. Examples include chip-on-board (COB) LEDs or surface-mount diode (SMD) LEDs. For SMD LEDs, the LED chip may be fused to a printed circuit board (PCB) which may have multiple electrical contacts that enable control of each diode on the chip. For example, a single SMD chip is typically limited to having three diodes (e.g., red, blue, or green) that are individually controllable and produce different colors. The size of an SMD LED chip may range from, for example, 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. For COB LEDs, each chip may have three or more diodes printed on the same PCB, for example, nine, twelve, tens, hundreds, or more. COB LED chips typically have one circuit and two contacts, regardless of the number of diodes, thereby providing a simple design and efficient mono-color applications. The ability and performance of LEDs to heat a substrate may be measured by the wattage of heat emitted by each LED. Such wattage of heat can directly contribute to heating the substrate.

[0213] Figure 6 shows a top view of a substrate heater having multiple LEDs. This substrate heater 122 includes a printed circuit board 126 and multiple LEDs 124, some of which are labeled. This illustrated plurality contains approximately 1,300 LEDs. An external connection 128 is connected by traces and supplies power to the multiple LEDs 124. As shown in Figure 6, the LEDs may be arranged along a number of arcs offset radially from the center 130 of the substrate heater 122 by different radii. In each arc, the LEDs may be placed at equal intervals from one another. For example, one arc 132 is enclosed by a partially shaded dotted line shape and contains 16 LEDs 124, and is part of a circle of radius R extending around the center 130. The 16 LEDs 124 may be considered to be placed at equal intervals from one another along this arc 132.

[0214] In some embodiments, the LEDs may also be arranged along a circle around the center of the substrate heater. In some cases, some LEDs may be arranged along a circle while others are arranged along an arc. Figure 7 shows a top view of another example of a substrate heater having 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 are arranged along a number of circles offset radially from the center 330 of the substrate heater 322 by different radii. In each circle, the LEDs may be spaced equally apart from one another. For example, one circle 334 is surrounded by a partially shaded ring and contains 78 LEDs 324, with a radius R extending around the center 330. The 78 LEDs 324 may be considered to be spaced equally apart from one another along this circle 334. The LED arrangement in Figure 7 may result in a more uniform light and heat distribution pattern across the entire back surface of the substrate. This is because, in particular, since the substrate and heater remain stationary relative to each other during processing and do not rotate, the area of ​​the substrate heater 122 in Figure 6, including the external connection part, may result in unheated cold spots on the wafer.

[0215] In some embodiments, the LEDs may comprise at least about 1,000 LEDs, which may include, for example, numbers of about 1,200, 1,500, 2,000, 3,000, 4,000, 5,000, or more than 6,000. Each LED may be configured to use no more than 4 watts at 100% power in some cases, which may include 3 watts at 100% power and 1 watt at 100% power. These LEDs may be arranged in individually controllable zones and electrically connected to allow temperature control and fine adjustment across the entire substrate. In some cases, the LEDs may be divided into, for example, at least 20 independent controllable zones, which may include, for example, at least about 25, 50, 75, 80, 85, 90, 95, or 100 zones. These zones may allow temperature control in the radial and azimuth (i.e., angular) directions. These zones can be arranged in a defined pattern, for example, a rectangular grid, a hexagonal grid, or other suitable pattern to generate a desired temperature profile. These zones may have various shapes, such as squares, trapezoids, rectangles, triangles, chamfered rectangles, ellipses, circles, rings (e.g., rings), partial rings (i.e., annular sectors), arcs, segments, and sectors that are arranged around the center of the heater and have a radius less than or equal to the overall radius of the PCB of the substrate heater. For example, in Figure 6, the LED has 88 zones, which are configured in at least 20, for example, 20 or 21 concentric rings. These zones can be configured to adjust the temperature at numerous locations across the wafer to construct a desired temperature profile, such as a more uniform temperature distribution and higher temperatures near the substrate edges than in the center of the substrate. Independent control of these zones may 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 cases, each zone may have one LED, which allows each LED to be controlled and adjusted individually, potentially leading to a more uniform heating profile on the substrate.Accordingly, in some embodiments, each of the multiple LEDs in the substrate heater may be individually controllable.

[0216] In certain embodiments, the substrate heater 122 is configured to heat the substrate to several temperatures and maintain each of such temperatures for varying durations. These durations may include, but are not limited to, 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 about 50°C to 600°C, and this range includes about 50°C to 150°C, for example, about 130°C, or about 150°C to 350°C. Other expected temperature ranges are described above. The substrate heater may be configured to maintain the substrate at a temperature within these ranges for a variety of durations, the durations of which, as non-limiting examples, include, for example, 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. In addition, in some embodiments, the substrate heater 122 is configured to heat the substrate to any temperature within these ranges for a time of, for example, 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, for example, at a rate of at least about 0.1°C / second to at least about 20°C / second.

[0217] The substrate heater can raise the temperature of the substrate by causing an LED 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% of the power. In some embodiments, the substrate heater is configured to output about 10W to 4000W, including at least about 10W, at least about 30W, at least about 0.3 kilowatts (kW), at least about 0.5kW, at least about 2kW, at least about 3kW, or at least about 4kW. The device is configured to supply power to the pedestal of about 0.1kW to 9kW. The power supply is connected to the substrate heater via the pedestal but is not shown. During temperature increase, the substrate heater may operate at high power or at low power levels (e.g., including power of about 5W to about 0.5kW) to maintain the temperature of the heated substrate.

[0218] The pedestal may include a reflective material on its internal surface, which, when in operation, reflects light emitted by the LEDs and directs it to the back surface of the substrate supported by the pedestal. In some such embodiments, the substrate heater may include such a reflective material placed on the top surface 140 of the PCB 126 on which a plurality of LEDs 124 are arranged, as shown in Figure 5. The reflective material may consist of aluminum such as polished aluminum, stainless steel, aluminum alloys, nickel alloys, and other protective layers that can prevent oxidation of the metal and / or enhance reflectivity at specific wavelengths, for example, resulting in reflectivity of more than 99% at a particular wavelength, as well as other durable reflective coatings. In addition or alternatively, the pedestal 104 may have a bowl 146 on which the substrate heater 122 is at least partially placed. The bowl 146 may have an exposed inner surface 148 of the side wall 149 of the pedestal, on which the reflective material may be placed. This reflective material conveniently guides light that would otherwise be absorbed by PCB126 and pedestal104 back onto the substrate, thereby increasing the heating efficiency of the substrate heater and reducing undesirable heating of PCB126 and pedestal104.

[0219] In some embodiments, the substrate heater may also include a pedestal cooler thermally connected to the LEDs, thereby allowing heat generated by multiple LEDs to be transferred from the LEDs to the pedestal cooler. This thermal connection is such that heat can be transferred from multiple LEDs to the pedestal cooler along one or more heat flow paths between these components. In some cases, the pedestal cooler is in direct contact with one or more elements of the substrate heater, while in other cases, another conductive element, such as a thermally conductive plate (including, for example, metal), is interposed between the substrate heater and the pedestal cooler. Referring again to Figure 5, the substrate heater includes a pedestal cooler 136 in direct contact with the bottom of the PCB 126. Heat is configured to flow from the LEDs to the PCB 126 and then to the pedestal cooler 136. The pedestal cooler 136 also includes a plurality of fluid conduits 138 through which a heat transfer fluid, such as water, flows 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 cases, the pedestal cooler may be configured to circulate water cooled to, for example, about 5°C to 20°C.

[0220] Where provided herein, it may be advantageous to actively heat the outer surface of the processing chamber 102. In some cases, it may be equally advantageous to heat the outer surface of the pedestal 104 to prevent undesirable condensation and deposition on the outer surface of the pedestal 104. As shown in Figure 5, the pedestal 104 may further include a pedestal heater 144 inside the pedestal 104, the pedestal heater 144 configured to heat the outer 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 through which a heating fluid flows. In some cases, both the pedestal cooler and the pedestal heater may have fluid conduits that are fluidically connected to each other so 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 50°C to 130°C, with this temperature range including approximately 90°C to 120°C.

[0221] The pedestal may also include a window to protect the substrate heater, which includes multiple LEDs, from damage caused by exposure to processing chemicals and pressures used during the processing operation. As shown in Figure 5, to construct a plenum volume within the pedestal that is fluidly separated from the inside of the chamber, the window 150 may be positioned above the substrate heater 122 and may be sealed to the side wall 149 of the pedestal 104. This plenum volume can be considered as the inside of the bowl 146. The window may consist of one or more materials that are optically transparent to visible light emitted by the LEDs, including light having wavelengths in the range of 400 nm to 800 nm. In some embodiments, this material may be quartz, sapphire, quartz with a sapphire coating, or calcium fluoride (CaF). The window may not have any holes or openings within it. In some embodiments, the heater may have a thickness of 15 to 30 mm, including 20 mm and 25 mm.

[0222] Figure 8 shows the pedestal of Figure 5 with additional features according to various embodiments. As can be seen in Figure 8, the window 150 includes an upper surface 152 facing the substrate 118 supported by the pedestal 104, and a lower surface 154 facing the substrate heater 122. In some embodiments, the upper surface 152 and the lower surface 154 may be flat and planar (or substantially flat, e.g., within ±10% or 5% of flat). In some other cases, the upper surface 152, the lower surface 154, or both the upper surface 152 and the lower surface 154 may be non-planar surfaces. The non-planarity of these surfaces may be configured to refract and / or guide the light emitted by the LED 124 of the substrate heater 122 to heat the wafer more efficiently and / or effectively. The non-planarity may also be along part or all of the surface. For example, the entire base surface may have a convex or concave curvature, while in another embodiment, the outer annular region of the base surface may have a convex or concave curvature, while the rest of the surface is planar. In further embodiments, these surfaces may have multiple, but different, non-planar portions, for example, a conical portion in the center of the surface, adjacent to a planar annular portion, and adjacent to that a frustoconical surface at the same or different angles as the conical portion. In some embodiments, the window 150 may be characterized by functioning as an array of lenses directed to focus the light emitted by one or more LEDs, e.g., each LED.

[0223] Since the window 150 is positioned above the substrate heater 122, the window 150 is heated by the substrate heater 122, which can affect the thermal environment around the substrate. Depending on the material used for the window 150, e.g., quartz, the window may retain heat, and may gradually retain more heat during the process of processing one or more substrates. This heat is radiated to the substrate and can therefore directly heat it. In some cases, the window can cause a temperature increase of 50°C to 80°C above the heater temperature. This heat can create a temperature gradient through the thickness of the window, i.e., vertically. In some cases, the top surface 152 is 30°C hotter than the bottom surface 154. Therefore, it may be advantageous to adjust and configure the chamber to account for the thermal effect of the window and reduce it. As will be described in more detail below, this may involve sensing the temperature of the substrate and adjusting the substrate heater to account for the heat retained by the window.

[0224] This may also include various configurations of the pedestal, such as actively cooling the window. In some embodiments, the window 150 may be offset from the substrate heater 122 by a first distance 156, as shown in Figures 5 and 8. In some embodiments, this first distance may be about 2 mm to 50 mm, and may include about 5 mm to 40 mm. To cool both the window 150 and the substrate heater 122, a cooling fluid, such as an inert gas, may be flowed between the window 150 and the substrate heater 122. The pedestal may have one or more inlets and one or more outlets to flow this gas into the plenum volume or bowl 146 of the pedestal 104. One or more inlets are fluidically connected to an inert gas source outside the chamber 102, and the inlets may include fluid through conduits that pass at least partially through the interior of the pedestal 104. One or more outlets are fluidically connected to exhaust or the environment outside the chamber 102, and the outlets may also be fluid through conduits extending within the pedestal. In Figure 18, which shows the pedestal of Figure 8 with additional features according to various embodiments, one or more inlets 151 are located within the side wall 149 and extend through the surface 148. One or more inlets are also fluidically connected to an inert gas source 1472, partially through a fluid conduit 155 via the pedestal 104. A single outlet 153 is located in the central region, i.e., adjacent to, but not at, the exact center of, the substrate heater 122. In some embodiments, one or more gas inlets and one or more outlets may be interchangeable, resulting in one or more outlets extending through the side wall 149 (i.e., they are articles 151 in Figure 18) and one or more inlets being in the central region of the substrate heater 122 (i.e., they are articles 153 in Figure 18). In some embodiments, there may be multiple outlets. 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, for example, a mounting bracket between the LED heater 122 and the pedestal sidewall 149.

[0225] In some embodiments, the window may be in direct thermal contact with a substrate heater, and the pedestal cooler may be configured to cool both the PCB and the window. In some embodiments, as also shown in Figures 5 and 8, the window 150 may be thermally connected to the side wall 149 of the pedestal 104 in order to transfer some of the heat held within the window 150 to the pedestal 104. This transferred heat may be further transferred out of the pedestal using, for example, a pedestal heater 144, which can flow a fluid heated to, for example, about 20°C to 100°C through the pedestal 104. This heated fluid may be colder than the temperature of the pedestal 104 at the thermal connection with the window 150. In some embodiments, the window 150 may have one or more fluid conduits within it, through which a clear cooling fluid may flow. These conduits may have various configurations, such as a single inlet, a single outlet, and a single channel with a meandering section, to ensure uniform cooling and temperature distribution within the window. The fluid may be supplied to the window from a fluid source or reservoir located outside the chamber, through a pedestal.

[0226] As shown in Figures 5 and 8, the substrate support 108 of the pedestal 104 is configured to support the substrate 118 above the window 150 and the substrate heater 122, offset from them. In certain embodiments, the temperature of the substrate can be controlled quickly and precisely by thermally levitating or thermally separating the substrate within the chamber. Heating and cooling of the substrate involves both the thermal mass of the substrate and the thermal mass of other articles in contact with the substrate. When the substrate is in thermal contact with a large body, such as when the entire back surface of the substrate rests on a large surface of the pedestal or electrostatic chuck, as in many conventional etching apparatuses, this body acts as a heat sink for the substrate, thereby affecting the ability to precisely control the substrate temperature and reducing the speed of heating and cooling the substrate. Therefore, it is desirable to position the substrate so that the minimum thermal mass is heated and cooled. This thermal levitation is configured to position the substrate so that it has the minimum thermal contact (including direct and radiative) with other objects in the chamber.

[0227] Accordingly, in some embodiments, the pedestal 104 is configured to support the substrate 118 by thermally levitating or thermally separating the substrate from 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 until it is 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. For example, the number of substrate supports 108 may range from at least 3 to at least 6, or may exceed that. The surface area of ​​the support surface 120 may also be the minimum area necessary to adequately support the substrate during processing (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%.

[0228] The substrate support is also configured to prevent the substrate from contacting other elements of the pedestal, including the surface of the pedestal and features beneath the substrate. As shown in Figures 5 and 8, the substrate support 108 holds the substrate 118 on the next adjacent surface to the pedestal 104, namely the upper surface 152 of the window 150 (as seen in Figure 8), and offset from that surface. As can be seen from these figures, there is a volume or void beneath the substrate, except for the contact area with the substrate support. As shown in Figure 8, the substrate 118 is offset by a distance of 158 from the upper surface 152 of the window 150. This distance 158 may affect the thermal effect induced on the substrate 118 by the window 150. The larger the distance 158, the smaller the effect. It has been found that when the distance 158 is 2 mm or less, significant thermal coupling occurs between the window and the substrate. Therefore, it is desirable to have a distance 158 greater than 2 mm, 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.

[0229] The substrate 118 is also offset by a distance of 160 from the substrate heater 122 (which may be the top surface of the LED 124 in some cases, measured from the top surface of the substrate heater 122). This distance 160 affects many aspects of heating the substrate 118. In some cases, the LED 124 results in an uneven heating pattern that increases as the distance 160 decreases. Conversely, this uneven heating pattern is reduced by increasing the distance 160. In some cases, as the distance 160 increases, the heating efficiency decreases across the substrate and further decreases in the edge regions, resulting in uneven heating of the substrate. In some embodiments, distances 160 of about 5 mm to about 100 mm, e.g., about 10 mm to about 90 mm, or about 10 mm to about 30 mm, or about 15 mm to 25 mm, provide a substantially uniform heating pattern and acceptable heating efficiency.

[0230] As described above, the substrate support 108 is configured to support the substrate 118 above the window. In some embodiments, these substrate supports are stationary and fixed in place, and the substrate supports 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 made of a material that is transparent to light emitted by the LED 124. This material may be quartz or sapphire in some cases. The transparency of these substrate supports 108 may allow visible light emitted by the LED of the substrate heater 122 to pass through the substrate support 108 to the substrate 118, and as a result, the substrate support 108 does not block this light, and the substrate 118 can be heated in the area in which it is supported. This can provide more uniform heating of the substrate 118 than in the case of a substrate support containing a material that is opaque to visible light. In some other embodiments, the substrate support 108 may be made of an opaque material such as zirconium dioxide (ZrO2).

[0231] In some embodiments, as shown in Figure 8, the substrate support 108 may be positioned closer to the central axis 162 of the window 150 when viewed from the outer diameter 164 of the window 150. In some cases, a portion of these substrate supports may extend over and above the window 150, so that the support surface 120 overlaps with the window 150 and is located above the window 150.

[0232] In some embodiments, each substrate support may include a temperature sensor configured to detect the temperature of a substrate placed on the support surface of the substrate support. Figure 9 shows the substrate supports of Figures 5 and 8 according to a disclosed embodiment. Here, the support surface 120 of the substrate support 108 is seen together with the temperature sensor 166. In some embodiments, the temperature sensor 166 extends through the support surface 120 so that the temperature sensor 166 is in direct contact with the substrate held by the support surface 120. In some other embodiments, the temperature sensor 166 is located within the substrate support 108 and 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 pass through the substrate support 108 and further through the pedestal 104.

[0233] Referring again to Figure 5, in some embodiments, the pedestal is configured to move further vertically. This movement may involve moving the pedestal so 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 will be described in more detail below, moving the pedestal vertically can enable active cooling of the substrate, as well as a rapid cycle time for processing operations, including gas flow and purging, due to the small volume formed between the gas distribution unit 110 and the substrate 118. This movement can also enable the formation of a small process volume between the substrate and the gas distribution unit, resulting in smaller purging and processing volumes, and therefore reduced purging and gas flow times, and increased throughput.

[0234] The gas distribution unit 110 is configured to flow a process gas, which may contain liquids and / or gases such as reactants, reforming molecules, conversion molecules, or removal molecules, onto a substrate 118 located inside the chamber 114. As shown in Figure 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 steam sources 174. In some embodiments, the gas lines and mixing chamber may be heated to prevent undesirable condensation of the steam and gases flowing through them. 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. One or more steam sources may include one or more sources of gases and / or liquids to be vaporized. Vaporization may be by a direct injection vaporizer, a flow-over vaporizer, or both. The gas distribution unit 110 also includes a faceplate 176 containing a plurality of through-holes 178 that fluidly connect the gas distribution unit 110 to the interior of the chamber 114. These through-holes 178 are fluidly connected to one or more fluid inlets 170 and further extend through a front surface 177 of the faceplate 176, the front surface 177 is configured to face the substrate 118. In some embodiments, the gas distribution unit 110 can be considered as an upper plate, and in some other embodiments, it can be considered as a showerhead.

[0235] The through-holes 178 may be configured in various ways to deliver a uniform gas flow onto the substrate. In some embodiments, all of these through-holes may have the same outer diameter, for example, about 0.03 inches to 0.05 inches (about 0.762 mm to 1.27 mm), including about 0.04 inches (1.016 mm). These through-holes of the faceplate may also be arranged throughout the faceplate to ensure a uniform flow out of the faceplate.

[0236] Figure 10 shows a plan view of an exemplary first faceplate 176, with the front surface 177 (the surface configured to face the substrate) and through-holes 178 visible. As can be seen from the figure, the through-holes 178 of the faceplate 176 extend through the faceplate 176 and the front surface 177. These through-holes are also arranged along a plurality of circles centered on the central axis of the faceplate, thereby offsetting the holes from one another. For example, the faceplate 176 may have a through-hole 178A located at the center of the central axis of the faceplate 176. Directly adjacent to this central through-hole 178A, there may be a plurality of holes equally spaced along a first circle 179 having a first diameter. Just radially outside this circle, there may be another circle 181 having a second plurality of holes, having more holes than the first plurality. This second plurality of holes may be equally spaced along this second circle. These equal intervals do not necessarily have to be strict and may be considered substantially equal, which may be due to manufacturing or other inconsistencies, and the intervals may be within approximately ±5% of the equal intervals. As illustrated, some circles of the through-hole 178 may have their centers coincide with the reference data 183, while other circles of the through-hole are offset from the reference data 183 at angles such as approximately 15° and 7.5°. Here, in the through-holes along the first circle 179, two through-holes have their centers coincide with the data, while the through-holes along the second circle do not have their centers coincide with the reference data 183 and are offset from the data 183 by approximately 15°. The concentric circles of the through-holes may alternate between holes that have their centers coincide with the data 183 and holes that are offset from the data 183.

[0237] Figure 11 shows a plan view of an exemplary second faceplate 176, with the front surface 177 (the surface configured to face the substrate) and through-holes 178 visible. As can be seen from the figure, the through-holes 178 of the faceplate 176 extend through the faceplate 176 and the front surface 177. These through-holes are arranged differently from those in Figure 10, with one through-hole 178 positioned so as to coincide with the central axis of the faceplate 176, and the through-holes 178 are arranged in six sectors, within each sector, the through-holes are spaced equally along the arc of the sector. For example, one sector 191 is included in a dashed shape, and the holes are arranged along multiple arcs within the sector, with the number of holes increasing as its radial distance from the center of the faceplate 176 increases. A first exemplary arc 193A is identified, along which six through-holes 178 are arranged at equal intervals, and a second exemplary arc 193B is identified, along which twelve through-holes are arranged at equal intervals. The second exemplary arc 193B is larger than the first exemplary arc 193A and has a radial distance R2 that is greater than the radial distance R1 of the first arc 193A.

[0238] Referring again to Figure 5, the gas distribution unit 110 also includes a unit heater 180 thermally connected to the faceplate 176, thereby allowing heat to 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 can flow. As described above, the heat transfer fluid may be heated to a temperature range of, for example, about 20°C to 120°C. In some cases, the gas distribution unit 110 may be heated using the unit heater 180 to prevent undesirable condensation of vapors and gases. In some such cases, this temperature may be at least about 90°C or 120°C.

[0239] 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 heating fluid, or both. By using two heaters 180 and 182 within the gas distribution unit 110, various heat transfers can be enabled within the gas distribution unit 110. This may include heating the faceplate 176 using the first and / or second unit heaters 180 and 182 to provide a temperature-controlled chamber as described above, in order to reduce or prevent undesirable condensation on the elements of the gas distribution unit 110.

[0240] The apparatus 100 may also be configured to cool the substrate. This cooling may include circulating 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 temperature transitions, thereby reducing processing time and improving throughput. In some embodiments, the substrate 118 may be cooled by using a first unit heater 180 through which a heat transfer fluid flows, thereby transferring heat transferred from the substrate 119 away from the faceplate 176. Thus, the substrate 118 may be placed close to the faceplate 176 with a gap 186 of 5 mm or less, such that heat in the substrate 118 is radiated to the faceplate 176 and then transferred away from the faceplate 176 by the heat transfer fluid in the first unit heater 180, thereby cooling the substrate 118. Therefore, the faceplate 176 can be considered a heat sink for the substrate 118, for cooling the substrate 118.

[0241] In some embodiments, the apparatus 100 may further include a cooling fluid source 173, which may include a cooling liquid (gas or liquid) and a cooler (not shown) configured to cool the cooling liquid to a desired temperature, such as at least about 90°C or lower, at least about 70°C or lower, at least about 50°C or lower, at least about 20°C or lower, at least about 10°C or lower, at least about 0°C or lower, at least about -50°C or lower, at least about -100°C or lower, at least about -150°C or lower, at least about -190°C or lower, at least about -200°C or lower, or at least about -250°C or lower. The apparatus 100 includes piping for delivering the cooling liquid to one or more fluid inlets 170 and a gas distribution unit 110 configured to flow the cooling liquid onto a substrate. In some embodiments, for example, when the chamber interior 114 is under low pressure conditions such as about 0.1 Torr to 100 Torr, or about 20 Torr to 200 Torr, or about 0.1 Torr to 10 Torr, the fluid may be in liquid form when flowing into the chamber 102 and may return to a vapor state when it reaches the chamber interior 114. The cooling liquid may be an inert element, such as nitrogen, argon, or helium. In some cases, the cooling fluid may contain or consist only of a non-inert element or a mixture, such as hydrogen gas. In some embodiments, the flow rate of the cooling liquid 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, for example, at least about 5°C / second, at least about 10°C / second, at least about 15°C / second, at least about 20°C / second, at least about 30°C / second, or at least about 40°C / second.

[0242] In some embodiments, the apparatus 100 may actively cool the substrate by both moving the substrate closer to the faceplate and circulating a cooling gas over the substrate. In some cases, active cooling may be more effective by circulating the 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. Figure 12 shows graphs of four different active cooling experiments. In these four experiments, the substrate was cooled from approximately 400°C to approximately 25°C using different gases and different gaps between the substrate and the faceplate. In the first experiment, the substrate was placed 2 mm away from the faceplate, and helium gas was flowed over the substrate to actively cool it at 400°C ("He 2mm"). In the second experiment, the substrate was placed 20 mm away from the faceplate, and helium gas was flowed over the substrate to actively cool it at 400°C ("He 20mm"). In the third experiment, the substrate was placed 2 mm away from the faceplate, and nitrogen gas was flowed over the substrate to actively cool it at 400°C ("N2 2mm"). In the fourth experiment, the substrate was placed 20 mm away from the faceplate, and nitrogen gas was flowed over the substrate to actively cool it at 400°C ("N2 20mm"). As can be seen from the figure, the first experiment cooled the substrate in the fastest time of approximately 150 seconds, followed by the third experiment in approximately 450 seconds. These first and third experiments used both cooling gases and a 2 mm gap, while the slower second and fourth experiments used a 20 mm gap.

[0243] Therefore, the apparatus provided herein can rapidly heat and cool a substrate. Figure 13 provides an exemplary temperature control sequence. At time 0, the substrate is approximately 20°C or 25°C, and the LED of the substrate heater provided herein emits 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 heating power of 1 kW to 2 kW supplied to the substrate heater by a supply power of approximately 9 kW. Between approximately 30 seconds and approximately 95 seconds, the substrate heater 122 maintains the substrate at 400°C using less power, for example, heating power of 0.3 to approximately 0.5 kW supplied by a supply power of approximately 2 kW. Between approximately 30 and 60 seconds, the substrate is actively cooled using both a cooling gas (e.g., hydrogen or helium) flowing over the substrate and heat transfer to the faceplate. Once cooled, the substrate heater uses approximately 10-30W of heating power supplied by a power supply of approximately 100W to heat the substrate and maintain its temperature at approximately 70°C. Various processing techniques may use this type of sequence once or repeatedly to process the substrate.

[0244] In some embodiments, the apparatus 100 may include a mixing plenum for blending and / or conditioning the process gas for delivery before it reaches the fluid inlet 170. One or more mixing plenum inlet valves may control the introduction of the process gas 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 fluidically connected to the through-hole 178, which may distribute the received fluid equally to the through-hole 178 to provide a uniform flow on the substrate.

[0245] 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 a number of temperature ranges of a silicon substrate. For example, it is desirable to detect the temperature of substrates that have undergone various treatments, such as whether silicon is doped or undoped, over various temperature ranges in which the treatment may occur, for example, below about 200°C, above about 200°C and below about 600°C, or above 600°C. However, conventional pyrometers cannot detect various substrates in these ranges. Conventional pyrometers determine the temperature of an object according to some calibration by measuring the light signal reflected or emitted by the surface of the object. However, many silicon wafers cannot be measured with these pyrometers because silicon is optically transparent at various temperatures and under various treatments. As mentioned above, Figure 17 shows various absorption rates of the substrate at various temperatures. For example, conventional pyrometers can detect emissions in the range of approximately 8 to 15 micrometers, but most silicon substrates below approximately 200°C do not have a consistent emission signal in the range of approximately 8 to 15 micrometers, and therefore cannot be detected by conventional pyrometers below 200°C.

[0246] A low-doped or undoped silicon substrate has an emission signal of approximately 0.95 to 1.1 micrometers when the substrate is below approximately 300°C, the doped silicon substrate has an emission signal of approximately 1 to 4 micrometers when the substrate is below approximately 200°C, the silicon substrate has an emission signal of approximately 1 micrometer when it is near room temperature, for example below approximately 100°C, including, for example, 20°C, and the silicon substrate has an emission signal of approximately 8 to 15 micrometers when the temperature exceeds approximately 600°C. Therefore, a novel pyrometer is configured to detect multiple emission ranges in order to detect multiple substrates, e.g., doped, low-doped, or undoped substrates, over a variety of temperature ranges. This includes configurations for detecting emission ranges of approximately 0.95 to approximately 1.1 micrometers, approximately 1 micrometer, approximately 1 to approximately 4 micrometers, and / or approximately 8 to 15 micrometers. The novel pyrometer is configured to detect the substrate temperature at shorter wavelengths to distinguish the signal from the thermal noise of the chamber.

[0247] A novel pyrometer may include an emitter configured to emit an infrared signal and a detector configured to receive the emission. Referring to Figure 5, the apparatus includes a novel pyrometer 188, which includes an emitter and a detector 190 within the pyrometer 188. The novel pyrometer may be configured to emit a signal onto either the top or bottom surface of a substrate and to receive a signal on the other surface of the substrate. For example, the emitter may emit a signal onto the top of the substrate, and the detector may be located below the substrate and receive the signal emitted through the substrate below the substrate. Thus, the apparatus may have at least a first port 192A, e.g., port 192A, located at the top of the chamber 102 and passing through the center of the gas distribution unit 110, and a second port 192B, passing through the pedestal 104 and the substrate heater 122. The emitter in the pyrometer 188 may be connected to one of ports 192A or 192B via an optical fiber connection, such as the first port 192A shown in Figure 5, and the detector is optically connected to the other port, such as the second port 192B in Figure 5. The first port 192A may include a port window 194 for sealing the first port 192A from chemicals inside the chamber 114. In Figure 5, it can be seen that the second port 192B extends through the pedestal 104 and the substrate heater, so that the emitter emission passes through the window 150, through the substrate, to the second port 192B, and then to the detector 190. The detector 190 may be located in the second port or may be optically connected to the second port via other optical fiber connections (not shown). In some other embodiments, the emitter and detector are inverted, with the emitter emitting through the second port 192B and the detector detecting through the first port 192A.

[0248] The apparatus 100 may also include one or more optical sensors 198 to detect one or more metrics of visible light emitted by the LEDs. In some embodiments, these optical sensors may be one or more photodetectors configured to detect the light intensity and / or thermal radiation of visible light emitted by the LEDs of the substrate heater. Figure 5 shows a single optical sensor 198 connected to the interior of the chamber 114 via an optical fiber connector so that the optical sensor 198 can detect the light emitted by the substrate heater 122. The optical sensor 198 and additional optical sensors may be placed in various locations within the chamber 102, for example, in the top and sides, to detect the emitted light at various locations within the chamber 102. As will be discussed below, this can enable measurement and adjustment of the substrate heater, for example, adjustment of one or more independently controllable zones of the LEDs. In some embodiments, there may be multiple optical sensors 198 arranged along a circle or a plurality of concentric circles to measure various areas of the LEDs throughout the chamber 102. In some embodiments, the optical sensors may be located inside the chamber 114.

[0249] In some embodiments, the apparatus may be further configured to generate plasma and use the plasma for several processes in various embodiments. This may include having a plasma source configured to generate plasma inside the chamber, such as a capacitively coupled plasma (CCP), an inductively coupled plasma (ICP), an upper remote plasma, and a lower remote plasma.

[0250] The apparatus described herein is not limited to ALE etching operations. These apparatus may be used in conjunction with any etching technique.

[0251] Heat treatment technology This section provides additional details on heat treatment methods applicable to various embodiments. In some embodiments, the chemicals described above are used in connection with the implementation of the methods described in this section. In some embodiments, the methods described in relation to Figures 1 to 4 may be carried out according to some or all of the details provided in this section.

[0252] Figure 14 shows a first technique for heat treatment according to the disclosed embodiment. In operation 1001, a substrate is provided into a chamber and is thermally suspended within the chamber by being placed on a substrate support of a pedestal. As described above, only the substrate support is in contact with the substrate. The substrate is not in contact with any other elements of the processing chamber. Each substrate support is in contact with the edge region of the substrate, as presented herein and, for example, as shown in Figures 5 and 8.

[0253] In operation 1003, the substrate is heated to a first temperature using a substrate heater as described herein while it is thermally suspended in the chamber, i.e., while the substrate is supported only by the substrate support. The substrate heater emits visible light having a wavelength of 400 nm to 800 nm from a plurality of LEDs. The first temperature may be any temperature given herein, which may include, for example, about 50°C to about 600°C, about 20°C to about 500°C, about 100°C to about 500°C, about 20°C to about 200°C, about 50°C to about 150°C, about 130°C, or about 150°C to about 350°C. The substrate may be heated rapidly to the first temperature in, for example, less than 60 seconds, about 45 seconds, less than about 30 seconds, or less than about 15 seconds. This may include driving the LEDs to their maximum power, which together may be 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 of the supplied power. Where provided herein, this heating does not involve plasma or plasma generation.

[0254] In operation 1005, the substrate is maintained at a first temperature. This may include the substrate heater operating at low power to maintain the substrate at a specific temperature. Thus, the LED may provide some heating at a non-zero power level lower than during the temperature increase, maintaining the substrate at the desired temperature. Embodiments may include about 5W to about 0.5kW, which may include at least about 10W, at least about 30W, at least about 0.3kW, or at least about 0.5kW.

[0255] In operation 1007, the substrate is etched while at a first temperature. This etching may involve passing one or more gases to remove one or more modified layers of the material. This etching also does not involve plasma or plasma generation. In various embodiments herein, the etching chemicals include the chemical species described above, e.g., HF, organic solvents and / or water, additives, and carrier gases.

[0256] In some embodiments, the substrate is actively cooled in an optional operation 1009. This active cooling may include, as described herein, circulating a cooling gas over the substrate, moving the substrate closer to the faceplate, or both. In some cases, this proximity is 5 mm or less, including 2 mm. The cooling gas may also include, for example, helium and nitrogen. In some cases, after operation 1009, operations 1003-1009 may be repeated, with each sequence being considered a cycle.

[0257] In some embodiments, operations 1003, 1005, and 1007 may also be performed while the outer surfaces of the chamber walls, faceplates, and / or pedestals are actively heated as described above. These articles may be heated to about 80°C to 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 inside of the chamber is under vacuum, which may be at a pressure of about 0.1 Torr to about 10 Torr, or about 0.2 Torr to about 10 Torr.

[0258] The techniques provided herein may result in various adjustments to the processing 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 performed in an open-loop manner based on empirical or calculated data. In some embodiments, for example, the technique may follow a sequence similar to that shown in Figures 13 and 14. In some other embodiments, the sequence may involve etching or part of one etching cycle while the substrate is at a first temperature, followed by a temperature increase to a higher second temperature, at which another etching cycle or another part of the same etching cycle is performed. After this, the substrate may be actively cooled, and etching may be repeated on the same substrate or a new substrate.

[0259] Figure 15 shows a second technique according to the disclosed embodiment, where operations 1101-1107 are identical to operations 1001-1007. After etching in operation 1007, in operation 1113, the heater power is adjusted to a different power than the power used during maintenance in operation 1005 in order to heat the substrate to a higher second temperature, provided in operation 1115. The substrate temperature may be maintained at this second temperature during further etching or modification of the substrate, as shown in operations 1117 and 1119. In various embodiments herein, the etching chemicals for operation 1119 include the aforementioned chemical species, e.g., HF, organic solvents and / or water, additives, and carrier gases. In some cases, the substrate may be modified at the second temperature, as described with respect to operation 205 in Figure 2, for example. In such cases, the chemicals used for operation 1107 may be selected to modify the material on the surface of the substrate in a desired form. After these operations, the substrate may be actively cooled in operation 1109. In some cases, etching operations 1103-1109 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 characteristic is not limiting. In some embodiments, for example, as described in relation to Figures 2 and 4, the first temperature (which can be used to accelerate the modification of the material on the substrate surface) may be higher than the second temperature (which can be used to accelerate the etching of the modified material on the substrate surface).

[0260] In some embodiments, heating and maintenance operations may be based on empirical and measured data of the apparatus, such as the pedestal window, e.g., empirically derived temperature drift. As described above, the window can retain heat throughout the process and can function as an independent heater to the substrate. To address this drift, the substrate heater may be adjusted, such as reducing the overall power supplied to the LEDs of the substrate heater during maintenance and etching operations, as described in 1005, 1105, 1007, and 1107. These adjustments may be linear or nonlinear, e.g., stepped or curved. This adjustment may further include adjusting 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 dissipate heat, while the edges of the window generate the least heat because some of this heat is transferred to the pedestal. Accordingly, to maintain uniform heating, one or more independently controllable zones of the LEDs in the center of the substrate heater may be cooled to account for the increased heat in the center of the window. As a result, heat is generated by both the window and the substrate heater, which may result in the same heat being transferred to the central region of the substrate. Similarly, one or more independently controllable zones of LEDs in the outer region of the substrate heater may be lowered or kept the same to account for any additional heating, if present, caused by the outer edge of the window.

[0261] In some embodiments described above, each LED may be individually controllable, and in some such embodiments, a single LED may be tuned to emit more or less light than one or more other LEDs. This tuning may be done to account for hot or cold spots on the substrate. For example, a point on a wafer may be hotter or colder than other parts of the substrate, and one LED located below or close to that point on the substrate may be tuned to adjust the temperature at that point. This may include reducing the light emitted by one LED to lower the temperature at that point, or increasing the light emitted by one LED to increase the temperature at that point.

[0262] The techniques provided herein may include feedback control loops for adjusting working parameters such as power for one or more zones of an LED. These feedback loops may be performed during the heating, holding, and etching operations described herein. This may include determining the temperature at the edge and at one or more locations inside the substrate using one or more of the sensors described herein, and adjusting the substrate heater based on these measurements.

[0263] Figure 16 shows a third technique according to the disclosed embodiment. Here, operations 1201-1211 are similar to operations 1001-1011, except that the techniques herein involve measuring the substrate temperature during one or more of these operations and adjusting the substrate heater based on these measurements. The temperature measurement is represented by operation 1221, and the adjustment is represented by operation 1223. The adjustment of the substrate heater may involve increasing or decreasing power to one or more independently controllable zones of the LEDs, including all of the LEDs. For example, as described above in relation to Figure 9, a temperature sensor within the substrate support may indicate that the substrate edge has reached or exceeded a first temperature during one or more of operations 1203, 1205, and 1207, and power supplied to all of the LEDs may be reduced to lower the substrate temperature. This may be because at least one of the sensors indicates that the substrate temperature is above a certain threshold, e.g., above a first temperature. In another example, one of the substrate supports might indicate that the substrate temperature is higher than the first temperature, and adjustments may be made to an independently controllable LED zone around this single sensor to reduce the heat supplied at that location rather than across the entire substrate.

[0264] Similarly, the pyrometer described above may also detect the temperature of the substrate at a location on the substrate, for example, at its center. This temperature measurement may also be used alone or in combination with a temperature sensor within the substrate support to adjust the substrate heater. For example, the pyrometer may indicate that the center of the substrate is at a higher temperature than a first temperature, and adjustments may be made to independently controllable LED zones around the center of the substrate, or to the entire substrate, to lower the temperature of the substrate at that location. While these embodiments are performed in relation to reducing the power of the LEDs, the adjustments are not limited to such embodiments, and the power of one or more independently controllable LED zones may be adjusted to raise the temperature at one or more locations on the substrate.

[0265] Other techniques may measure the light emitted by the LEDs and, based on that measurement, adjust one or more independently controllable LED zones. This may include measuring one or more metrics of the visible light emitted by the LEDs using one or more sensors configured to emit visible light having wavelengths of 400 nm to 800 nm from the LEDs and to detect the visible light emitted from multiple 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.

[0266] In some embodiments, the apparatus described herein may include a controller configured to control various aspects of the apparatus in order to carry out the technology described herein. For example, referring again to Figure 5, the apparatus 100 includes a controller 131 (which may include one or more physical or logical controllers), which is communicatively connected to the processing chamber and controls 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 which, when the disclosed embodiments are carried out, controls, for example, flow rate and duration, substrate heating unit, substrate cooling unit, loading and unloading of substrates in the chamber, thermal flotation of substrates, and process gas unit. 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 chemicals, the selected recipe, the reactor architecture, and other factors.

[0267] In some embodiments, the controller 131 is part of an apparatus or system that may be part of the embodiments described above. Such systems and 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 (such as a gas flow system, a substrate heating unit, a substrate cooling unit, etc.). These systems may be incorporated into electronic equipment for controlling pre-processing, in-processing, and post-processing operations on semiconductor wafers or substrates. The electronic equipment may be referred to as a “controller” that controls various components or sub-components of the system (one or more). Depending on the processing parameters and / or the type of system, the controller 131 may be programmed to control any process disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, position and work settings, loading and unloading of wafers to and from tools and other transport tools connected to or interfaced with a particular system and / or load lock.

[0268] Broadly speaking, the controller 131 may be defined as an electronic device having various integrated circuits, logic, memory, and / or software, which receives and issues instructions, controls operations, enables cleaning operations, and enables endpoint measurements. The integrated circuit may include a chip in the form of firmware that stores program instructions, a chip defined as a digital signal processor (DSP), an application-specific integrated circuit (ASIC), and / or one or more microprocessors, or a microcontroller that executes program instructions (e.g., software). Program instructions are instructions communicated to the controller in the form of various individual settings (or program files) that define work parameters for performing a particular process on or against a semiconductor wafer, or against a system. In some embodiments, the work parameters may be part of a recipe defined by a process engineer to perform one or more processing operations when fabricating one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0269] In some implementations, the controller 131 may be part of or coupled to a computer that is integrated into, coupled to, networked to, or a combination thereof within the system. For example, the controller may be in the “cloud” or all or part of a fab host computer system, thereby enabling remote access to wafer processing. The computer may enable remote access to the system to monitor the current progress of fabrication work, investigate the history of past fabrication work, investigate trends or performance metrics from multiple fabrication work, modify parameters of the current process, set up subsequent processing tasks, or start a new process. In some embodiments, a remote computer (e.g., a server) may provide process recipes to the system via a network that may include a local network or the internet. The remote computer may include a user interface that enables input or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller 131 receives instructions in data format that specify parameters for each processing task 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 tools the controller is configured to interface with or control. Therefore, as described above, the controller 131 may be distributed by comprising one or more individual controllers, which are networked together and operate toward common purposes such as the processes and controls described herein. An example of a distributed controller for such purposes might be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (e.g., at the platform level or as part of a remote computer), which together control the process in the chamber.

[0270] As described above, depending on the process work performed by the device, the controller 131 may communicate with one or more of the following: other device circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout the factory, a main computer, another controller, or tools used for material handling to load and unload wafer containers between tool locations and / or load ports within the semiconductor manufacturing plant.

[0271] As stated above, the controller is configured to implement any of the above-described technologies. This may include causing a substrate transfer robot to place the substrate in the chamber onto a plurality of substrate supports, supplying power to LEDs to emit visible light having a wavelength of 400 nm to 800 nm to heat the substrate to a first temperature such as 100°C to 600°C, and flowing an etching gas into the chamber to etch the substrate. This may further 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 moving a pedestal vertically so that the substrate is offset by a first non-zero distance from the faceplate of the gas distribution unit, thereby transferring heat from the substrate to the faceplate via non-contact radiation. This may further include controlling the chemicals delivered to the reaction chamber as described herein.

[0272] conclusion While the embodiments described above are presented in some detail for the purpose of clarifying understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are numerous alternative ways of implementing the processes, systems, and apparatus of these embodiments. Accordingly, these embodiments are illustrative and should not be considered limiting, and embodiments should not be limited to the details presented herein.

Claims

1. A method for etching a substrate, wherein the method is a. Providing the substrate in a reaction chamber, wherein the substrate includes a target material that will be partially or completely removed from the substrate during etching; b. Supplying a gas mixture into the reaction chamber and exposing the substrate to the gas mixture while the pressure in the reaction chamber is approximately 0.2 to 10 Torr, wherein the gas mixture is in the vapor phase, i. Halogen source, ii. Organic solvents and / or water, iii. Additives, and, iv. Supply of a gas mixture, including a carrier gas; c. A method comprising supplying thermal energy to the reaction chamber to induce a reaction that partially or completely etches the target material from the substrate, wherein the substrate is not exposed to plasma during etching.

2. A method according to claim 1, further comprising, prior to (b), supplying a second gas mixture into the reaction chamber and exposing the substrate to thermal energy and the second gas mixture, wherein the thermal energy causes 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 completely etching the target material.

3. A method according to claim 1, wherein the organic solvent and / or water comprises an alcohol.

4. A method according to claim 3, wherein the alcohol comprises an alcohol 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.

5. A method according to claim 1, wherein the organic solvent and / or water includes a laboratory solvent.

6. A method according to claim 5, wherein the laboratory solvent is selected from the group consisting of acetonitrile, dichloromethane, carbon tetrachloride, and combinations thereof.

7. A method according to claim 1, wherein the organic solvent and / or water comprises a ketone.

8. A method according to claim 7, wherein the ketone comprises a ketone selected from the group consisting of acetone, acetophenone, and combinations thereof.

9. A method according to claim 1, wherein the organic solvent and / or water comprises water.

10. A method according to claim 9, wherein the organic solvent and / or water does not contain any organic solvent.

11. A method according to claim 1, wherein the organic solvent and / or water comprises an alkane.

12. A method according to claim 11, wherein the alkane comprises an alkane selected from the group consisting of pentane, hexane, octane, cyclopentane, cyclohexane, and combinations thereof.

13. A method according to claim 1, wherein the organic solvent and / or water comprises an aromatic solvent.

14. A method according to claim 13, wherein the aromatic solvent is an aromatic solvent selected from the group consisting of toluene and benzene.

15. A method according to claim 1, wherein the organic solvent and / or water comprises an ether.

16. A method according to claim 15, wherein the ether comprises tetrahydrofuran.

17. A method according to claim 1, wherein the organic solvent and / or water comprises a nitrile.

18. A method according to claim 17, wherein the nitrile comprises acetonitrile.

19. A method according to any one of claims 1 to 18, wherein the carrier gas is N 2 A method comprising a gas selected from the group consisting of He, Ne, Ar, Kr, and Xe.

20. A method according to any one of claims 1 to 18, wherein the additive comprises a heterocycle.

21. A method according to claim 20, wherein the heterocycle is a heterocyclic aromatic compound.

22. A method according to claim 21, wherein the heterocyclic aromatic compound comprises a heterocyclic aromatic compound selected from the group consisting of picoline, pyridine, pyrrole, imidazole, thiophene, N-methylimidazole, N-methylpyrrolidone, benzimidazole, 2,2-bipyridine, dipicolinic acid, 2,6-lutidine, 4-N,N-dimethylaminopyridine, azulene, and combinations thereof.

23. A method according to claim 21, wherein the heterocycle is a halogen-substituted aromatic compound.

24. A method according to claim 23, wherein the halogen-substituted aromatic compound comprises a halogen-substituted aromatic compound selected from the group consisting of 4-bromopyridine, chlorobenzene, 4-chlorotoluene, and fluorobenzene.

25. A method according to claim 20, wherein the heterocycle is a heterocyclic aliphatic compound.

26. A method according to claim 25, wherein the heterocyclic aliphatic compound is pyrrolidine.

27. A method according to any one of claims 1 to 18, wherein the additive comprises an amine.

28. A method according to claim 27, wherein the amine is an amine selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, 1,2-ethylenediamine, aniline, aniline derivatives, N-ethyldiisopropylamine, tert-butylamine, guanidine, and combinations thereof.

29. A method according to claim 27, wherein the amine comprises a fluoroamine.

30. A method according to claim 29, wherein the fluoroamine is 4-trifluoromethylaniline.

31. A method according to any one of claims 1 to 18, wherein the additive comprises an amino acid.

32. A method according to claim 31, wherein the amino acid comprises an amino acid selected from the group consisting of histidine and alanine.

33. A method according to any one of claims 1 to 18, wherein the additive comprises an organophosphorus compound.

34. A method according to claim 33, wherein the organophosphorus compound comprises a phosphazene.

35. A method according to any one of claims 1 to 18, wherein the additive comprises an oxidizing agent.

36. A method according to claim 35, wherein the oxidizing agent is an oxidizing agent selected from the group consisting of hydrogen peroxide, sodium hypochlorite, tetramethylammonium hydroxide, and combinations thereof.

37. A method according to any one of claims 1 to 18, wherein the additive comprises a bifluoride source.

38. A method according to claim 37, wherein the bifluoride source comprises a bifluoride source selected from the group consisting of ammonium fluoride, hydrogen fluoride, buffer oxide etching mixture, pyridine hydrogen fluoride, and combinations thereof.

39. The method according to claim 38, wherein the bifluoride source reacts with HF before or after delivery to the reaction chamber. 2 - A method for forming something.

40. A method according to any one of claims 1 to 18, wherein the additive comprises an aldehyde.

41. A method according to claim 40, wherein the aldehyde comprises an aldehyde selected from the group consisting of acrolein, acetaldehyde, formaldehyde, benzaldehyde, propionaldehyde, butyraldehyde, cinnamaldehyde, vanillin, and tolualdehyde.

42. A method according to any one of claims 1 to 18, wherein the additive comprises a carbene.

43. A method according to any one of claims 1 to 18, wherein the additive comprises an organic acid.

44. A method according to claim 43, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, and combinations thereof.

45. The method according to any one of claims 1 to 18, wherein the halogen source is hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen bromide (HBr), fluorine (F 2 ), chlorine (Cl 2 ), bromine (Br 2 ), chlorine trifluoride (ClF 3 ), nitrogen trifluoride (NF 3 ), nitrogen trichloride (NCl 3 ), and nitrogen tribromide (NBr 3 ), and is selected from the group consisting of.

46. A method according to any one of claims 1 to 18, wherein the halogen source is an organic halide.

47. The method according to claim 46, wherein the organic halogen is fluoroform (CHF 3 ), chloroform (HCl 3 ), bromoform (CHBr 3 ), carbon tetrafluoride (CF 4 ), carbon tetrachloride (CCl 4 ), carbon tetrabromide (CBr 4 ), perfluorobutene (C 4 F 8 ), and perchlorobutene (C 4 Cl 8 A method selected from the group consisting of the following.

48. A method according to any one of claims 1 to 18, wherein the halogen source is silicon halide.

49. The method according to claim 48, wherein the silicon halide is silicon tetrafluoride (SiF 4 ), silicon tetrachloride (SiCl 4 ), silicon tetrabromide (SiBr 4 ), and Six 6 A method comprising selecting from the group consisting of constituent compounds, where X is a halogen.

50. A method according to any one of claims 1 to 18, wherein the halogen source is a metal halide.

51. The method according to claim 50, wherein the metal halide is molybdenum hexafluoride (MoF 6 ), molybdenum hexachloride (MoCl 6 ), molybdenum hexabromide (MoBr 6 ), tungsten hexafluoride (WF 6 ), tungsten hexachloride (WCl 6 ), tungsten hexabromide (WBr 6 ), Titanium tetrafluoroide (TiF 4 ), titanium tetrachloride (TiCl 4 ), Titanium tetrabromide (TiBr 4 ), zirconium fluoride (ZrF 4 ), zirconium chloride (ZrCl 4 ), and zirconium bromide (ZrBr 4 A method selected from the group consisting of the following.

52. A method according to any one of claims 1 to 18, wherein the additive is in an amount of about 0.1 to 5% by weight of the total amount of the additive and the organic solvent and / or water.

53. A method according to any one of claims 1 to 18, wherein the volume ratio of the halogen source to the additive is 10 or less.

54. A method according to claim 53, wherein the target material is an oxide, the substrate further comprises a second material different from the target material, and (c) comprises selectively etching the target material with respect to the second material.

55. A method according to claim 54, wherein the target material is silicon oxide and the second material is silicon nitride.

56. A method according to claim 54, wherein the target material is silicon oxide and the second material is silicon (Si) or silicon germanium (SiGe).

57. An apparatus for etching a substrate, wherein the apparatus is a. A reaction chamber configured to withstand an internal pressure of approximately 0.2 to 10 Tors; b. A substrate support configured to support the substrate during etching; c. An inlet for introducing the gaseous mixture into the reaction chamber; d. An outlet for removing gaseous chemical species from the reaction chamber; and, e. An apparatus comprising a controller configured to carry out the method described in any one of claims 1 to 56.

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