Vapor-phase etching of metal-containing materials

Abstract

The subject matter disclosed and claimed relates to a process for performing selective hot-air etching of metals including Ti, Co, Ni, Cu, Mo, Ru, Ta and / or W, and compounds thereof (such as oxides, hydroxides, oxyhydroxides, carbonates, carbides, fluorides, or chlorides), without requiring the use of plasma or halogenated volatilizers.

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 496,230, filed Apr. 14, 2023, and is incorporated herein by reference in its entirety as if fully set forth herein.

Background Art

[0002] Technical Field

[0003] The disclosed and claimed subject matter relates to a process for performing vapor etching of films containing Co, Cu, Ni, Mo, or similar materials using a halogen - free volatilizing agent. The disclosed and claimed subject matter further includes (1) a selective vapor etching process in which a volatilizing agent is introduced to selectively etch a thin film of material on a substrate of different materials, and (2) a selective atomic layer etching (ALE) process in which a surface - modifying reagent is introduced and then a volatilizing agent is introduced to selectively etch the modified surface material. In both cases, the amount of material to be etched can be controlled by repeating the process a plurality of times.

[0004] Related Art

[0005] The miniaturization of features in the semiconductor industry is a major factor in the continuous performance improvement of devices. This trend is expected to continue in at least the next few generations of computer chips. In this regard, existing methods for manufacturing nanometer - scale components are reaching physical limits, and new chemical processes with high selectivity and atomic layer precision are needed.

[0006] In the manufacturing of microelectronic logic devices, highly selective etching is required to precisely remove specific materials or groups of materials from exposed surfaces, including many materials such as metals, dielectrics, and semiconductors. Metal etching is particularly necessary in back-end-of-line (BEOL) processes that form interconnects between logic transistors and their peripheral devices, targeting materials such as Co, Cu, Mo, Ru, W, TiN, and TaN. Several approaches to scaling down BEOL processes, such as the fully self-aligned via (FSAV) method, require selectively retreating specific metals or groups of metals by a few nanometers relative to the dielectric material, following the planarization of the patterned wafer. Residues of metals or etching agents remaining on the dielectric material surface can impair device performance. Therefore, it is desirable to effectively and selectively remove all residues during and / or after the etching process.

[0007] Vapor-phase etching or cleaning methods are suitable for this problem. Vapor-phase methods allow etching to a smaller critical dimension than wet etching and produce less residue. Compared to plasma etching, vapor-phase etching can also be performed with less damage to exposed materials that are not the target of etching. Therefore, vapor-phase etching or cleaning processes that selectively remove specific materials or groups of materials, such as thin metal oxide layers formed by exposing metals to the atmosphere or an oxidizing agent, are desirable. In some implementation configurations, the vapor-phase etchant can be introduced continuously. In some implementation configurations, there is a single continuous introduction-purge cycle that can be repeated.

[0008] Atomic layer deposition (ALD) is a technology with expanding applications in the semiconductor industry and is currently the most precise method for controlling the amount of material deposited. In ALD, an atomic layer is typically deposited on all surfaces exposed to a precursor in the gas phase. The thickness of this layer can be up to one atomic layer. By sequentially exposing the surface to two different precursors, a layer of material with the desired thickness is deposited. A typical example of such a process is the deposition of aluminum oxide (Al2O3) from trimethylaluminum (TMA, Al(CH3)3) and water (H2O), in which methane (CH4) is removed from the two reactants. Coating thin, narrow vias and other high aspect ratio features using ALD has been demonstrated in numerous publications.

[0009] Atomic layer etching (ALE or ALEt) can be considered as removing material layer by layer, in contrast to ALD which adds material layer by layer. In ALE, a layer of atoms is removed from the surface of a specific material or "all" of a specific group of materials exposed to a precursor in the gas phase. The thickness of this layer is ideally the same as the thickness of one atomic layer at most. ALE is performed by successively exposing the surface to at least two different precursors. That is, the first precursor activates a layer of surface atoms, and the second precursor promotes the sublimation of this activated layer of atoms. The first precursor may be called a surface modifier or surface modifier, and the second precursor may be called a volatilizer or volatilizer. A third precursor may be used to regenerate the surface to a state where the first precursor can be activated.

[0010] As described above, isotropic ALE involves repeating a cycle of introducing a reactant into a vacuum chamber containing the workpiece to be etched, and then purging the chamber to remove excess reactant and any reaction products. In some implementations, there are two consecutive introduction-purge subcycles, each with a different reactant or combination of reactants. In some implementations, there are three or more consecutive introduction-purge subcycles, each with a different reactant or combination of reactants.

[0011] Cobalt (Co) and its alloys are considered promising materials for use in middle-of-line (MOL) and back-end-of-line (BEOL) processing of semiconductor logic devices and memory devices, either as primary conductive wiring materials or as liners or barriers between other conductive wiring materials and interlayer dielectric films (ILDs). Other metals relevant to such applications include Cu, Mo, Ru, W, TiN, and TaN.

[0012] Several cobalt etching procedures have been described. For example, see Zhao et al., Applied Surface Science, 455, 438 (2018); Konh et al., Journal of Vacuum Science & Technology A, 37, 021004 (2019); Wang et al., Journal of Vacuum Science & Technology A, 38, 022611 (2020); and Kim et al., Applied Surface Science, 619, 156751 (2023). In one of these procedures, cobalt was etched at a temperature above 377°C and the cobalt surface (containing native oxides) was exposed to 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Hhfac). Next, the treated surface was heated to induce sublimation of cobalt 1,1,1,5,5,5-hexafluoro-2,4-pentanedione. In a modified version, the cobalt surface was etched at a temperature higher than 140°C by sequentially exposing it to the following substances: (A) Chlorine. This oxidizes the cobalt layer to cobalt chloride (surface activation); and (B) Acetylacetone (1,1,1,5,5,5-hexafluoro-2,4,pentanedione (Hhfac), etc.). This reacts with cobalt chloride surface species to produce volatile cobalt chloroacetylacetonate species (sublimation).

[0013] Alternatively, cobalt etching was achieved at temperatures above 80°C, with etching rates reaching 28 Å / cycle. See, for example, Chen et al., J.Vac.Sci.Technol., A 35, 05C305 (2017). This process involves sequentially exposing the cobalt surface to the following substances: (A) Oxygen plasma. This oxidizes multiple cobalt layers to cobalt oxide (surface activation); and (B) Formic acid. This reacts with cobalt oxide surface species to produce volatile cobalt formate species (sublimation).

[0014] As an alternative method, thin films of cobalt and copper were etched using supercritical CO2 and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione under high pressure at 100°C and 250°C. See, for example, Rasadujjaman et al., Microelectron.Eng.153,5 (2016).

[0015] A copper etching process using plasma to chlorine copper and produce CuCl2 was described. See, for example, Tamirisa et al., Microelectron.Eng.84,105(2007); Wu et al., J.Electrochem.Soc.,157,H474(2010); and Hess DW, Workshop on Atomic-Layer-Etch and Clean Technology, San Francisco, Ca(2014). The CuCl2 layer was then etched with hydrogen plasma to produce volatile Cu3Cl3. Although this process can be performed at a low temperature of 20°C, its application to etching Cu on small features has been limited due to the resulting significant tapered shape.

[0016] Another method involves etching copper at temperatures exceeding 275°C, with reported etching rates of 0.09 nm / cycle. See, for example, Mohimi et al., ECS Journal of Solid State Science and Technology, 7, P491 (2018). This process involves sequentially exposing the copper surface to the following substances: (A) Oxygen. This is a mild oxidizing agent and oxidizes the copper layer to copper oxide (surface activation); and (B) Acetylacetone (1,1,1,5,5,5-hexafluoro-2,4,pentanedione (Hhfac), etc.). This reacts with copper oxide surface species to produce volatile copper acetylacetonate species (sublimation).

[0017] Another method involves etching tungsten. See, for example, Johnson NR and George SM, ACS Applied Materials & Interfaces, 9, 34435 (2017). In this process, tungsten can be etched (128°C to 207°C) by sequentially exposing a tungsten surface with a native oxide layer to the following materials: (A) A mixture of oxygen and ozone. This oxidizes the additional layer of tungsten, producing tungsten oxide (surface activation); (B) Boron trichloride. This reacts with some of the tungsten oxide to produce non-volatile boron oxide and volatile tungsten oxychloride (sublimation of tungsten-containing species; some tungsten oxide remains beneath the boron oxide); and (C) Hydrogen fluoride. This reacts with boron oxide to produce volatile water vapor and volatile boron trifluoride (regeneration of a new tungsten oxide surface).

[0018] Several implementations of ALE include, within a vacuum chamber tool such as an atomic layer deposition (ALD) reactor, the following steps are repeated: (1) introducing a first chlorinating agent to convert solid surface Co into solid CoCl2; (2) a first purging step of the reactor; (3) introducing a second volatilizing agent to convert solid CoCl2 into gaseous metal-organic complexes or adducts; and (4) a second purging step of the reactor.

[0019] In contrast to some of the examples above, the disclosed method does not require plasma and does not require the use of corrosive halogenated gases. The disclosed method may also use halogen-free volatilizers that reduce the possibility of harmful surface contamination by the etching process.

[0020] In the disclosed and claimed subject matter, a metal-containing surface material (e.g., a thin layer of a metal compound on a metal with an oxidation state greater than zero) is exposed in the gas phase to a halogen-free acid such as propionic acid, isobutyric acid, or pivalic acid. The metal-containing surface material reacts with the halogen-free acid to form a volatile metal-organic complex, but the underlying material remains unaffected. In a further embodiment of the disclosed and claimed subject matter, the introduction of the halogen-free acid is alternately repeated with inert gas purging to improve etching control. In a further embodiment of the disclosed and claimed subject matter, an atomic layer etching (ALE) process is described. In this process, a surface modifier such as a chlorinating agent is introduced to form a metal compound on the surface, and a halogen-free acid is introduced to the surface to remove the newly formed metal compound, enabling controlled removal of the metal. [Overview of the Initiative]

[0021] In one embodiment, the disclosed and claimed subject matter relates to a method for the selective thermal vapor etching of a metal-containing material that includes a metal, a metal alloy, and a metal compound. The method generally includes (i) exposing the metal-containing material to one or more volatilizing agents to produce a volatile by-product containing one or more metals from the metal-containing material, and (ii) a purging step that comprises, consists essentially of, or consists of a volatilization step. The volatilization step can be repeated a desired number of times to selectively remove a metal compound of a desired thickness.

[0022] In another embodiment, the disclosed and claimed subject matter relates to a method for selectively thermally vapor etching a metal-containing material that includes a metal, a metal alloy, and a metal compound. The method comprises, consists essentially of, or consists of the volatilization step and a surface modification step described above. The surface modification step includes (a) exposing the metal-containing material to one or more surface modification agents to form a volatile metal-containing material that is different from the metal-containing material prior to exposure to the one or more surface modification agents, and (b) a purging step that comprises, consists essentially of, or consists of the same.

[0023] In another embodiment, the disclosed and claimed subject matter relates to repeating steps (a), (b), (i), and (ii) a desired number of times to selectively remove a metal of a desired thickness.

[0024] In a further aspect of this embodiment, the surface modification agent contains a halogen. In a further aspect of this embodiment, the surface modification agent contains chlorine.

[0025] In another embodiment, the disclosed and claimed subject matter relates to a method for a thermal vapor etching process in which a particular material (such as a metal, a metal compound, etc.) or a group of such materials is etched while another material (such as another metal, a metal compound, a non-metal, a non-metal compound, etc.) or a group of such materials is not etched.

[0026] In another embodiment, the disclosed and claimed subject matter relates to a method for a thermal vapor etching process in which a thin layer of a metal compound is etched while a metal or metal alloy is not etched. In another embodiment, the metal compound includes one or more elements of the metal or metal alloy. In another embodiment, the metal compound includes a thin film on the metal or metal alloy.

[0027] In one aspect, the disclosed and claimed subject matter relates to a process for the thermal vapor etching of metals including Co, Ni, Cu, Mo, Ru, and W. In another aspect, the disclosed and claimed subject matter relates to a process for the thermal vapor etching of a metal compound including a compound containing Ti, Co, Ni, Cu, Mo, Ru, Ta, and / or W. In another aspect, the disclosed and claimed subject matter relates to a process for atomic layer etching (ALE) of metals including Co, Ni, Cu, Mo, Ru, and W. In another aspect, the disclosed and claimed subject matter relates to a process for the vapor etching of compounds such as oxides, hydroxides, oxyhydroxides, carbonates, carbides, nitrides, fluorides, or chlorides of metals including Ti, Co, Ni, Cu, Mo, Ru, Ta, and / or W.

[0028] This summary section of the invention does not specify all embodiments and / or progressively novel aspects of the disclosed and claimed subject matter. Instead, this summary of the invention only provides a preliminary discussion of different embodiments and corresponding points of novelty over the prior art and known techniques. For further details and / or possible aspects of the disclosed and claimed subject matter and embodiments, the reader is referred to the section on the mode for carrying out the invention and the corresponding figures of this disclosure as further discussed below.

[0029] The discussion of the order of different processes described herein is presented for clarity. In general, the processes disclosed herein can be performed in any preferred order. In addition, each of the different features, techniques, configurations, etc., disclosed herein may be discussed in different places in this disclosure, but each of the concepts is intended to be performed independently of or in combination with each other as appropriate. Thus, the subject matter disclosed and claimed can be embodied and seen in many different ways. [Brief explanation of the drawing]

[0030] The attached drawings are included to provide a further understanding of the disclosed subject matter, are incorporated herein and constitute part of this specification, illustrate embodiments of the disclosed subject matter, and, together with the detailed description, help to illustrate the principles of the disclosed subject matter. The drawings are as follows: [Figure 1] An exemplary cycle of the disclosed and claimed process for vapor-phase etching of a metal-containing material is shown. [Figure 2] This document illustrates an exemplary cycle of the disclosed and claimed process for vapor-phase etching (i.e., ALE) of metal-containing materials by surface modification and volatilization. [Figure 3] This document illustrates an exemplary cycle of the disclosed and claimed process for cobalt ALE.

[0031] definition Unless otherwise specified, the following terms used in this specification and in the claims have the following meanings in this application:

[0032] For the purposes of the subject matter disclosed and claimed, the numbering scheme for the families of the periodic table follows the IUPAC periodic table of elements.

[0033] In this specification, the term "and / or" as used in phrases such as "A and / or B" is intended to include "A and B", "A or B", "A", and "B".

[0034] The terms "substituent," "radical," "group," and "moiety" can be used interchangeably.

[0035] As used herein, the terms “metal-containing complex” (or more simply “complex”) and “precursor” are used interchangeably and refer to metal-containing molecules or compounds that can be used to prepare metal-containing films by deposition processes such as ALD or CVD. Metal-containing complexes can be deposited, adsorbed, decomposed, delivered, and / or passed through a substrate or its surface to form a metal-containing film.

[0036] As used herein, the term “metal-containing film” includes not only elemental metal films, as more fully defined below, but also films containing metal along with one or more elements, such as metal oxide films, metal nitride films, metal silicide films, metal carbide films, and so on. As used herein, the terms “elemental metal film” and “pure metal film” are used interchangeably and refer to films consisting of or essentially made of pure metal. For example, an elemental metal film may contain a metal with 100% purity, or an elemental metal film may contain a metal with one or more impurities with a purity of at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, at least about 99%, at least about 99.9%, or at least about 99.99%. Unless the context requires otherwise, the term “metal film” shall be interpreted as meaning an elemental metal film.

[0037] As used herein, the term “deposition process” is used to refer to any type of vapor deposition technique, including but not limited to CVD and ALD. In various embodiments, CVD may take the form of conventional (i.e., continuous flow) CVD, liquid injection CVD, or photo-assisted CVD. CVD may also take the form of pulsed techniques, i.e., pulsed CVD. ALD is used to form metal-containing films by vaporizing and / or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes, see, for example, George SM, et al. J. Phys. Chem., 1996, 100, 13121-13131. In other embodiments, ALD may take the form of conventional (i.e., pulse injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma-enhanced ALD. The term “deposition process” further encompasses a variety of deposition techniques. This vapor deposition technique is described in *Chemical Vapor Deposition: Precursors, Processes, and Applications* by Jones, AC and Hitchman, ML, Eds., The Royal Society of Chemistry, Cambridge, 2009; Chapter 1, pp. 1-36.

[0038] As used herein, the term “feature” refers to an opening in a substrate that can be defined by one or more side walls, bottom surfaces, and top corners. In various embodiments, a feature may be a via, trench, contact, dual damascene, and so on.

[0039] The terms "about" or "approximately," when used in relation to a measurable numerical variable, refer to the stated value of the variable and all values ​​of the variable within the experimental error of the stated value (e.g., within the 95% confidence interval of the mean) or within a percentage of the stated value (e.g., ±10%, ±5%), whichever is greater.

[0040] The volatilizers and surface modifiers are preferably substantially water-free. As used herein, the term “substantially water-free” means less than 5000 ppm (by weight) as measured by proton NMR or Karl Fischer titration, preferably less than 3000 ppm as measured by proton NMR or Karl Fischer titration, more preferably less than 1000 ppm as measured by proton NMR or Karl Fischer titration, and most preferably less than 100 ppm as measured by proton NMR or Karl Fischer titration.

[0041] A halo or halide refers to a halogen, F, Cl, Br, or I bonded to an organic or metallic part by one bond. In some embodiments, the halogen is F. In other embodiments, the halogen is Cl. In other embodiments, the halogen is Br. In other embodiments, the halogen is I.

[0042] Alkyl halides are C1-C atoms that are completely or partially halogenated. 20 It refers to alkyl groups.

[0043] Perfluoroalkyl refers to a linear, cyclic, or branched saturated alkyl group as defined above, in which all hydrogen atoms are replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoroisopropyl, perfluorocyclohexyl, etc.).

[0044] The disclosed and claimed precursors are preferably substantially free of organic impurities originating from either the starting materials used in the synthesis or the by-products generated during the synthesis. Examples include, but are not limited to, alkanes, alkenes, alkynes, dienes, ethers, esters, acetates, amines, ketones, amides, and aromatic compounds. As used herein, the term “free of organic impurities” means less than 1000 ppm by GC, preferably less than 500 ppm by GC (by weight), and most preferably less than 100 ppm by GC or other assay analytical methods (by weight). Importantly, when used as a precursor for depositing ruthenium-containing films, the precursors should have a purity of preferably 98% by weight or more, more preferably 99% by weight or more, as measured by GC.

[0045] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described herein. All documents or parts of documents cited herein, including but not limited to patents, patent applications, articles, books, and professional works, are expressly incorporated herein by reference in whole for any purpose. If any incorporated document or similar material defines a term in a manner that conflicts with the definitions of terms in this application, this application shall prevail. [Modes for carrying out the invention]

[0046] It should be understood that both the general description above and the detailed description below are illustrative and descriptive, and do not limit the subject matter claimed. The purpose, features, advantages, and ideas of the disclosed subject matter will be apparent to those skilled in the art from the descriptions provided herein, and the disclosed subject matter is readily implementable by those skilled in the art based on the descriptions present herein. Any descriptions of “preferred embodiments” and / or examples illustrating a preferred way of carrying out the disclosed subject matter are included for descriptive purposes and are not intended to limit the scope of the claims.

[0047] It will also be apparent to those skilled in the art that various modifications can be made to how the disclosed subject matter is implemented in accordance with the embodiments described herein, without departing from the spirit and scope of the disclosed subject matter.

[0048] The subject matter disclosed and claimed is a process for selectively etching a metal-containing material from the surface of a substrate, comprising, essentially comprising, or comprising a volatilization step ( schematically shown in Figure 1), wherein the volatilization step is (i) Exposing a metal-containing material to one or more volatile agents to produce volatile by-products containing one or more metals from the metal-containing material; and (ii) relating to a process that includes, essentially consists of, or comprises purging. This process can be optionally combined with a surface modification process (schematically shown in Figure 2), and the surface modification process is... (a) Exposing a metal-containing material to one or more surface modifiers to form a volatile metal-containing material different from the metal-containing material before exposure to the one or more surface modifiers; and (b) including, essentially consisting of, or comprising purging.

[0049] Therefore, in one embodiment schematically shown in Figure 1, the subject matter disclosed and claimed relates to a volatilization process for selective vapor-phase etching of metal-containing materials. These processes are (i) A step of exposing the surface of a metal-containing material to one or more volatile agents to produce volatile by-products containing one or more metals from the metal-containing material; and (ii) A purging process, or a process that is essentially composed of such a process or consists of such a process.

[0050] In a further embodiment of this model, the method comprises steps (i) and (ii). The steps of the process can be repeated as many times as necessary to remove a metal or metallic compound of a desired thickness.

[0051] In another embodiment (one example of which is schematically shown in Figure 2), the subject matter disclosed and claimed relates to a process for selective ALE of metal-containing materials, which includes, essentially consists of, or comprises both a volatilization step and a surface modification step. Thus, in this embodiment, these processes are (a) A step of exposing a metal-containing material to one or more surface modifiers to form a volatile metal-containing material different from the metal-containing material before exposure to the one or more surface modifiers, and (b) Purge process, and, (i) A volatilization step including exposing the modified surface to one or more volatilizing agents to generate volatile by-products, (ii) A purging process, which is either essentially derived from or consists of such processes.

[0052] In a further embodiment of this embodiment, the surface modifier is a halogenating agent. In a further embodiment of this embodiment, the surface modifier converts the metal-containing material on the surface into a volatile metal halide.

[0053] In a further embodiment of this model, the method comprises steps (a), (b), (i), and (ii). The steps of the process can be repeated as many times as necessary to remove a metal-containing material of a desired thickness. When the process comprises both a volatilization step and a surface modification step, or comprises both, the volatilization step may precede the surface modification step, or the surface modification step may precede the volatilization step.

[0054] Number of cycles

[0055] As described above, the disclosed and claimed etching process allows for the removal of a metal or metallic compound to a desired thickness by repeating the process as many times as necessary. In some of the embodiments described above, and in some of the other embodiments described herein, the described process defines one cycle of the process. As will be understood by those skilled in the art (and as described above), the disclosed and claimed process includes a purging step between the introduction of the gas phase reagent. The purging step does not need to be performed between iterations of a single process (i.e., between multiple iterations of step (i) or between multiple iterations of step (a)).

[0056] In one embodiment, a single cycle of the vapor-phase etching process is understood to begin when the first iteration of step (i) is performed, regardless of the number of purging steps performed during the process, and to end when the last purging step (ii) is performed and another iteration (i) is performed again. It is understood that the cycle can be repeated until the desired film thickness is obtained.

[0057] In another embodiment, a single cycle of the ALE etching process is to be understood as beginning when the first iteration of step (a) is performed, regardless of the number of purging steps performed during the process, and ending when the last purging step (ii) is performed and another iteration of step (a) is performed again. It is to be understood that the cycle can be repeated until the desired film thickness is obtained.

[0058] In one embodiment, the number of cycles is approximately 100 to 1000. In one embodiment, the number of cycles is approximately 20 to 250. In one embodiment, the number of cycles is approximately 10 to 150. In one embodiment, the number of cycles is approximately 5 to 100. In one embodiment, the number of cycles is approximately 5 to 75. In one embodiment, the number of cycles is approximately 5 to 50. In one embodiment, the number of cycles is approximately 5 to 30. In one embodiment, the number of cycles is approximately 5 to 20. In one embodiment, the number of cycles is approximately 15 to 400. In one embodiment, the number of cycles is approximately 20 to 300. In one embodiment, the number of cycles is approximately 25 to 250. In one embodiment, the number of cycles is approximately 35 to 200. In one embodiment, the number of cycles is approximately 45 to 170. In one embodiment, the number of cycles is approximately 50 to 150. In one embodiment, the number of cycles is approximately 75 to 125. In one embodiment, the number of cycles is approximately 25 to 100. In one embodiment, the number of cycles is approximately 50 to 100. In another embodiment, the number of cycles is approximately 75 to 100.

[0059] In one embodiment, the number of cycles is approximately 5. In one embodiment, the number of cycles is approximately 10. In one embodiment, the number of cycles is approximately 15. In one embodiment, the number of cycles is approximately 20. In one embodiment, the number of cycles is approximately 25. In one embodiment, the number of cycles is approximately 30. In one embodiment, the number of cycles is approximately 35. In one embodiment, the number of cycles is approximately 40. In one embodiment, the number of cycles is approximately 45. In one embodiment, the number of cycles is approximately 50. In one embodiment, the number of cycles is approximately 75. In one embodiment, the number of cycles is approximately 100. In one embodiment, the number of cycles is approximately 125. In one embodiment, the number of cycles is approximately 150. In one embodiment, the number of cycles is approximately 175. In one embodiment, the number of cycles is approximately 200. In one embodiment, the number of cycles is approximately 225. In one embodiment, the number of cycles is approximately 250. In one embodiment, the number of cycles is approximately 275. In one embodiment, the number of cycles is approximately 300. In one embodiment, the number of cycles is approximately 325. In one embodiment, the number of cycles is approximately 350. In one embodiment, the number of cycles is approximately 400. In one embodiment, the number of cycles is approximately 450. In one embodiment, the number of cycles is approximately 500. In one embodiment, the number of cycles is approximately 750. In one embodiment, the number of cycles is approximately 1000.

[0060] The volatilization step and surface modification step of the etching process disclosed and claimed are described in more detail below. These steps are listed in order of implementation in one embodiment of the ALE process in which the surface modification step precedes the volatilization step.

[0061] Surface modification process

[0062] Process (a)

[0063] In step (a), the metal-containing material on the substrate surface is exposed to one or more surface modifiers to convert the metal-containing material into the corresponding metal halide species, thereby creating a volatile metal halide surface as shown in Figure 2. After this conversion, the surface metal halide is then converted into a volatile species (for example, by a volatilization step described later), which can remove some or all of the metal-containing material on the substrate surface.

[0064] metal-containing materials

[0065] The metal-containing material includes acceptable and / or desirable metals, metal alloys, or metal compounds. In one embodiment, the metal-containing material includes one or more of Co, Ni, Cu, Mo, Ru, W, TiN, or TaN. In one embodiment, the metal-containing material includes Co. In one embodiment, the metal-containing material includes Ni. In one embodiment, the metal-containing material includes Cu. In one embodiment, the metal-containing material includes Mo. In one embodiment, the metal-containing material includes Ru. In one embodiment, the metal-containing material includes W. In one embodiment, the metal-containing material includes TiN. In one embodiment, the metal-containing material includes TaN.

[0066] Surface modifier

[0067] In some embodiments, the surface modifier comprises, is essentially, or consists of one or more halogenating agents (i.e., halogenators).

[0068] In a preferred embodiment, the surface modifier contains, is essentially composed of, or comprises one or more chlorinating agents. In one embodiment, the surface modifier contains, is essentially composed of, or comprises one or more of SOCl2, Cl2, BCl3, HCl, or TiCl4. In one embodiment of this embodiment, the surface modifier contains SOCl2. In one embodiment of this embodiment, the surface modifier contains Cl2. In one embodiment of this embodiment, the surface modifier contains BCl3. In one embodiment of this embodiment, the surface modifier contains HCl. In one embodiment of this embodiment, the surface modifier contains TiCl4.

[0069] In another embodiment, the surface modifier comprises, essentially comprises, or consists of one or more brominaters. In one embodiment, the surface modifier comprises, essentially comprises, or consists of one or more of SOBr2, Br2, BBr3, HBr, or TiBr4. In one embodiment of this embodiment, the surface modifier comprises SOBr2. In one embodiment of this embodiment, the surface modifier comprises Br2. In one embodiment of this embodiment, the surface modifier comprises BBr3. In one embodiment of this embodiment, the surface modifier comprises HBr. In one embodiment of this embodiment, the surface modifier comprises TiBr4.

[0070] In another embodiment, the surface modifier contains, essentially consists of, or comprises one or more iodinating agents. In one embodiment, the surface modifier contains, essentially consists of, or comprises one or more of I2, BI3, HI, or TiI4. In one embodiment of this embodiment, the surface modifier contains I2. In one embodiment of this embodiment, the surface modifier contains BI3. In one embodiment of this embodiment, the surface modifier contains HI. In one embodiment of this embodiment, the surface modifier contains TiI4.

[0071] situation

[0072] time

[0073] As described above, in step (a), one or more metals or metal compounds are exposed to a surface modifier for a certain period of time ("exposure time") before moving to step (b), and as a result, a thin metal halide is formed on the surface. In one embodiment, the exposure time to the surface modifier in step (a) is about 0.5 seconds to about 30 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 0.5 seconds to about 10 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 1 second to about 7 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 7 seconds to about 10 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 10 seconds to about 20 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 20 seconds to about 30 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is about 0.25 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 0.5 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 1 second. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 2 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 3 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 4 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 5 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 6 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 7 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 8 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 9 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 10 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 12 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 15 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 17 seconds. In one embodiment, the exposure time to the surface modifier in step (a) is approximately 20 seconds.In one embodiment, the exposure time to the surface modifier in step (a) is approximately 25 seconds. In another embodiment, the exposure time to the surface modifier in step (a) is approximately 30 seconds.

[0074] Introduction of surface modifiers

[0075] In one embodiment, the surface modifier is flowed at a distance of approximately 5 sccm to approximately 500 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 0.5 sccm to approximately 100 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 1 sccm to approximately 200 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 1 sccm to approximately 100 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 1 sccm to approximately 50 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 5 sccm to approximately 25 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 10 sccm to approximately 20 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 15 sccm to approximately 25 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 5 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 10 sccm. In one embodiment, the surface modifier is flowed at a distance of approximately 15 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 20 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 25 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 30 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 35 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 40 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 45 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 50 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 60 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 70 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 80 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 90 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 100 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 125 sccm. In one embodiment, the surface modifier is flowed at a rate of approximately 150 sccm. In one embodiment, the surface modifier is flowed at approximately 200 sccm. In one embodiment, the surface modifier is flowed at approximately 250 sccm. In one embodiment, the surface modifier is flowed at approximately 300 sccm. In one embodiment, the surface modifier is flowed at approximately 350 sccm. In one embodiment, the surface modifier is flowed at approximately 400 sccm.In one embodiment, the surface modifier is flowed at approximately 450 sccm. In another embodiment, the surface modifier is flowed at approximately 500 sccm.

[0076] In one embodiment, the surface modifier is supplied separately.

[0077] In one embodiment, the surface modifier is supplied with a suitable carrier gas. In one embodiment, the carrier gas includes argon. In one embodiment, the carrier gas includes nitrogen.

[0078] In one embodiment, the surface modifier is supplied by steam suction.

[0079] In one embodiment, the surface modifier is introduced as a component of the plasma.

[0080] pressure

[0081] The surface modification in step (a) can be carried out at any appropriate chamber pressure. In one embodiment, the pressure is approximately 0.05 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 100 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 15 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 5 Torr. In one embodiment, the pressure is approximately 0.2 Torr to approximately 2 Torr. In one embodiment, the pressure is approximately 0.05 Torr. In one embodiment, the pressure is approximately 0.1 Torr. In one embodiment, the pressure is approximately 0.2 Torr. In one embodiment, the pressure is approximately 0.5 Torr. In one embodiment, the pressure is approximately 1 Torr. In one embodiment, the pressure is approximately 1.5 Torr. In one embodiment, the pressure is approximately 2 Torr. In one embodiment, the pressure is approximately 2.5 Torr. In one embodiment, the pressure is approximately 5 Torr. In one embodiment, the pressure is approximately 10 Torr. In one embodiment, the pressure is approximately 15 Torr. In one embodiment, the pressure is approximately 20 Torr. In one embodiment, the pressure is approximately 25 Torr. In one embodiment, the pressure is approximately 30 Torr. In one embodiment, the pressure is approximately 40 Torr. In one embodiment, the pressure is approximately 50 Torr. In one embodiment, the pressure is approximately 60 Torr. In one embodiment, the pressure is approximately 75 Torr. In one embodiment, the pressure is approximately 100 Torr.

[0082] Example process (a)

[0083] In an exemplary embodiment of the chlorination in step (a), as shown in Figure 3, the Co surface is exposed to thionyl chloride (SOCl2), thereby converting solid Co to solid CoCl2, along with the release of volatile O, S, and / or Cl compounds.

[0084] Process (b)

[0085] In step (b), any suitable inert purge gas can be used. In one embodiment, the purge gas contains argon. In one embodiment, the purge gas contains nitrogen.

[0086] time

[0087] In one embodiment, the purging time for process (b) is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the purging time for process (b) is approximately 0.25 seconds to approximately 10 seconds. In one embodiment, the purging time for process (b) is approximately 1 second to approximately 7 seconds. In one embodiment, the purging time for process (b) is approximately 7 seconds to approximately 10 seconds. In one embodiment, the purging time for process (b) is approximately 10 seconds to approximately 20 seconds. In one embodiment, the purging time for process (b) is approximately 20 seconds to approximately 30 seconds. In one embodiment, the purging time for process (b) is approximately 30 seconds to approximately 60 seconds. In one embodiment, the purging time for process (b) is approximately 0.25 seconds. In one embodiment, the purging time for process (b) is approximately 0.5 seconds. In one embodiment, the purging time for process (b) is approximately 1 second. In one embodiment, the purging time for process (b) is approximately 2 seconds. In one embodiment, the purging time for process (b) is approximately 3 seconds. In one embodiment, the purging time for process (b) is approximately 4 seconds. In one embodiment, the purging time for process (b) is approximately 5 seconds. In one embodiment, the purging time for process (b) is approximately 6 seconds. In one embodiment, the purging time for process (b) is approximately 7 seconds. In one embodiment, the purging time for process (b) is approximately 8 seconds. In one embodiment, the purging time for process (b) is approximately 9 seconds. In one embodiment, the purging time for process (b) is approximately 10 seconds. In one embodiment, the purging time for process (b) is approximately 12 seconds. In one embodiment, the purging time exposure in process (b) is approximately 15 seconds. In one embodiment, the purging time for process (b) is approximately 17 seconds. In one embodiment, the purging time for process (b) is approximately 20 seconds. In one embodiment, the purging time for process (b) is approximately 25 seconds. In one embodiment, the purging time for process (b) is approximately 30 seconds. In one embodiment, the purging time for process (b) is approximately 35 seconds. In one embodiment, the purging time for step (b) is approximately 40 seconds. In one embodiment, the purging time for step (b) is approximately 50 seconds. In one embodiment, the purging time for step (b) is approximately 60 seconds.

[0088] flow rate

[0089] In one embodiment, the purge gas is flowed at a rate of approximately 100 sccm to approximately 5000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 500 sccm to approximately 2500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1000 sccm to approximately 2000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 100 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 200 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 300 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 400 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 2000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 2500 sccm. In one embodiment, the purge gas is flowed at approximately 3000 sccm. In one embodiment, the purge gas is flowed at approximately 3500 sccm. In one embodiment, the purge gas is flowed at approximately 4000 sccm. In one embodiment, the purge gas is flowed at approximately 4500 sccm. In one embodiment, the purge gas is flowed at approximately 5000 sccm.

[0090] pressure

[0091] The purging step of step (b) can be performed at any appropriate chamber pressure. In one embodiment, the pressure is approximately 0.05 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 100 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 15 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 5 Torr. In one embodiment, the pressure is approximately 0.2 Torr to approximately 2 Torr. In one embodiment, the pressure is approximately 0.05 Torr. In one embodiment, the pressure is approximately 0.1 Torr. In one embodiment, the pressure is approximately 0.2 Torr. In one embodiment, the pressure is approximately 0.5 Torr. In one embodiment, the pressure is approximately 1 Torr. In one embodiment, the pressure is approximately 1.5 Torr. In one embodiment, the pressure is approximately 2 Torr. In one embodiment, the pressure is approximately 2.5 Torr. In one embodiment, the pressure is approximately 5 Torr. In one embodiment, the pressure is approximately 10 Torr. In one embodiment, the pressure is approximately 15 Torr. In one embodiment, the pressure is approximately 20 Torr. In one embodiment, the pressure is approximately 25 Torr. In one embodiment, the pressure is approximately 30 Torr. In one embodiment, the pressure is approximately 40 Torr. In one embodiment, the pressure is approximately 50 Torr. In one embodiment, the pressure is approximately 60 Torr. In one embodiment, the pressure is approximately 75 Torr. In one embodiment, the pressure is approximately 100 Torr.

[0092] Volatilization process

[0093] Process (i)

[0094] In step (i), the metal-containing material on the substrate surface is exposed to one or more volatile agents for a sufficient amount of time to generate volatile by-products (i.e., volatile metal-containing species) through a reaction between the one or more volatile agents and the metal-containing material. As a result of being converted into volatile products, some or all of the metal-containing material on the substrate surface can be removed. See Figure 1.

[0095] Volatile agent

[0096] The volatilizer comprises, essentially comprises, or consists of, one or more compounds that provide one or more ligands capable of forming a coordination complex with a metal-containing material or its chlorinated metal surface. In one embodiment, the volatilizer comprises, essentially comprises, or consists of, a halogen-free acid or a mixture of halogen-free acids.

[0097] In one embodiment, one or more volatile agents include propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2E)-buta-2-enoic acid, (Z)-2-butenoic acid, and one or more combinations thereof. In one embodiment, one or more volatile agents include propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-butenoic acid, and one or more combinations thereof. In one embodiment, one or more volatile agents include propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, and one or more combinations thereof. In one embodiment, one or more volatile agents include propionic acid, isobutyric acid, pivalic acid, and one or more combinations thereof. In one embodiment of this design, one or more volatile agents include propionic acid. In one embodiment of this design, one or more volatile agents include isobutyric acid. In one embodiment of this design, one or more volatile agents include pivalic acid. In one embodiment of this design, one or more volatile agents include acetic acid. In one embodiment of this design, one or more volatile agents include butanoic acid. In one embodiment of this design, one or more volatile agents include acrylic acid. In one embodiment of this design, one or more volatile agents include methacrylic acid. In one embodiment of this design, one or more volatile agents include 2-methylbutanoic acid. In one embodiment of this design, one or more volatile agents include 3-methylbutanoic acid. In one embodiment of this design, one or more volatile agents include 3-butenoic acid. In one embodiment of this design, one or more volatile agents include cyclopropanecarboxylic acid. In one embodiment of this design, one or more volatile agents include pentanoic acid. In one embodiment of this design, one or more volatile agents include (2E)-buta-2-enoic acid. In one embodiment of this model, one or more volatile agents include (Z)-2-butenic acid. In one embodiment of this model, one or more volatile agents include a mixture of one or more propionic acid, isobutyric acid, and pivalic acid.In one embodiment of this model, one or more volatile agents include a mixture of two or more propionic acid, isobutyric acid, and pivalic acid. In one embodiment of this model, one or more volatile agents include a mixture of halogen-free acids containing one or more propionic acid, isobutyric acid, and pivalic acid.

[0098] situation

[0099] time

[0100] In one embodiment, the volatilization time of step (i) is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the volatilization time of step (i) is approximately 0.5 seconds to approximately 10 seconds. In one embodiment, the volatilization time of step (i) is approximately 1 second to approximately 7 seconds. In one embodiment, the volatilization time of step (i) is approximately 7 seconds to approximately 10 seconds. In one embodiment, the volatilization time of step (i) is approximately 10 seconds to approximately 20 seconds. In one embodiment, the volatilization time of step (i) is approximately 20 seconds to approximately 30 seconds. In one embodiment, the volatilization time of step (i) is approximately 0.25 seconds. In one embodiment, the volatilization time of step (i) is approximately 0.5 seconds. In one embodiment, the volatilization time of step (i) is approximately 1 second. In one embodiment, the volatilization time of step (i) is approximately 2 seconds. In one embodiment, the volatilization time of step (i) is approximately 3 seconds. In one embodiment, the volatilization time of step (i) is approximately 4 seconds. In one embodiment, the volatilization time of step (i) is approximately 5 seconds. In one embodiment, the volatilization time of step (i) is approximately 6 seconds. In one embodiment, the volatilization time of step (i) is approximately 7 seconds. In one embodiment, the volatilization time of step (i) is approximately 8 seconds. In one embodiment, the volatilization time of step (i) is approximately 9 seconds. In one embodiment, the volatilization time of step (i) is approximately 10 seconds. In one embodiment, the volatilization time of step (i) is approximately 12 seconds. In one embodiment, the exposure time for volatilization of step (i) is approximately 15 seconds. In one embodiment, the volatilization time of step (i) is approximately 17 seconds. In one embodiment, the volatilization time of step (i) is approximately 20 seconds. In one embodiment, the volatilization time of step (i) is approximately 25 seconds. In one embodiment, the volatilization time of step (i) is approximately 30 seconds.

[0101] Flow rate of volatile agent

[0102] In one embodiment, the volatile agent is flowed at a rate of approximately 1 sccm to approximately 500 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 5 sccm to approximately 500 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 0.5 sccm to approximately 100 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 1 sccm to approximately 50 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 5 sccm to approximately 25 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 10 sccm to approximately 20 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 15 sccm to approximately 25 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 5 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 10 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 15 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 20 sccm. In one embodiment, the volatile agent is flowed at a rate of approximately 25 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 30 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 35 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 40 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 45 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 50 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 60 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 70 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 80 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 90 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 100 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 125 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 150 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 200 sccm. In one embodiment, the volatile agent is flushed at a rate of approximately 250 sccm. In one embodiment, the volatile agent is flushed at approximately 300 sccm. In one embodiment, the volatile agent is flushed at approximately 350 sccm. In one embodiment, the volatile agent is flushed at approximately 400 sccm. In one embodiment, the volatile agent is flushed at approximately 450 sccm. In one embodiment, the volatile agent is flushed at approximately 500 sccm.

[0103] In one embodiment, the volatile agent is supplied separately.

[0104] In one embodiment, the volatilizer is supplied with a suitable carrier gas. In one embodiment, the carrier gas includes argon. In one embodiment, the carrier gas includes nitrogen.

[0105] In one embodiment, the volatilizing agent is supplied by vapor suction.

[0106] pressure

[0107] In one embodiment, the pressure is approximately 0.05 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 100 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 15 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 5 Torr. In one embodiment, the pressure is approximately 0.2 Torr to approximately 2 Torr. In one embodiment, the pressure is approximately 0.05 Torr. In one embodiment, the pressure is approximately 0.1 Torr. In one embodiment, the pressure is approximately 0.2 Torr. In one embodiment, the pressure is approximately 0.5 Torr. In one embodiment, the pressure is approximately 1 Torr. In one embodiment, the pressure is approximately 1.5 Torr. In one embodiment, the pressure is approximately 2 Torr. In one embodiment, the pressure is approximately 2.5 Torr. In one embodiment, the pressure is approximately 5 Torr. In one embodiment, the pressure is approximately 10 Torr. In one embodiment, the pressure is approximately 15 Torr. In one embodiment, the pressure is approximately 20 Torr. In one embodiment, the pressure is approximately 25 Torr. In one embodiment, the pressure is approximately 30 Torr. In one embodiment, the pressure is approximately 40 Torr. In one embodiment, the pressure is approximately 50 Torr. In one embodiment, the pressure is approximately 60 Torr. In one embodiment, the pressure is approximately 75 Torr. In one embodiment, the pressure is approximately 100 Torr.

[0108] Example process (i)

[0109] In an exemplary embodiment of the volatilization in step (i), as shown in Figure 3, the layer of CoCl2 on the surface of Co (above) undergoes ligand exchange with propionic acid to form volatile cobalt(II) propionate and volatile HCl.

[0110] Process (ii)

[0111] In the purging step (ii), any suitable inert purge gas can be used. In one embodiment, the purge gas contains argon. In one embodiment, the purge gas contains nitrogen.

[0112] time

[0113] In one embodiment, the purging time for process (ii) is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the purging time for process (ii) is approximately 0.25 seconds to approximately 10 seconds. In one embodiment, the purging time for process (ii) is approximately 1 second to approximately 7 seconds. In one embodiment, the purging time for process (ii) is approximately 7 seconds to approximately 10 seconds. In one embodiment, the purging time for process (ii) is approximately 10 seconds to approximately 20 seconds. In one embodiment, the purging time for process (ii) is approximately 20 seconds to approximately 30 seconds. In one embodiment, the purging time for process (ii) is approximately 30 seconds to approximately 60 seconds. In one embodiment, the purging time for process (ii) is approximately 0.25 seconds. In one embodiment, the purging time for process (ii) is approximately 0.5 seconds. In one embodiment, the purging time for process (ii) is approximately 1 second. In one embodiment, the purging time for process (ii) is approximately 2 seconds. In one embodiment, the purging time for step (ii) is approximately 3 seconds. In one embodiment, the purging time for step (ii) is approximately 4 seconds. In one embodiment, the purging time for step (ii) is approximately 5 seconds. In one embodiment, the purging time for step (ii) is approximately 6 seconds. In one embodiment, the purging time for step (ii) is approximately 7 seconds. In one embodiment, the purging time for step (ii) is approximately 8 seconds. In one embodiment, the purging time for step (ii) is approximately 9 seconds. In one embodiment, the purging time for step (ii) is approximately 10 seconds. In one embodiment, the purging time for step (ii) is approximately 12 seconds. In one embodiment, the purging time exposure for step (ii) is approximately 15 seconds. In one embodiment, the purging time for step (ii) is approximately 17 seconds. In one embodiment, the purging time for step (ii) is approximately 20 seconds. In one embodiment, the purging time for step (ii) is approximately 25 seconds. In one embodiment, the purging time for step (ii) is approximately 30 seconds. In one embodiment, the purging time for step (ii) is approximately 35 seconds. In one embodiment, the purging time for step (ii) is approximately 40 seconds. In one embodiment, the purging time for step (ii) is approximately 50 seconds. In one embodiment, the purging time for step (ii) is approximately 60 seconds.

[0114] flow rate

[0115] In one embodiment, the purge gas is flowed at a rate of approximately 100 sccm to approximately 5000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 500 sccm to approximately 2500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1000 sccm to approximately 2000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 100 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 200 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 300 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 400 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 1500 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 2000 sccm. In one embodiment, the purge gas is flowed at a rate of approximately 2500 sccm. In one embodiment, the purge gas is flowed at approximately 3000 sccm. In one embodiment, the purge gas is flowed at approximately 3500 sccm. In one embodiment, the purge gas is flowed at approximately 4000 sccm. In one embodiment, the purge gas is flowed at approximately 4500 sccm. In one embodiment, the purge gas is flowed at approximately 5000 sccm.

[0116] pressure

[0117] The purging step of step (ii) can be performed at any appropriate chamber pressure. In one embodiment, the pressure is approximately 0.05 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 100 Torr. In one embodiment, the pressure is approximately 0.5 Torr to approximately 15 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 10 Torr. In one embodiment, the pressure is approximately 1 Torr to approximately 5 Torr. In one embodiment, the pressure is approximately 0.2 Torr to approximately 2 Torr. In one embodiment, the pressure is approximately 0.05 Torr. In one embodiment, the pressure is approximately 0.1 Torr. In one embodiment, the pressure is approximately 0.2 Torr. In one embodiment, the pressure is approximately 0.5 Torr. In one embodiment, the pressure is approximately 1 Torr. In one embodiment, the pressure is approximately 1.5 Torr. In one embodiment, the pressure is approximately 2 Torr. In one embodiment, the pressure is approximately 2.5 Torr. In one embodiment, the pressure is approximately 5 Torr. In one embodiment, the pressure is approximately 10 Torr. In one embodiment, the pressure is approximately 15 Torr. In one embodiment, the pressure is approximately 20 Torr. In one embodiment, the pressure is approximately 25 Torr. In one embodiment, the pressure is approximately 30 Torr. In one embodiment, the pressure is approximately 40 Torr. In one embodiment, the pressure is approximately 50 Torr. In one embodiment, the pressure is approximately 60 Torr. In one embodiment, the pressure is approximately 75 Torr. In one embodiment, the pressure is approximately 100 Torr.

[0118] Chamber (reactor) temperature

[0119] Lid heater (process chamber gas delivery zone)

[0120] In one embodiment, the chamber lid heater is set to approximately 100°C to approximately 200°C. In one embodiment, the chamber lid heater is set to approximately 100°C. In one embodiment, the chamber lid heater is set to approximately 130°C. In one embodiment, the chamber lid heater is set to approximately 150°C. In one embodiment, the chamber lid heater is set to approximately 200°C.

[0121] Internal heater (i.e., process chamber or sample pedestal)

[0122] In one embodiment, the internal chamber heater is set to approximately 100°C to approximately 400°C. In one embodiment, the internal chamber heater is set to approximately 100°C. In one embodiment, the internal chamber heater is set to approximately 150°C. In one embodiment, the internal chamber heater is set to approximately 160°C. In one embodiment, the internal chamber heater is set to approximately 175°C. In one embodiment, the internal chamber heater is set to approximately 200°C. In one embodiment, the internal chamber heater is set to approximately 250°C. In one embodiment, the internal chamber heater is set to approximately 275°C. In one embodiment, the internal chamber heater is set to approximately 300°C. In one embodiment, the internal chamber heater is set to approximately 325°C. In one embodiment, the internal chamber heater is set to approximately 350°C. In one embodiment, the internal chamber heater is set to approximately 400°C.

[0123] Film properties

[0124] The subject matter disclosed and claimed further includes films prepared by the method described herein.

[0125] Film aspect ratio

[0126] In one embodiment, a film etched by the method described herein has trenches, vias, or other geometric features having an aspect ratio of about 0 to about 60. In a further embodiment of this embodiment, the aspect ratio is about 0 to about 0.5. In a further embodiment of this embodiment, the aspect ratio is about 0.5 to about 1. In a further embodiment of this embodiment, the aspect ratio is about 1 to about 50. In a further embodiment of this embodiment, the aspect ratio is about 1 to about 40. In a further embodiment of this embodiment, the aspect ratio is about 1 to about 30. In a further embodiment of this embodiment, the aspect ratio is about 1 to about 20. In a further embodiment of this embodiment, the aspect ratio is about 1 to about 10. In a further embodiment of this embodiment, the aspect ratio is about 0.1. In a further embodiment of this embodiment, the aspect ratio is about 0.2. In a further embodiment of this embodiment, the aspect ratio is about 0.3. In a further embodiment of this embodiment, the aspect ratio is about 0.4. In a further embodiment of this embodiment, the aspect ratio is about 0.5. In a further embodiment of this model, the aspect ratio is about 0.6. In a further embodiment of this model, the aspect ratio is about 0.8. In a further embodiment of this model, the aspect ratio is about 1. In a further embodiment of this model, the aspect ratio is greater than about 1. In a further embodiment of this model, the aspect ratio is greater than about 2. In a further embodiment of this model, the aspect ratio is greater than about 5. In a further embodiment of this model, the aspect ratio is greater than about 10. In a further embodiment of this model, the aspect ratio is greater than about 15. In a further embodiment of this model, the aspect ratio is greater than about 20. In a further embodiment of this model, the aspect ratio is greater than about 30. In a further embodiment of this model, the aspect ratio is greater than about 40. In a further embodiment of this model, the aspect ratio is greater than about 50. In the aforementioned embodiments and further embodiments thereof, the metal includes cobalt, nickel, molybdenum, ruthenium, and tungsten. In the aforementioned embodiments and further embodiments thereof, the metal includes cobalt. In the aforementioned embodiments and further embodiments thereof, the metal includes nickel.In the embodiments described above and in further embodiments thereof, the metal includes molybdenum. In the embodiments described above and in further embodiments thereof, the metal includes ruthenium. In the embodiments described above and in further embodiments thereof, the metal includes tungsten.

[0127] resistivity

[0128] In another embodiment, a film etched by the method described herein has a resistivity of about 1 μΩ·cm to about 250 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 1 μΩ·cm to about 5 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 3 μΩ·cm to about 4 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 5 μΩ·cm to about 10 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 10 μΩ·cm to about 50 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 10 μΩ·cm to about 25 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 15 μΩ·cm to about 25 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 25 μΩ·cm to about 35 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 50 μΩ·cm to about 100 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 100 μΩ·cm to about 250 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 1 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 2 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 3 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 4 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 5 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 7.5 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 10 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 15 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 20 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 25 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 30 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 35 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 40 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 50 μΩ·cm.In a further embodiment of this embodiment, the film has a resistivity of about 60 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 80 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 100 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 150 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 200 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 250 μΩ·cm.

[0129] In a further embodiment of this embodiment, the film has a resistivity of about 2 μΩ·cm to about 4 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 3 μΩ·cm to about 4 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 1 μΩ·cm to about 5 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 5 μΩ·cm to about 10 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 15 μΩ·cm to about 25 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 20 μΩ·cm to about 30 μΩ·cm. In a further embodiment of this embodiment, the film has a resistivity of about 25 μΩ·cm to about 35 μΩ·cm.

[0130] Substrate surface (i.e., surface of metal-containing material)

[0131] In the embodiments described above and in further embodiments thereof, the metal-containing material includes titanium, cobalt, nickel, copper, molybdenum, ruthenium, tantalum, or tungsten. In the embodiments described above and in further embodiments thereof, the metal-containing material includes titanium. In the embodiments described above and in further embodiments thereof, the metal-containing material includes cobalt. In the embodiments described above and in further embodiments thereof, the metal-containing material includes nickel. In the embodiments described above and in further embodiments thereof, the metal-containing material includes copper. In the embodiments described above and in further embodiments thereof, the metal-containing material includes molybdenum. In the embodiments described above and in further embodiments thereof, the metal-containing material includes ruthenium. In the embodiments described above and in further embodiments thereof, the metal-containing material includes tantalum. In the embodiments described above and in further embodiments thereof, the metal-containing material includes tungsten.

[0132] In the embodiments described above and further embodiments thereof, the metal-containing material includes titanium nitride or tantalum nitride. [Examples]

[0133] Herein, we refer to more specific embodiments of the present disclosure and experimental results supporting such embodiments. The examples are given below to more fully illustrate the disclosed subject matter and should not be construed in any way as limiting the disclosed subject matter.

[0134] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed subject matter and the specific examples provided herein without departing from the spirit and scope of the disclosed subject matter. Accordingly, the disclosed subject matter, including the descriptions provided by the following examples, is intended to cover modifications and variations of the disclosed subject matter that fall within the scope of any claim and its equivalents.

[0135] Materials and methods:

[0136] The hot gas phase etching process involves repeatedly exposing the material to be etched to different gas phase reactants in a vacuum chamber. After each exposure, the chamber is purged with an inert gas to remove excess reactant and reaction products.

[0137] The following embodiment was carried out in an ALD system equipped with a showerhead lid heated to 130°C. This ALD system can accommodate wafer sizes up to 300 mm in diameter. This ALD system has a heated pedestal for positioning the wafer.

[0138] Thionyl chloride, isobutyric acid, and propionic acid were obtained from MilliporeSigma. Thionyl chloride was maintained at 30°C in a stainless steel ampoule. Propionic acid was maintained at 40°C in a stainless steel ampoule. Isobutyric acid was maintained at 50°C in a stainless steel ampoule.

[0139] In all examples, the test substrate was prepared by physical vapor deposition (PVD) on a silicon wafer or silicon piece completely covered with approximately 3000 Å of thermally grown SiO2 before metal deposition. Co was uniformly deposited on a 200 mm silicon wafer. Mo was deposited as circular spots (45 mm in diameter) on a 300 mm silicon wafer. Subsequently, the wafer was cut into 44 mm x 44 mm coupons, so that the center of each PVD spot was located at the center of each coupon. Ni was uniformly deposited on the 44 mm x 44 mm silicon coupons. In all cases, the thickness of the deposited metal film was approximately 200 Å. The 44 mm x 44 mm coupons were loaded onto a 300 mm carrier wafer for ALE treatment. The thickness of the sample was measured using X-ray fluorescence. The sample resistance was measured using the four-probe method, and the metal resistivity was calculated from the sample resistance and film thickness.

[0140] [Table 1]

[0141] Example 1: ALE of Co, Ni, and Mo by thionyl chloride and propionic acid

[0142] The process chamber's pedestal heater was set to 325°C, and 20, 40, or 60 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 310°C. In step (i), propionic acid was introduced. The results are shown in the table below. Co, Ni, and Mo were etched at a rate of 0.5 Å / cycle or higher. Etching delays occurred in Co and Mo, but in Ni, the etching per cycle increased significantly in the first few ALE cycles. The etching process reduced the resistivity of Co, likely due to thermal annealing of the film, and the resistivity of Mo also decreased slightly. [Table 2] [Table 3]

[0143] Example 2: ALE of Co, Ni, and Mo by thionyl chloride and isobutyric acid

[0144] The process chamber's pedestal heater was set to 325°C, and 20, 40, or 60 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 310°C. In step (i), isobutyric acid was introduced. The results are shown in the table below. Co, Ni, and Mo were etched at a rate exceeding 0.5 Å / cycle, with an etching delay of approximately 10 cycles for Co. The etching process reduced the resistivity of Co, likely due to thermal annealing of the film, and slightly reduced the resistivity of Mo. [Table 4] [Table 5]

[0145] Example 3: Hot vapor phase etching of native oxides

[0146] In a predictive example, test substrates containing exposed thin films of Co, Ni, Cu, Mo, Ru, W, TiN, and / or TaN can be placed in a thermal etching chamber. These test substrates may be conditioned such that metallic compounds are formed on their surface. The conditioning may consist of designed conditioning treatments such as exposure to air that can form native oxides on the metal surface, or chemical treatments in a process prior to converting the surface metal to a metallic compound. The hot vapor phase etching process, consisting of the above process steps (i) and (ii), can selectively remove metallic compounds, leaving a metal surface substantially free of metallic compounds, by repeating the process from one to about 100 times. Possible volatilizers include propionic acid, isobutyric acid, pivalic acid, or any combination thereof.

[0147] As described above, the vapor-phase etching processes described herein, including the ALE process described herein, can be easily controlled (i.e., adjusted) to provide a specific amount of etching for a desired application. By adjusting the selection of surface modifiers, volatilizers, process temperature, process pressure, and dilution flow, the amount of etching per cycle and / or process selectivity can be changed, that is, a specific material or a portion of a group of materials exposed to the etching process can be etched while minimizing the impact on other exposed materials.

[0148] While the disclosed and claimed subject matter has been described and illustrated in some detail, this disclosure is for illustrative purposes only, and a person skilled in the art will understand that numerous changes to the conditions and sequence of the process can be made without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A method for etching a metal-containing material from the surface of a substrate, (i) Exposing the metal-containing material to one or more volatile agents to generate volatile by-products from the metal-containing material, (ii) A volatilization process including purging, Optional, (a) Exposing the metal-containing material to one or more surface modifiers to form a metal-containing material different from the metal-containing material before exposure to the one or more surface modifiers, and (b) A method comprising a surface modification step, which includes purging.

2. The method according to claim 1, comprising the volatilization step and the surface modification step.

3. The method according to claim 1, comprising the volatilization step and the surface modification step, wherein the volatilization step precedes the surface modification step.

4. The method according to claim 1, comprising the volatilization step and the surface modification step, wherein the surface modification step precedes the volatilization step.

5. The method according to claim 1, wherein the metal comprises one or more of Co, Ni, Cu, Mo, Ru, W, TiN, and TaN.

6. The method according to claim 1, wherein the metal-containing material includes Co.

7. The method according to claim 1, wherein the metal-containing material includes Ni.

8. The method according to claim 1, wherein the metal-containing material includes Cu.

9. The method according to claim 1, wherein the metal-containing material includes Mo.

10. The method according to claim 1, wherein the metal-containing material includes Ru.

11. The method according to claim 1, wherein the metal-containing material includes W.

12. The method according to claim 1, wherein the metal-containing material includes TiN.

13. The method according to claim 1, wherein the metal-containing material includes TaN.

14. The method according to claim 1, wherein in step (a), the one or more surface modifiers comprises one or more halogenating agents.

15. The method according to claim 1, wherein in step (a), the one or more surface modifiers include one or more chlorinating agents.

16. In step (a), the one or more surface modifiers are SOCl ２ , Cl ２ , BCl ３ HCl and TiCl ４ The method according to claim 1, comprising one or more chlorinating agents selected from the group.

17. In step (a), the one or more surface modifiers are SOCl ２ The method according to claim 1, including the method described in claim 1.

18. In step (a), the one or more surface modifiers are Cl ２ The method according to claim 1, including the method described in claim 1.

19. In step (a), the one or more surface modifiers are BCl ３ The method according to claim 1, including the method described in claim 1.

20. The method according to claim 1, wherein in step (a), the one or more surface modifiers include HCl.

21. In step (a), the one or more surface modifiers are TiCl ４ The method according to claim 1, including the method described in claim 1.

22. The method according to claim 1, wherein in step (a), one or more surface modifiers are introduced as components of the plasma.

23. The method according to claim 1, wherein in step (a), one or more surface modifiers are introduced as plasma.

24. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 0.5 seconds to approximately 30 seconds.

25. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 0.5 seconds.

26. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 1 second.

27. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 5 seconds.

28. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 10 seconds.

29. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 15 seconds.

30. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 20 seconds.

31. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 25 seconds.

32. The method according to claim 1, wherein in step (a), the exposure time of the one or more surface modifiers is approximately 30 seconds.

33. The method according to claim 1, wherein in step (a), one or more surface modifiers are flowed at a rate of about 100 sccm to about 5000 sccm.

34. The method according to claim 1, wherein step (a) is performed at a pressure of about 0.5 Torr to about 100 Torr.

35. The method according to claim 1, wherein in step (i), the one or more volatile agents include one or more halogen-free chloroacetic acids.

36. The method according to claim 1, wherein in step (i), the one or more volatile agents include one or more halogen-free volatile acids selected from the group consisting of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2E)-buta-2-enoic acid and (Z)-2-butenoic acid.

37. The method according to claim 1, wherein in step (i), the one or more volatile agents include one or more halogen-free acids selected from the group consisting of propionic acid, isobutyric acid, pivalic acid, and combinations thereof.

38. The method according to claim 1, wherein in step (i), the one or more volatile agents include propionic acid.

39. The method according to claim 1, wherein in step (i), the one or more volatile agents include isobutyric acid.

40. The method according to claim 1, wherein in step (i), the one or more volatile agents include pivalic acid.

41. The method according to claim 1, wherein in step (i), the one or more volatile agents include acetic acid.

42. The method according to claim 1, wherein in step (i), the one or more volatile agents include butanoic acid.

43. The method according to claim 1, wherein in step (i), the one or more volatile agents include acrylic acid.

44. The method according to claim 1, wherein in step (i), the one or more volatile agents include methacrylic acid.

45. The method according to claim 1, wherein in step (i), the one or more volatile agents include 2-methylbutanoic acid.

46. The method according to claim 1, wherein in step (i), the one or more volatile agents include 3-methylbutanoic acid.

47. The method according to claim 1, wherein in step (i), the one or more volatile agents include 3-butenic acid.

48. The method according to claim 1, wherein in step (i), the one or more volatile agents include cyclopropanecarboxylic acid.

49. The method according to claim 1, wherein in step (i), the one or more volatile agents include pentanoic acid.

50. The method according to claim 1, wherein in step (i), the one or more volatile agents include (2E)-buta-2-enoic acid.

51. The method according to claim 1, wherein in step (i), the one or more volatile agents include (Z)-2-butenic acid.

52. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 0.5 seconds to approximately 30 seconds.

53. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 0.5 seconds.

54. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 1 second.

55. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 5 seconds.

56. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 10 seconds.

57. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 15 seconds.

58. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 20 seconds.

59. The method according to claim 1, wherein in step (i), the exposure time to the one or more volatile agents is approximately 25 seconds.

60. The method according to claim 1, wherein in step (i), one or more volatile agents are flowed at a rate of about 1 sccm to about 500 sccm.

61. The method according to claim 1, wherein step (i) is performed at a pressure of about 0.05 Torr to about 10 Torr.

62. The method according to any one of claims 1 to 4, comprising approximately 100 to approximately 1000 cycles.

63. The method according to any one of claims 1 to 4, comprising approximately 25 to approximately 250 cycles.

64. The method according to any one of claims 1 to 4, comprising approximately 5 cycles.

65. The method according to any one of claims 1 to 4, comprising approximately 10 cycles.

66. The method according to any one of claims 1 to 4, comprising approximately 20 cycles.

67. The method according to any one of claims 1 to 4, comprising approximately 25 cycles.

68. The method according to any one of claims 1 to 4, comprising approximately 35 cycles.

69. The method according to any one of claims 1 to 4, comprising approximately 50 cycles.

70. The method according to any one of claims 1 to 4, comprising approximately 75 cycles.

71. The method according to any one of claims 1 to 4, comprising approximately 100 cycles.

72. The method according to any one of claims 1 to 4, comprising approximately 200 cycles.

73. The method according to any one of claims 1 to 4, comprising approximately 250 cycles.

74. The method according to any one of claims 1 to 4, comprising approximately 300 cycles.

75. The method according to any one of claims 1 to 4, comprising approximately 325 cycles.

76. The method according to any one of claims 1 to 4, comprising approximately 400 cycles.

77. The method according to any one of claims 1 to 4, comprising approximately 500 cycles.

78. The method according to any one of claims 1 to 4, comprising approximately 750 cycles.

79. The method according to any one of claims 1 to 4, comprising approximately 1,000 cycles.

80. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 0 to approximately 60.

81. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 1 to approximately 10.

82. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 0.

83. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 1.

84. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 2.

85. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 5.

86. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 10.

87. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 20.

88. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 30.

89. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 40.

90. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 50.

91. A metal-containing film etched by the method of any one of claims 1 to 79, comprising a geometric feature having an aspect ratio of approximately 60.

92. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 1 μΩ·cm to approximately 250 μΩ·cm.

93. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 1 μΩ·cm to approximately 5 μΩ·cm.

94. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 5 μΩ·cm to approximately 10 μΩ·cm.

95. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 10 μΩ·cm to approximately 25 μΩ·cm.

96. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 25 μΩ·cm to approximately 50 μΩ·cm.

97. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 50 μΩ·cm to approximately 100 μΩ·cm.

98. A metal-containing film etched by the method of any one of claims 1 to 79, having a resistivity of approximately 100 μΩ·cm to approximately 250 μΩ·cm.

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