Vapor-phase thermal etching of metal oxides

Abstract

The disclosed and claimed subject matter relates to a gas-phase process for etching metal oxide films without requiring the use of plasma or corrosive halogenated gases, and includes (1) a process for selectively removing thin layers of oxidized metal-containing material on a metal such as Mo or W, and (2) a process for performing thermal atomic layer etching (ALE) of films comprising ZrO2, HfO2, (Hf-Zr)O2 alloys or similar materials. The disclosed and claimed subject matter further includes metal-insulator-metal capacitor (MIMcap) devices having unique properties enabled by ALE of high-k dielectric films.

Description

[Technical Field]

[0001] The disclosed and claimed subject matter relates to a gas-phase process for etching metal oxide films that does not require the use of plasma or corrosive halogenated gases. The disclosed and claimed subject matter further includes a process for performing thermally selective gas-phase etching of a thin layer of oxidized metal-containing material present on a metal. The disclosed and claimed subject matter further includes an atomic layer etching (ALE) process for etching metal oxide films comprising ZrO2, HfO2, (Hf-Zr)O2 alloy, or similar materials. The disclosed and claimed subject matter further includes a metal-insulator-metal capacitor (MIMcap) having unique properties enabled by the ALE process described herein. [Background technology]

[0002] The miniaturization of features in the semiconductor industry is a major driver of continuous device performance improvements. This trend is expected to continue in computer chips for at least the next few generations. In this regard, ultrathin (<5nm) layers of high-k dielectrics are required for volatile and non-volatile memories, including DRAM, NAND flash, and ferroelectric memory. To continue this trend, several technical challenges must be successfully overcome. In the manufacturing of microelectronic logic devices, highly selective etching is required to precisely remove one or a set of materials from an exposed surface, involving many materials including metals, metal oxides, dielectric materials, and semiconductors.

[0003] The material to be etched may be a material with desirable properties that must be thinned or removed in a specific area. The material to be etched may also be an undesirable by-product of chemical treatment or air exposure, such as native oxides on a metal surface. In such cases, etching must selectively remove the undesirable material while leaving the underlying desired material intact.

[0004] 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 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 with ALD has been demonstrated in numerous publications.

[0005] 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, an atomic layer is removed from all surfaces exposed to a precursor in the gas phase. The thickness of this layer is ideally at most one atomic layer. ALE is performed by successively exposing the surface to at least two different precursors, where the first precursor activates a layer of surface atoms, the second precursor facilitates the sublimation of this activated layer of atoms, and sometimes a third precursor is used to regenerate the surface to a state where the first precursor is activated. Several etching procedures are described that convert the metal into a metal compound, and then perform a volatilization step in which the metal compound is removed but the metal is not. See, for example, 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 exceeding 377°C and the cobalt surface (containing native oxides) was exposed to 1,1,1,5,5,5-hexafluoro-2,4,-pentanedione (Hhfac). The treated surface was then heated, resulting in the sublimation of cobalt 1,1,1,5,5,5-hexafluoro-2,4,-pentanedione. In the museum, the cobalt surface is: (A) Chlorine that oxidizes the cobalt layer to cobalt chloride (surface activation), (B) Cobalt was etched at temperatures exceeding 140°C by sequential exposure to acetylacetone (e.g., 1,1,1,5,5,5-hexafluoro-2,4,-pentanedione (Hhfac)) which reacts with cobalt chloride surface species to produce volatile cobalt chloroacetylacetonate species (sublimation).

[0006] 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 etched the cobalt surface: (A) An oxygen plasma that oxidizes multiple cobalt layers to cobalt oxide (surface activation), (B) This involved sequential exposure to (sublimated) formic acid, which reacts with surface species of cobalt oxide to produce volatile cobalt formate species.

[0007] 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 etches the copper surface: (A) It is a mild oxidizing agent, and the copper layer is oxidized to copper oxide (surface activated) by oxygen, (B) The procedure involved sequential exposure to acetylacetone (e.g., 1,1,1,5,5,5-hexafluoro-2,4,-pentanedione (Hhfac)) which reacts with copper oxide surface species to produce volatile copper acetylacetonate species (sublimation).

[0008] Another method involved etching tungsten. See, for example, Johnson NR and George SM, ACS Applied Materials & Interfaces, 9, 34435 (2017). This process involves etching a tungsten surface with a native oxide layer: (A) A mixture of oxygen and ozone that oxidizes (surface-activates) an additional layer of tungsten to tungsten oxide, (B) Boron trichloride 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), (C) Tungsten could be etched (128°C~207°C) by sequential exposure to hydrogen fluoride, which reacts with boron oxide to produce volatile water vapor and volatile boron trifluoride (regeneration of a fresh tungsten oxide surface).

[0009] Films of several nanometers in thickness of ZrO2 and HfO2 have different functional properties based on the film thickness and crystal structure. 0.5 Zr 0.5 The ferroelectric crystalline phase of O2 can only be stabilized beyond a certain minimum film thickness of approximately 5–7 nm. If films thinner than 5–7 nm are desired (e.g., to maximize capacitance and / or reduce device size), a thicker film must first be grown and processed (i.e., to crystallize the film), and then a portion of the film material must be removed. Such material removal methods require sub-nanometer precision, and the removal may need to be isotropic (e.g., to conformally etch high aspect ratio features in 3D nanoarchitectures such as DRAM capacitors or 3D memory stacks). The best approach for this is isotropic ALE.

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

[0011] Several implementations of ZrO2ALE involve repeating the following steps within a vacuum chamber tool such as an atomic layer deposition (ALD) reactor: (1) dosing a first fluorinating agent to convert solid surface ZrO2 to solid ZrF4; (2) a first purging step of the reactor; (3) dosing a second chlorinating agent to convert solid ZrF4 to gaseous ZrCl4 via a ligand exchange reaction between ZrF4 and the chlorinating agent; and (4) a second purging step of the reactor. Optionally, (5) a surface modification step and (6) a third purging step may be included in the cycle.

[0012] In the fluorination step (1), metal-free fluorinating agents such as anhydrous HF (aHF), XeF2, or SF4 may be used. For example, see JAMurdzek, SMGeorge, “Effect of crystallinity on thermal atomic layer etching of hafnium oxide, zirconium oxide, and hafnium zirconium oxide”, J.Vac.Sci.Technol.A, 38, 022608 (2020). Alternatively, volatile metal fluorides such as WF6, NbF5, and TaF5 can be used. For example, see U.S. Patent No. 10,283,319; U.S. Patent No. 10,273,584; and PCLemaire and GNParsons, “Thermal Selective Vapor Etching of TiO2: Chemical Vapor Etching via WF6 and Self-Limiting Atomic Layer Etching Using WF6 and BCl3,” Chem. Mater., 29, 6653-6665 (2017). In the chlorination step (3), volatile metal chlorides such as dimethylaluminum chloride (DMAC) or TiCl4 may be used. For example, see Y. Lee, C. Huffman, SMGeorge, “Selectivity in thermal atomic layer etching using sequential, self-limiting fluorination and ligand-exchange reactions,” Chem. Mater., 28, 7657-7665 (2016); JAMurdzek, SMGeorge, “Effect of crystallinity on thermal atomic layer etching of hafnium oxide, zirconium oxide, and hafnium zirconium oxide”, J. Vac. Sci. Technol. A, 38, 022608 (2020).

[0013] Methods for thermal ALE of oxides including ZrO2, HfO2, Al2O3, and TiO2 are described. See, for example, Y. Lee, C. Huffman, and SMGeorge, Chem. Mater., 28, 7657-7665 (2016); PCLemaire and GNParsons, Chem. Mater., 29, 6653-6665 (2017); JAMurdzek and SMGeorge, J. Vac. Sci. Technol. A, 38, 022608 (2020); and H. Saare, Ph.D. dissertation, North Carolina State U., 2021. These methods typically involve two repeated steps: fluorination of the oxide surface in the first step and volatilization of the resulting surface fluoride in the second step. In the first step, the fluorinating agent may be hydrogen fluoride (HF), anhydrous hydrogen fluoride stabilized with pyridine (HF-pyridine), sulfur tetrafluoride (SF4), sulfur hexafluoride (SF6) remote plasma, tungsten hexafluoride (WF6), or xenon difluoride (XeF2). In the second step, the volatile agent may be trimethylaluminum (TMA), dimethylaluminum chloride (DMAC), silicon tetrachloride (SiCl4), or titanium tetrachloride (TiCl4).

[0014] Methods for thermal ALE of Al2O3, ZrO2, HfZrO4, and HfO2 were described by Lee et al. (Y. Lee, C. Huffman, and SMGeorge, Chem. Mater., 28, 7657-7665 (2016)) and Murdzek and George (JAMurdzek and SMGeorge, J. Vac. Sci. Technol. A, 38, 022608 (2020)).

[0015] In Lee, Huffman, and George, the ALE tests were conducted at process temperatures in the range of 150 °C to 350 °C. All of these metal oxides were effectively fluorinated using anhydrous HF supplied from an HF-pyridine ampule. Al2O3 could be etched by circulating a dose of anhydrous HF with either tin(II) acetylacetonate Sn(acac)2, trimethylaluminum (TMA), dimethylaluminum chloride (DMAC), or silicon tetrachloride (SiCl4). ZrO2 could be etched by circulating a dose of anhydrous HF with either Sn(acac)2, DMAC, or SiCl4. HfO2 could be etched by circulating a dose of anhydrous HF with either Sn(acac)2, TMA, or DMAC.

[0016] In Murdzek and George, the ALE tests were conducted at a process temperature of 250 °C. HF, SF4, and XeF2 were used as fluorinating agents, and DMAC and TiCl4 were used as ligand exchangers. For all chemistries tested, crystalline ZrO2, HfZrO4, and HfO2 were etched at lower rates than amorphous ZrO2, HfZrO4, and HfO2, respectively. XeF2 was found to have a much higher etch amount per cycle than HF or SF4.

[0017] The methods of thermal ALE of TiO2 and ZrO2 have been described by Lemaire and Parsons (P.C. Lemaire and G.N. Parsons, Chem. Mater., 29, 6653-6665 (2017)) and Saare (H. Saare, PhD dissertation, North Carolina State U., 2021). In Lemaire and Parsons, the ALE tests were conducted at process temperatures in the range of 120 °C to 220 °C. WF6 was used as the fluorinating agent and BCl3 was used as the ligand exchange agent. In this process, ALE of TiO2 was obtained, but residues of B or W remained on the surface. In Saare, the ALE tests were conducted at process temperatures in the range of 160 °C to 325 °C. WF6 was used as the fluorinating agent and BCl3, TiCl4, and SOCl2 were used as the ligand exchange agents. In each ALE process, ALE of TiO2 and ZrO2 was obtained.

[0018] Some of the chemicals used in the above methods have practical drawbacks. Fluorinating gases such as HF and SF4 are toxic, corrosive, require costly equipment installation, and pose significant environmental health and safety concerns. Metallic fluoride gases such as NbF5 and metallic chloride vapors such as TiCl4 may leave undesirable residues on the workpiece surface, which can be difficult to remove. Therefore, it may be desirable to use fluorinators and chlorinators that do not contain metals and can be packaged in a condensed (liquid or solid) phase (i.e., easily adaptable to ALD, ALD-like, or ALE reactors), but release a considerable partial pressure (on the order of 1 to 100 Torr) of the fluorinating or chlorinating chemical in the gas phase. Examples of these in the art include HF-pyridine, thionyl chloride (SOCl2), and sulfuryl chloride (SO2Cl2).For example, Y. Lee, C. Huffman, SMGeorge, “Selectivity in thermal atomic layer etching using sequential, self-limiting fluorination and ligand-exchange reactions,” Chem. Mater., 28, 7657-7665 (2016); H. Saare, “Investigations of Atomic Layer Deposition and Thermal Atomic Layer Etching: Nucleation Trends, Area-Selectivity, and See Phase Change Memory Materials, “PhD dissertation, North Carolina State University, 2021-08-23; JAMurdzek, A. Lii-Rosales, SMGeorge, “Thermal Atomic Layer Etching of Nickel Using Sequential Chlorination and Ligand-Addition Reactions,” Chem. Mater., 33, 9174-9183 (2021).

[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. [Overview of the project]

[0020] In one embodiment, the subject matter disclosed and claimed relates to a process for selective gas-phase removal of metal compounds.

[0021] In another embodiment, the subject matter disclosed and claimed relates to the selective gas-phase volatilization of metal-containing surface materials that do not etch underlying metals. In a further embodiment, the selective gas-phase volatilization essentially comprises or consists of (a) volatilization, which includes exposing a metal oxide-containing surface or a metal fluoride-containing surface to one or more chlorine-supplying volatilizing agents to generate one or more chlorine-containing volatile byproducts containing one or more metals from the metal oxide-containing surface or the metal fluoride-containing surface; and (b) purging. In another embodiment, the subject matter disclosed and claimed relates to ZrO2, HfO2, Hf x Zr 1-x The present invention relates to vapor phase etching (e.g., isotropic thermal ALE of metal oxides) of materials including O2 (wherein x is a value from 0 to 1, including but not limited to 0.5), as well as other materials based on ZrO2 and HfO2 having artificial impurities or dopants, TiO2, Al2O3, and combinations thereof. The process includes, essentially consists of, or comprises: (i) a surface modification step of exposing the surface of a metal oxide substrate to one or more fluorinated surface modifiers to generate a fluorinated metal compound on the surface; (ii) a purging step; (iii) a volatilization step of exposing the fluorinated surface to one or more chlorine-supplied volatilizers to generate a chlorine-containing volatile byproduct containing one or more metals from the fluorinated metal compound; (iv) a purging step; (v) a surface cleaning step of exposing the surface to one or more oxidizing agents to remove contaminants and convert at least a portion of the surface to a metal oxide; and (vi) a purging step. The steps of the process can be repeated as many times as necessary to remove a desired thickness of metal oxide. This process is repeated as many times as necessary to remove the desired thickness of metal oxide. An optional oxidative post-treatment step (vii) may be added to remove any impurities remaining on the surface after several cycles.

[0022] In another embodiment, the disclosed and claimed subject matter relates to a metal-insulator-metal capacitor ("MIMcap") device fabricated using the disclosed and claimed ALE process. In a further embodiment, the MIMcap device ideally exhibits a higher dielectric constant (k) and lower leakage current than other equivalent MIMcaps fabricated without using the disclosed and claimed ALE process.

[0023] This summary section of the invention does not specify all embodiments and / or progressively novel aspects of the subject matter disclosed and claimed. Instead, this summary provides only a preliminary discussion of different embodiments and corresponding aspects of novelty to the prior art and known art. For further details and / or possible aspects of the subject matter and embodiments disclosed and claimed, readers should refer to the sections on modes for carrying out the invention and the corresponding figures in this disclosure, as will be discussed further below.

[0024] The discussion of the different order of steps described herein is presented for clarity. In general, the steps 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 in many different forms. [Brief explanation of the drawing]

[0025] 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] This shows an exemplary cycle of the ALE process that is disclosed and claimed. [Figure 2] The X-ray photoelectron spectroscopy (XPS) results obtained for the sample from Example 1 are shown. [Figure 3] The X-ray photoelectron spectroscopy (XPS) results obtained for the sample in Example 5 are shown.

[0026] definition

[0027] Unless otherwise specified, the following terms used in this specification and in the claims have the following meanings in this application:

[0028] 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.

[0029] 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".

[0030] The terms "substituent," "radical," "group," and "moiety" can be used interchangeably.

[0031] 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.

[0032] 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, metal halide 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.

[0033] 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.

[0034] 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, features may be vias, trenches, contacts, dual damascenes, and the like.

[0035] 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.

[0036] The disclosed and claimed precursors are preferably substantially free of water. As used herein, the term "substantially free" in relation to water means less than 5000 ppm (by weight), preferably less than 3000 ppm, more preferably less than 1000 ppm, and most preferably less than 100 ppm, measured by proton NMR or Karl Fischer titration.

[0037] The disclosed and claimed precursors also preferably contain, + (Li), + Na, + (Na), 2+ K, 2+ (K), 3+ Mg, 2+ (Mg), 3+ Ca, 2+ (Ca), 3+ Al, 20 (Al), Fe, (Fe), Fe, (Fe), Ni, (Ni), Cr, (Cr), titanium (Ti), vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn), and are substantially free of the unintended presence of metal ions or metals such as these. These metal ions or metals may potentially be present from the starting materials / reactors used to synthesize the precursors. As used herein, the term "substantially free" in relation to the unintended presence of Li, Na, K, Mg, Ca, Al, Fe, Ni, Cr, Ti, V, Mn, Co, Ni, Cu, or Zn means less than 5 ppm (by weight), preferably less than 3 ppm, more preferably less than 1 ppm, and most preferably 0.1 ppm, measured by ICP-MS.

[0038] Unless otherwise specified, "alkyl" can be straight-chain, branched-chain (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.) or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.) C1-C 20This refers to hydrocarbon groups. These alkyl portions may be substituted or unsubstituted, as described below. The term "alkyl" refers to C1-C 20 This refers to such a carbon-containing portion. For structural reasons, it is understood that linear alkyls begin at C1, while branched and linear alkyls begin at C3. Furthermore, it is further understood that the alkyls described below, e.g., the portions derived from alkyloxy and perfluoroalkyls, have the same carbon number range unless otherwise indicated. If the length of an alkyl group is specified as other than those described above, the above definition of alkyl remains valid with respect to encompassing all types of alkyl portions as described above, and the structural considerations regarding the minimum carbon number of a given type of alkyl group still apply.

[0039] A halo or halide refers to a halogen, F, Cl, Br, or I bonded to the organic part by one bond. In some embodiments, the halogen is F. In other embodiments, the halogen is Cl.

[0040] Alkyl halides are C1-C atoms that are completely or partially halogenated. 20 It refers to alkyl groups.

[0041] Perfluoroalkyl refers to a linear, cyclic, or branched saturated alkyl group as defined above, in which all hydrogen atoms are replaced by fluorine (for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoroisopropyl, perfluorocyclohexyl, etc.).

[0042] The disclosed and claimed precursors are preferably substantially free of organic impurities originating from either the starting materials used in the synthesis or 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 analytical assay methods (by weight). Importantly, when the precursor is used as a precursor for depositing a ruthenium-containing film, the precursor has a purity of preferably 98% by weight or more, more preferably 99% by weight or more, as measured by GC.

[0043] 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]

[0044] 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.

[0045] 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 based on the embodiments described herein, without departing from the spirit and scope of the disclosed subject matter.

[0046] As described above, the subject matter disclosed and claimed relates to processes for hot vapor phase treatment and etching. In a first embodiment, process (Process I) includes, essentially consists of, or comprises volatilization, which includes (a) exposing a metal oxide-containing surface or a metal fluoride-containing surface to one or more chlorine-supplied volatilizers to produce one or more chlorine-containing volatile byproducts containing one or more metals from the metal oxide-containing surface or the metal fluoride-containing surface. In a further embodiment of this embodiment, Process I further includes, essentially consists of, or comprises (b) a purging step. In a further embodiment of this embodiment, Process I may include additional steps constituting a vapor phase etching process, and / or steps or parts of other multi-stage vapor phase etching processes. In a further embodiment of this embodiment, Process I selectively removes a metal oxide-containing surface or a metal fluoride-containing surface without removing any underlying metal or metal compound.

[0047] In a further embodiment of this design, the material to be etched includes a layer of metal oxide on a metal. In a further embodiment, the material to be etched includes native oxides (e.g., those formed during exposure to an oxidizing environment such as the atmosphere). In a further embodiment, the metals include cobalt, nickel, molybdenum, ruthenium, tungsten, and combinations thereof.

[0048] In one embodiment, the subject matter disclosed and claimed relates to a selective vapor phase etching process. In another embodiment, the subject matter disclosed and claimed relates to selective isotropic thermal ALE of metal oxides. The vapor phase etching process ("Process 2") consists of the following steps: (i) A surface modification step comprising exposing a metal oxide surface to one or more fluorinated surface modifiers to generate one or more fluorinated metal compounds on the surface, (ii) Purge process, (iii) A volatilization step comprising exposing a fluorinated metal compound to one or more chlorine-supplying volatile agents to produce one or more chlorine-containing volatile by-products containing one or more metals of the fluorinated metal compound, (iv) Purge process, (v) A surface cleaning step comprising exposing the surface to one or more oxidizing agents to remove contaminants and converting at least a portion of the surface to a metal oxide, (vi) A purging process, which includes, essentially consists of, or comprises. In a further embodiment of this embodiment, the method essentially comprises steps (i), (ii), (iii), (iv), (v), and (vi). In a further embodiment of this embodiment, the method comprises steps (i), (ii), (iii), (iv), (v), and (vi). In a further embodiment of this embodiment, the method essentially comprises steps (i), (ii), (iii), and (iv). In a further embodiment of this embodiment, the method comprises steps (i), (ii), (iii), and (iv). In a further embodiment of this embodiment, the method essentially comprises steps (iii) and (iv). In a further embodiment of this embodiment, the method comprises steps (iii) and (iv). The steps of the process can be repeated as many times as necessary to remove a metal or metallic compound of a desired thickness. In a further embodiment, any of the embodiments described above may further include an oxidative post-treatment step of step (vii) to remove impurities remaining on the surface after several cycles.

[0049] In a further embodiment of this design, the material to be etched is ZrO2, HfO2, Hf x Zr 1-x This includes O2 (wherein x is a value between 0 and 1), as well as other materials based on ZrO2 and HfO2 having artificial impurities or dopants, TiO2, Al2O3, and combinations thereof.

[0050] Number of cycles

[0051] As described above, the disclosed and claimed etching process allows for the removal of a metal oxide of a desired thickness by repeating the process as many times as necessary. In the embodiments described above, and in other embodiments described herein, the described steps define one cycle of the process. As those skilled in the art will understand (and as described above), the disclosed and claimed process II includes a purging step (ii) when moving from step (i) to step (iii), a purging step (iv) when moving from step (iii) to step (v), and an additional purging step (vi) before starting a new cycle (i.e., moving from step (v) to step (i)). However, the purging steps do not need to be performed between iterations of a single step (e.g., between multiple iterations of step (i), between multiple iterations of step (iii), or between multiple iterations of step (v)). This is also true for process I (i.e., between multiple iterations of step (a)).

[0052] Therefore, a single cycle in Process I should be understood as the number of repetitions of step (a). A single cycle in Process II should be understood as beginning when the first iteration of step (i) is performed, regardless of the number of purging steps performed during the process, and ending after the last purging step (vi) has been performed and another iteration of step (i) is performed again. It should be understood that the cycle can be repeated until the desired film thickness is obtained.

[0053] 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 another embodiment, the number of cycles is approximately 50 to 100. In yet another embodiment, the number of cycles is approximately 75 to 100.

[0054] 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.

[0055] The steps of the process that are disclosed and claimed are described in more detail below.

[0056] Process (i) Surface modification

[0057] In the surface modification of step (i), one or more fluorinated surface modifiers are used to add one or more metal oxides (e.g., ZrO2, HfO2, Hf x Zr 1-xA surface containing, essentially composed of, or made from O2 (wherein x is a value between 0 and 1), as well as other materials based on ZrO2 and HfO2, Al2O3, or TiO2, which have artificial impurities or dopants, is converted to the corresponding fluorinated species, thereby producing a fluorinated metal surface. In this step, one or more metal oxides are exposed to a fluorinating agent for a certain period of time before proceeding to step (ii).

[0058] As those skilled in the art will understand, initial exposure of a metal oxide surface to a fluorinating agent (not shown in Figure 1) generates by-products on the surface that contaminate the surface and slow down or stop the etching process over time. Therefore, the disclosed and claimed process includes step (v), in which such species are oxidized to species that can readily volatilize when exposed to the fluorinating agent as step (i) is repeated in the next cycle. For example, when Ishikawa's reagent (N,N-diethyl-(1,1,2,3,3,3-hexafluoropropyl)amine) is used for fluorination, residues of N,N-diethyl-(E)-pentafluoropropenylamine containing C, N, and F or its decomposition products may remain. These light element surface contaminants can be burned by oxidation to form carbon oxides (e.g., CO, CO2), nitrogen oxides (e.g., NO, NO2, N2O) and their by-products (e.g., N2), as well as volatile fluorinated compounds (e.g., anhydrous HF). Similarly, pyridine hydrogen fluoride may leave residues of pyridine or its decomposition products containing C and N during the fluorination process. These light element surface contaminants can burn by oxidation to form carbon oxides, nitrogen oxides, and their by-products.

[0059] a) Metal oxide-containing surface and / or metal oxide

[0060] Metal oxide-containing surfaces and / or metal oxides include any acceptable, incidental, and / or desirable metals and / or metal oxides. Therefore, metal oxide-containing surfaces and / or metal oxides may include, essentially consist of, or consist of one or more of zirconium (Zr), hafnium (Hf), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), molybdenum (Mo), ruthenium (Ru), tungsten (W), and combinations thereof. In one embodiment, the metal oxide-containing surface includes cobalt (Co). In one embodiment, the metal oxide-containing surface includes nickel (Ni). In one embodiment, the metal oxide-containing surface includes molybdenum (Mo). In one embodiment, the metal oxide-containing surface includes ruthenium (Ru). In one embodiment, the metal oxide-containing surface includes tungsten (W). In one embodiment, the metal oxide is ZrO2, HfO2, Hf x Zr 1-x The metal oxide comprises one or more of the following: O2 (wherein x is a value between 0 and 1), other materials based on ZrO2 and HfO2 having artificial impurities or dopants, TiO2, Al2O3, and combinations thereof. In one embodiment of this embodiment, the metal oxide comprises ZrO2. In one embodiment of this embodiment, the metal oxide comprises HfO2. In one embodiment of this embodiment, the metal oxide is Hf x Zr 1-xIt contains O2 (wherein x is a value between 0 and 1). In one embodiment of this particular embodiment, m = 0.1. In one embodiment of this particular embodiment, m = 0.2. In one embodiment of this particular embodiment, m = 0.3. In one embodiment of this particular embodiment, m = 0.4. In one embodiment of this particular embodiment, m = 0.5. In one embodiment of this particular embodiment, m = 0.6. In one embodiment of this particular embodiment, m = 0.7. In one embodiment of this particular embodiment, m = 0.8. In one embodiment of this particular embodiment, m = 0.9. In one embodiment of this particular embodiment, m = 0.95. In one embodiment of this embodiment, the metal oxide includes materials based on ZrO2 and HfO2 having artificial impurities. In one embodiment of this embodiment, the metal oxide includes TiO2. In one embodiment of this embodiment, the metal oxide includes Al2O3.

[0061] In one embodiment of this design, the metal oxide is in contact with a different material present beneath it. In one embodiment, the metal oxide is deposited on a substrate by atomic layer deposition (ALD). In one embodiment, the substrate is a metal. In one embodiment, the substrate is a metal nitride. In one embodiment, the substrate is a different metal oxide. In one embodiment, the substrate is Ti, TiN, TiO2, Ta, TaN, W, Al, Ni, Ru, Pt, Al2O3, ZrO2, HfO2, Hf x Zr 1-x It contains one or more of the following: O2 (where x is a value between 0 and 1), Si, Si3N4, and SiO2.

[0062] (b) Fluorinated surface modifiers

[0063] The fluorinated surface modifier includes a fluorinating agent that does not contain one or more metals, or is substantially free of metals.

[0064] In one embodiment of this model, the fluorinated surface modifier comprises one or more of Ishikawa's reagent, ammonium difluoride, sodium difluoride, potassium difluoride, pyridine hydrogen fluoride, triethylamine trishydrofluoride, hydrogen fluoride, and combinations thereof. In one embodiment of this model, the fluorinated surface modifier comprises two or more of Ishikawa's reagent, ammonium difluoride, sodium difluoride, potassium difluoride, pyridine hydrogen fluoride, triethylamine trishydrofluoride, or hydrogen fluoride. In one embodiment of this model, one or more fluorinated surface modifiers comprises Ishikawa's reagent. In one embodiment of this model, one or more fluorinated surface modifiers comprises ammonium difluoride. In one embodiment of this model, one or more fluorinated surface modifiers comprises sodium difluoride. In one embodiment of this model, one or more fluorinated surface modifiers comprises potassium difluoride. In one embodiment of this model, one or more fluorinated surface modifiers comprises pyridine hydrogen fluoride. In one embodiment of this model, one or more fluorinated surface modifiers include triethylamine trishydrofluoride. In one embodiment of this model, one or more fluorinated surface modifiers include hydrogen fluoride.

[0065] In one embodiment of this model, the fluorinated surface modifier is a liquid at room temperature. In one embodiment of this model, the fluorinated surface modifier is a solid at room temperature.

[0066] (c) Conditions

[0067] dosing

[0068] The fluorinated surface modifier can be dosed as a vapor. In one embodiment of this embodiment, the fluorinated surface modifier is dosed as a surface-modifying vapor. In another embodiment of this embodiment, the fluorinated surface modifier is decomposed in the container as a surface-modifying vapor and by-products.

[0069] time

[0070] As described above, in step (i), one or more metal oxides are exposed to a fluorinated surface modifier for a certain period of time ("exposure time") before proceeding to step (ii). In one embodiment, the surface modification exposure time in step (i) is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 0.5 seconds to approximately 10 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 1 second to approximately 7 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 7 seconds to approximately 10 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 10 seconds to approximately 20 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 20 seconds to approximately 30 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 0.25 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 0.5 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 1 second. In one embodiment, the surface modification exposure time in step (i) is approximately 2 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 3 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 4 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 5 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 6 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 7 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 8 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 9 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 10 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 12 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 15 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 17 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 20 seconds. In one embodiment, the surface modification exposure time in step (i) is approximately 25 seconds. In another embodiment, the surface modification exposure time in step (i) is approximately 30 seconds.

[0071] Flow rate of fluorinated surface modifier (vapor)

[0072] In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 0.5 sccm to approximately 500 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 0.5 sccm to approximately 100 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 1 sccm to approximately 200 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 1 sccm to approximately 100 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 1 sccm to approximately 50 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 5 sccm to approximately 25 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 10 sccm to approximately 20 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 15 sccm to approximately 25 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at a rate of approximately 5 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 10 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 15 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 20 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 25 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 30 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 35 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 40 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 45 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 50 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 60 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 70 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 80 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 90 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 100 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 125 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 150 sccm.In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 200 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 250 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 300 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 350 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 400 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 450 sccm. In one embodiment, the fluorinated surface modifier vapor is flowed at approximately 500 sccm.

[0073] In one embodiment, the fluorinated surface modifier vapor is supplied separately.

[0074] In one embodiment, the fluorinated surface modifier vapor is supplied together with a suitable carrier gas. In one embodiment, the carrier gas includes argon. In one embodiment, the carrier gas includes nitrogen.

[0075] pressure

[0076] The surface modification in step (i) can be carried out at any suitable chamber pressure. In one embodiment, the pressure is about 0.5 torr to about 100 torr. The surface modification in step (i) can be carried out at any suitable chamber pressure. In one embodiment, the pressure is about 5 torr to about 100 torr. In one embodiment, the pressure is about 0.5 torr to about 15 torr. In one embodiment, the pressure is about 1 torr to about 12 torr. In one embodiment, the pressure is about 1 torr to about 10 torr. In one embodiment, the pressure is about 1 torr to about 5 torr. In one embodiment, the pressure is about 1 torr to about 2 torr. In one embodiment, the pressure is about 0.5 torr to about 5 torr. In one embodiment, the pressure is about 0.2 torr to about 2 torr. In one embodiment, the pressure is about 0.2 torr. In one embodiment, the pressure is about 0.5 torr. In one embodiment, the pressure is about 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.

[0077] (d) Similar process (i)

[0078] In an exemplary embodiment of the surface modification in step (i), as shown in Figure 1A, the ZrO2 surface is exposed to anhydrous hydrogen fluoride (HF) (which can be produced from, for example, ammonium difluoride, sodium difluoride, potassium difluoride, or triethylamine trishydrofluoride) to convert the solid ZrO2 on the surface into solid ZrF4 and water vapor (i.e., ZrO2(s) + 4HF(g) → ZrF4(s) + 2H2O(g)). In another embodiment shown in Figure 1B, Ishikawa's reagent is used as a fluorinated surface modifier instead of HF.

[0079] Volatilization of process (a) and / or process (iii)

[0080] In the volatilization of step (a) and / or step (iii), the fluorinated metal surface is exposed to one or more chlorine-supplying volatilizers to produce chlorine-containing volatile byproducts containing one or more metals of the fluorinated metal compound.

[0081] (a) Volatile agents

[0082] The chlorine-supplying volatile agent comprises one or more chlorine-supplying ligands or species capable of exchanging fluoride ions for chloride ions. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises one or more of the following: thionyl chloride (SOCl2), chlorine (Cl2), dimethylaluminum chloride (DMAC, Al(CH3)2Cl), diethylaluminum chloride (DEAC, Al(C2H5)2Cl), titanium tetrachloride (TiCl4), boron trichloride (BCl3), and combinations thereof. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises DMAC. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises DEAC. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises TiCl4. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises BCl3. In one embodiment of this embodiment, the one or more chlorine-supplying volatile agents comprises two or more combinations of DMAC, DEAC, TiCl4, and BCl3.

[0083] As those skilled in the art will understand, DMAC, DEAC, TiCl4, and BCl3 contain elements that can deposit on an etched surface to form a solid residue that may contain aluminum, titanium, or boron. Therefore, in one embodiment, the chlorine-supplying volatilizer is metal- or substantially metal-free of boron. In another embodiment, the chlorine-supplying volatilizer contains thionyl chloride (SOCl2). In yet another embodiment, the volatilizer contains chlorine (Cl2).

[0084] (b) Conditions

[0085] time

[0086] As described above, in step (a) and / or step (iii), the fluorinated metal surface is exposed to one or more chlorine-supplying volatile agents for a certain time ("exposure time") before moving to the next step. In one embodiment, the exposure time in step (a) and / or step (iii) is about 0.5 seconds to about 30 seconds. In one embodiment, the exposure time in step (a) and / or step (iii) is about 0.5 seconds to about 10 seconds. In one embodiment, the exposure time in step (a) and / or step (iii) is about 1 second to about 7 seconds. In one embodiment, the exposure time in step (a) and / or step (iii) is about 7 seconds to about 10 seconds. In one embodiment, the exposure time in step (a) and / or step (iii) is about 10 seconds to about 20 seconds. In one embodiment, the exposure time in step (a) and / or step (iii) is about 20 seconds to about 30 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 0.25 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 0.5 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 1 second. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 2 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 3 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 4 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 5 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 6 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 7 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 8 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 9 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 10 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 12 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 15 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 17 seconds.In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 20 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 25 seconds. In one embodiment, the exposure time for step (a) and / or step (iii) is approximately 30 seconds.

[0087] Flow rate of chlorine supply volatilizer

[0088] In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 1 sccm to approximately 500 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 5 sccm to approximately 500 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 0.5 sccm to approximately 100 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 1 sccm to approximately 50 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 5 sccm to approximately 25 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 10 sccm to approximately 20 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 15 sccm to approximately 25 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 5 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 10 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 15 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at a rate of approximately 20 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 25 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 30 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 35 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 40 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 45 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 50 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 60 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 70 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 80 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 90 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 100 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 125 sccm. In one embodiment, the chlorine-supplying volatile agent is flushed at a rate of approximately 150 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 200 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 250 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 300 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 350 sccm. In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 400 sccm.In one embodiment, the chlorine-supplying volatile agent is flowed at approximately 450 sccm. In another embodiment, the chlorine-supplying volatile agent is flowed at approximately 500 sccm.

[0089] In one embodiment, the chlorine-supplying volatile agent is supplied separately.

[0090] In one embodiment, the chlorine supply volatilizer is supplied together with a suitable carrier gas. In one embodiment, the carrier gas includes argon. In one embodiment, the carrier gas includes nitrogen.

[0091] pressure

[0092] Step (a) and / or step (iii) can be performed at any preferred chamber pressure. In one embodiment, the pressure is about 0.5 torr to about 100 torr. In one embodiment, the pressure is about 5 torr to about 100 torr. In one embodiment, the pressure is about 0.5 torr to about 15 torr. In one embodiment, the pressure is about 1 torr to about 12 torr. In one embodiment, the pressure is about 1 torr to about 10 torr. In one embodiment, the pressure is about 1 torr to about 5 torr. In one embodiment, the pressure is about 1 torr to about 2 torr. In one embodiment, the pressure is about 0.5 torr to about 5 torr. In one embodiment, the pressure is about 0.2 torr to about 2 torr. In one embodiment, the pressure is about 0.2 torr. In one embodiment, the pressure is about 0.5 torr. In one embodiment, the pressure is about 1 torr. In one embodiment, the pressure is about 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.

[0093] (d) Exemplary process (iii)

[0094] In exemplary embodiments of step (a) and / or step (iii), as shown in Figure 1, the layer of ZrF4 on the surface of ZrO2 undergoes ligand exchange with thionyl chloride (SOCl2) to produce byproducts that may include volatile ZrCl4 vapor and volatile thionyl fluoride (SOF2) vapor (i.e., ZrF4(s) + 2SOCl2 → ZrCl4(g) + 2SOF2(g)).

[0095] Process (v) Surface cleaning

[0096] In the surface cleaning of step (v), the etched metal oxide surface is exposed to one or more oxidizing agents for a sufficient time to oxidize the metal by-products present on the etched metal surface to species that can be readily volatile when exposed to a fluorinating agent when step (i) is repeated in the next cycle. As described above, the fluorinating agent may generate surface contaminants that slow down or stop the etching process over time. The oxidation step converts these by-products into volatile species that can be readily reacted and removed when exposed to a fluorinating agent when step (i) is repeated in the next cycle. Furthermore, exposure of the metal surface to one or more oxidizing agents converts at least a portion of the surface to metal oxide before the next cycle of the process.

[0097] In one embodiment, one or more oxidizing agents include oxygen (O2), ozone (O3), nitric oxide (NO), water (H2O) vapor, hydrogen peroxide (H2O2), and oxygen plasma (O2O2). * ), N x O y(wherein the formula x=1 or 2 and y=1, 2, 3, or 4) and one or more combinations thereof. In one embodiment of this embodiment, one or more oxidizing agents include oxygen. In one embodiment of this embodiment, one or more oxidizing agents include ozone. In one embodiment of this embodiment, one or more oxidizing agents include nitric oxide. In one embodiment of this embodiment, one or more oxidizing agents include water vapor. In one embodiment of this embodiment, one or more oxidizing agents include hydrogen peroxide. In one embodiment of this embodiment, one or more oxidizing agents include oxygen and ozone. In one embodiment of this embodiment, one or more oxidizing agents include oxygen plasma. In one embodiment of this embodiment, one or more oxidizing agents include N x O y (wherein the formula x=1 or 2 and y=1, 2, 3, or 4). In one embodiment, one or more oxidizing agents are vapors.

[0098] In one embodiment, exposure of an etched metal oxide surface to one or more oxidizing agents includes continuous exposure to a first oxidizing agent, followed by exposure to a second oxidizing agent different from the first oxidizing agent. In one aspect of this embodiment, the first oxidizing agent is either oxygen or ozone, and the second oxidizing agent is the other of oxygen or ozone.

[0099] (b) Conditions

[0100] time

[0101] In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 0.5 seconds to approximately 10 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 1 second to approximately 7 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 7 seconds to approximately 10 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 10 seconds to approximately 20 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 20 seconds to approximately 30 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 30 seconds to approximately 60 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 1 second to approximately 60 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 0.25 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 0.5 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 1 second. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 2 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 3 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 4 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 5 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 6 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 7 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 8 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 9 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 10 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 12 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 15 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 17 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 20 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 25 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 30 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 35 seconds. In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 40 seconds.In one embodiment, the flow time of the oxidizing agent in step (v) is approximately 50 seconds. In another embodiment, the flow time of the oxidizing agent in step (v) is approximately 60 seconds.

[0102] flow rate

[0103] In one embodiment, the oxidizing agent is flowed at a rate of approximately 10 sccm to approximately 3000 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 50 sccm to approximately 3000 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 10 sccm to approximately 1000 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 500 sccm to approximately 1000 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 1000 sccm to approximately 2000 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 50 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 75 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 100 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 200 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 300 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 400 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 500 sccm. In one embodiment, the oxidizing agent is flowed at a rate of approximately 1000 sccm. In one embodiment, the oxidizing agent is flowed at approximately 1500 sccm. In one embodiment, the oxidizing agent is flowed at approximately 2000 sccm. In one embodiment, the oxidizing agent is flowed at approximately 2500 sccm. In one embodiment, the oxidizing agent is flowed at approximately 3000 sccm.

[0104] In one embodiment, the oxidizing agent is supplied separately.

[0105] In one embodiment, the oxidizing agent is supplied together with a suitable carrier gas. In one embodiment, the carrier gas includes argon. In one embodiment, the carrier gas includes nitrogen.

[0106] pressure

[0107] The surface cleaning step (v) can be performed at any suitable chamber pressure. In one embodiment, the pressure is about 0.5 torr to about 100 torr. In one embodiment, the pressure is about 5 torr to about 100 torr. In one embodiment, the pressure is about 0.5 torr to about 15 torr. In one embodiment, the pressure is about 1 torr to about 12 torr. In one embodiment, the pressure is about 1 torr to about 10 torr. In one embodiment, the pressure is about 1 torr to about 5 torr. In one embodiment, the pressure is about 1 torr to about 2 torr. In one embodiment, the pressure is about 0.5 torr to about 5 torr. In one embodiment, the pressure is about 0.2 torr to about 2 torr. In one embodiment, the pressure is about 0.2 torr. In one embodiment, the pressure is about 0.5 torr. In one embodiment, the pressure is about 1 torr. In one embodiment, the pressure is about 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] (d) Exemplary process (v)

[0109] In an exemplary embodiment of the surface cleaning of step (v), as shown in Figure 1, the etched metal oxide surface is exposed to an oxidizing agent, thereby converting surface contaminant atoms into a more oxidized form. In one embodiment, the surface contaminant atoms may include carbon, nitrogen, fluorine, sulfur, or chlorine.

[0110] Purging of processes (b), (ii), (iv), and (vi)

[0111] In each of the purging steps (b), (ii), (iv), and (vi) ("purging steps"), any suitable inert purge gas may be used. In one embodiment, the purge gas includes argon. In one embodiment, the purge gas includes nitrogen. In one embodiment, the same inert gas is used for each of the purging steps.

[0112] time

[0113] In one embodiment, the purge time is approximately 0.5 seconds to approximately 30 seconds. In one embodiment, the purge time is approximately 0.5 seconds to approximately 10 seconds. In one embodiment, the purge time is approximately 1 second to approximately 7 seconds. In one embodiment, the purge time is approximately 7 seconds to approximately 10 seconds. In one embodiment, the purge time is approximately 10 seconds to approximately 20 seconds. In one embodiment, the purge time is approximately 20 seconds to approximately 30 seconds. In one embodiment, the purge time is approximately 30 seconds to approximately 60 seconds. In one embodiment, the purge time is approximately 60 seconds to approximately 120 seconds. In one embodiment, the purge time is approximately 0.25 seconds. In one embodiment, the purge time is approximately 0.5 seconds. In one embodiment, the purge time is approximately 1 second. In one embodiment, the purge time is approximately 2 seconds. In one embodiment, the purge time is approximately 3 seconds. In one embodiment, the purge time is approximately 4 seconds. In one embodiment, the time is approximately 5 seconds. In one embodiment, the purge time is approximately 6 seconds. In one embodiment, the purge time is approximately 7 seconds. In one embodiment, the purge time is approximately 8 seconds. In one embodiment, the process purge time is approximately 9 seconds. In one embodiment, the purge time is approximately 10 seconds. In one embodiment, the purge time is approximately 12 seconds. In one embodiment, the purge exposure time is approximately 15 seconds. In one embodiment, the purge time is approximately 17 seconds. In one embodiment, the purge time is approximately 20 seconds. In one embodiment, the purge time is approximately 25 seconds. In one embodiment, the purge time is approximately 30 seconds. In one embodiment, the purge time is approximately 35 seconds. In one embodiment, the purge time is approximately 40 seconds. In one embodiment, the purge time is approximately 50 seconds. In one embodiment, the purge time is approximately 60 seconds. In one embodiment, the purge time is approximately 75 seconds. In one embodiment, the purge time is approximately 90 seconds. In one embodiment, the purge time is approximately 120 seconds. In one embodiment, each of the purging processes uses approximately the same purge time.

[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 process can be carried out at any suitable chamber pressure. In one embodiment, the pressure is about 0.05 torr to about 5 torr. In one embodiment, the pressure is about 1 torr to about 5 torr. In one embodiment, the pressure is about 1 torr to about 2 torr. In one embodiment, the pressure is about 0.5 torr to about 5 torr. In one embodiment, the pressure is about 0.05 torr to about 2 torr. In one embodiment, the pressure is about 0.05 torr. In one embodiment, the pressure is about 0.1 torr. In one embodiment, the pressure is about 0.2 torr. In one embodiment, the pressure is about 0.5 torr. In one embodiment, the pressure is about 1 torr. In one embodiment, the pressure is about 1.5 torr. In one embodiment, the pressure is about 2 torr. In one embodiment, the pressure is about 2.5 torr. In one embodiment, the pressure is about 5 torr.

[0118] Post-etching treatment

[0119] As described above, Process II disclosed and claimed further includes, is essentially, or consists of an oxidative post-treatment of optional step (vii) that can remove impurities remaining on the metal oxide surface after several cycles. In one embodiment of this embodiment, the post-treatment of optional step (vii) includes treating the metal oxide surface with one or more oxidizing agents for a desired time (e.g., about 10 seconds to about 500 seconds). In one embodiment of this embodiment, the post-treatment of optional step (vii) includes treating the metal oxide surface with one or more of oxygen (O2) and ozone (O3) for a desired time (e.g., about 10 seconds to about 500 seconds). In one embodiment of this embodiment, the post-treatment of optional step (vii) includes treating the metal oxide surface with oxygen (O2). In one embodiment of this embodiment, the post-treatment of optional step (vii) includes treating the metal oxide surface with ozone (O3). In one embodiment of this design, the post-treatment of an optional step (vii) includes treatment of the metal oxide surface with a combination of oxygen (O2) and ozone (O3).

[0120] Substrate temperature

[0121] In one embodiment, the substrate is heated to a temperature of approximately 100°C to approximately 450°C. In one embodiment, the substrate is heated to a temperature of approximately 100°C. In one embodiment, the substrate is heated to a temperature of approximately 150°C. In one embodiment, the substrate is heated to a temperature of approximately 200°C. In one embodiment, the substrate is heated to a temperature of approximately 250°C. In one embodiment, the substrate is heated to a temperature of approximately 300°C. In one embodiment, the internal chamber heater is set to approximately 350°C. In one embodiment, the substrate is heated to a temperature of approximately 400°C. In one embodiment, the substrate is heated to a temperature of approximately 450°C.

[0122] Film properties

[0123] The subject matter disclosed and claimed further includes films prepared by the method described herein.

[0124] Film aspect ratio

[0125] In one embodiment, a film etched by the method described herein has trenches, vias, or other topographic features having an aspect ratio of about 0 to about 60. 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 10 to about 100. In a further embodiment of this embodiment, the aspect ratio is about 0. In a further embodiment of this embodiment, the aspect ratio is about 1. In a further embodiment of this embodiment, the aspect ratio is about 2. In a further embodiment of this embodiment, the aspect ratio is about 5. In a further embodiment of this embodiment, the aspect ratio is about 10. In a further embodiment of this embodiment, the aspect ratio is about 20. In a further embodiment of this embodiment, the aspect ratio is about 30. In a further embodiment of this embodiment, the aspect ratio is about 40. In a further embodiment of this embodiment, the aspect ratio is about 50. In a further embodiment of this embodiment, the aspect ratio is about 60. In a further embodiment of this design, the aspect ratio is approximately 80. In a further embodiment of this design, the aspect ratio is approximately 100.

[0126] Dielectric constant

[0127] In another embodiment, the film etched by the method herein has a dielectric constant of 5 to 10. In another embodiment, the film etched by the method herein has a dielectric constant of 10 to 30. In another embodiment, the film etched by the method herein has a dielectric constant of 30 to 50. In another embodiment, the film etched by the method herein has a dielectric constant of 50 to 80. In another embodiment, the film etched by the method herein has a dielectric constant of about 1.5. In another embodiment, the film etched by the method herein has a dielectric constant of about 2. In another embodiment, the film etched by the method herein has a dielectric constant of about 3. In another embodiment, the film etched by the method herein has a dielectric constant of about 4. In another embodiment, the film etched by the method herein has a dielectric constant of about 5. In another embodiment, the film etched by the method herein has a dielectric constant of about 6. In another embodiment, the film etched by the method herein has a dielectric constant of about 7. In another embodiment, the film etched by the method herein has a dielectric constant of about 8. In another embodiment, the film etched by the method herein has a dielectric constant of about 9. In another embodiment, the film etched by the method herein has a dielectric constant of about 10. In another embodiment, the film etched by the method herein has a dielectric constant of about 12. In another embodiment, the film etched by the method herein has a dielectric constant of about 14. In another embodiment, the film etched by the method herein has a dielectric constant of about 16. In another embodiment, the film etched by the method herein has a dielectric constant of about 18. In another embodiment, the film etched by the method herein has a dielectric constant of about 20. In another embodiment, the film etched by the method herein has a dielectric constant of about 25. In another embodiment, the film etched by the method herein has a dielectric constant of about 30.In another embodiment, the film etched by the method herein has a dielectric constant of about 35. In another embodiment, the film etched by the method herein has a dielectric constant of about 40. In another embodiment, the film etched by the method herein has a dielectric constant of about 45. In another embodiment, the film etched by the method herein has a dielectric constant of about 50. In another embodiment, the film etched by the method herein has a dielectric constant of about 55. In another embodiment, the film etched by the method herein has a dielectric constant of about 60. In another embodiment, the film etched by the method herein has a dielectric constant of about 65. In another embodiment, the film etched by the method herein has a dielectric constant of about 70. In another embodiment, the film etched by the method herein has a dielectric constant of about 75. In another embodiment, the film etched by the method herein has a dielectric constant of about 80.

[0128] Crystal structure

[0129] In one embodiment, the film etched by the method described herein is crystalline, and the desired crystal structure accounts for the majority of the film. In one embodiment, the cubic structure accounts for the majority of the film composed of ZrO2, HfO2, a combination of HfO2 and ZrO2, or any of these materials, having artificial impurities (i.e., dopants). In one embodiment, the tetragonal structure accounts for the majority of the film composed of ZrO2, HfO2, a combination of HfO2 and ZrO2, or any of these materials, having artificial impurities (i.e., dopants). In one embodiment, the orthorhombic structure accounts for the majority of the film composed of ZrO2, HfO2, a combination of HfO2 and ZrO2, or any of these materials, having artificial impurities (i.e., dopants). In one embodiment, the non-centrosymmetric crystal structure accounts for the majority of the film composed of ZrO2, HfO2, a combination of HfO2 and ZrO2, or any of these materials, having artificial impurities (i.e., dopants). In one embodiment, the desired crystal structure accounts for approximately 50% to 90% of the film. In another embodiment, the desired crystal structure accounts for approximately 90% to 95% of the film. In yet another embodiment, the desired crystal structure accounts for approximately 95% to 100% of the film.

[0130] MIMcap device

[0131] In another embodiment, the disclosed and claimed subject matter relates to a metal-insulator-metal capacitor "MIMcap" device comprising, essentially comprising, or comprising a first electrode, a dielectric layer fabricated using the disclosed and claimed ALE process, and a second electrode. In a further embodiment, the MIMcap device ideally exhibits a higher dielectric constant (k) and lower leakage current than other equivalent MIMcaps fabricated without using the disclosed and claimed ALE process.

[0132] In a further embodiment, the first electrode and the second electrode are independently selected from TiN, W, Ni, Ru, Pt, and Al.

[0133] In a further embodiment, the first and second electrodes are made of TiN. In a further embodiment, the thickness of the initial dielectric layer before ALE is about 5 nm to about 10 nm. In a further embodiment, the thickness of the etched dielectric layer is about 1 nm to about 6 nm.

[0134] In a further embodiment, the capacitor has an ultrathin (<5 nm) ZrO2 dielectric layer that has superior properties (i.e., lower leakage current, higher k) compared to similar capacitors manufactured by other methods. [Examples]

[0135] 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.

[0136] 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.

[0137] Materials and methods:

[0138] The ALE 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.

[0139] The following examples were 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. The ALD system has a heated pedestal for placing the wafer. In each experiment, a 44 mm × 44 mm test substrate was placed on the first 300 mm silicon carrier wafer.

[0140] The Ishikawa reagent and thionyl chloride were obtained from MilliporeSigma. The Ishikawa reagent was maintained at 35°C in a stainless steel ampoule. The thionyl chloride was maintained at 30°C in a stainless steel ampoule.

[0141] [Table 1]

[0142] [Table 2]

[0143] [Table 3]

[0144] [Table 4]

[0145] Experimental conditions for Examples 9 and 10:

[0146] In the predictive examples 9 and 10, the general forms of steps (i) to (vi) are used, but alternative chemicals are used, and there are no specific restrictions on flow rate, concentration, administration time, etc.

[0147] [Table 5]

[0148] Example 1: ALE of ZrO2 using Ishikawa reagent, SOCl2, and ozone

[0149] The test substrates were prepared by ALD of ZrO2 on a 300 mm silicon wafer and then cut into 44 mm × 44 mm test substrates. The film thickness of ZrO2 was approximately 54–60 Å. The pedestal heater of the process chamber was set to either 315°C, 345°C, or 375°C, and 10–30 ALE cycles were performed. These correspond to calibrated sample temperatures of approximately 300°C, 325°C, or 350°C, respectively. The results are shown in Table 1 below. Significant etching was observed from 300°C to 350°C, and the amount of etching increased with increasing temperature. Linear approximation of the data at 350°C indicates that the amount of ZrO2 etching per cycle is approximately 1.5 Å / cycle, and the etching delay is approximately 3 cycles. [Table 6]

[0150] As shown in Figure 1, samples subjected to 10, 20, or 30 ALE cycles at 350°C were measured by X-ray photoelectron spectroscopy (XPS). Compared to similar samples that did not undergo ALE, each of these samples contained a measurable amount of fluorine. While not theoretically bound, this may be due to the formation of surface oxyfluorides that are not completely removed by the chlorination process. Surface carbon residue increased slightly with increasing cycle count. Each sample was substantially free of nitrogen or sulfur surface residue.

[0151] Example 2: ALE of HfO2 using Ishikawa reagent, SOCl2, and ozone

[0152] The test substrates were prepared on a 300 mm silicon wafer by ALD of HfO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 46–48 Å of HfO2. The pedestal heater of the process chamber was set to either 315°C, 345°C, or 375°C, and 10–50 ALE cycles of process steps (i)–(vi) were performed. These correspond to calibrated sample temperatures of approximately 300°C, 325°C, or 350°C, respectively. The results are shown in Table 2 below. Significant etching was observed from 325°C to 350°C, and the amount of etching increased with increasing temperature. Linear approximation of the data at 350°C indicates that the amount of HfO2 etching per cycle is approximately 0.5 Å / cycle, and the etching delay is approximately 4 cycles. [Table 7]

[0153] Example 3: ALE of ZrO2 using Ishikawa reagent and SOCl2 with an alternative oxidizing agent

[0154] The test substrate was prepared on a 300 mm silicon wafer by ALD of ZrO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 65 Å of ZrO2. The process chamber pedestal heater was set to 375°C, and 30 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. The oxidizing agent used in step (v) was replaced with either O2 or a mixture of approximately 4% O3 + approximately 96% O2. When O2 was used as the oxidizing agent, approximately 5 ± 2 Å of ZrO2 was removed. When a mixture of approximately 4% O3 + approximately 96% O2 was used as the oxidizing agent, approximately 37 ± 2 Å of ZrO2 was removed.

[0155] Example 4: ALE of HfO2 using Ishikawa reagent and SOCl2 with an alternative oxidizing agent

[0156] The test substrate was prepared on a 300 mm silicon wafer by ALD of HfO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 47 Å for HfO2. The process chamber pedestal heater was set to 375°C, and 30 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. The oxidizing agent used in step (v) was replaced with either O2 or a mixture of approximately 4% O3 + approximately 96% O2. When O2 was used as the oxidizing agent, no significant amount of HfO2 was removed. When the mixture of approximately 4% O3 + approximately 96% O2 was used as the oxidizing agent, approximately 10 ± 2 Å of ZrO2 was removed.

[0157] Example 5: ALE of ZrO2 using Ishikawa reagent and SOCl2 without an oxidation step

[0158] The test substrate was prepared by ALD of ZrO2 on a 300 mm silicon wafer, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 56 Å of ZrO2. The process chamber pedestal heater was set to 375°C, and either 30, 60, or 90 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. Steps (v) and (vi) were omitted from the ALE process cycle, i.e., only process steps (i) to (iv) were repeated. The number of doses for steps (i) and (iii) was increased as described above.

[0159] After 30 ALE cycles, approximately 16±2 Å of ZrO2 was removed. After 60 ALE cycles, approximately 27±2 Å of ZrO2 was removed. After 90 ALE cycles, approximately 32±2 Å of ZrO2 was removed.

[0160] As shown in Figure 2, samples subjected to 30, 60, or 90 ALE cycles of process steps (i) to (iv) at 350°C were measured by X-ray photoelectron spectroscopy (XPS). Compared to similar samples that did not undergo ALE, each of these samples contained a measurable amount of fluorine. While not theoretically bound, this may be due to the formation of surface oxyfluorides that are not completely removed by the chlorination step. Measurable amounts of carbon, nitrogen, and sulfur residues are present and increase with increasing number of ALE cycles. This data suggests that in the absence of the oxidation step (process step (v) above), the accumulated light element residues prevent etching by either blocking the surface and / or providing alternative surface reaction pathways that do not etch the surface.

[0161] Example 6: ALE of HfO2 using Ishikawa reagent and SOCl2 without an oxidation step

[0162] The test substrate was prepared on a 300 mm silicon wafer by ALD of HfO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 46–47 Å of HfO2. The process chamber pedestal heater was set to 375°C, and either 30, 60, or 90 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. Steps (v) and (vi) were omitted from the ALE process cycle, i.e., only process steps (i)–(iv) were repeated. The number of doses in steps (i) and (iii) was increased as described above.

[0163] After 30 ALE cycles, approximately 3 ± 2 Å of HfO2 was removed. After 60 ALE cycles, approximately 5 ± 2 Å of HfO2 was removed. After 90 ALE cycles, approximately 6 ± 2 Å of HfO2 was removed.

[0164] Example 7: ALE of ZrO2 using Ishikawa reagent, DMAC, and ozone

[0165] The test substrate was prepared on a 300 mm silicon wafer by ALD of ZrO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 65 Å of ZrO2. The process chamber pedestal heater was set to 375°C, and 30 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. As described above, the ALE cycle was modified in step (iii) to dose dimethyl aluminum chloride (DMAC) instead of SOCl2.

[0166] After 30 ALE cycles, approximately 27±2 Å of ZrO2 was removed.

[0167] Example 8: ALE of HfO2 using Ishikawa reagent, DMAC, and ozone

[0168] The test substrate was prepared on a 300 mm silicon wafer by ALD of HfO2, and then cut into 44 mm × 44 mm test substrates. The film thickness was approximately 47 Å with HfO2. The process chamber pedestal heater was set to 375°C, and 30 ALE cycles were performed. This corresponds to a calibrated sample temperature of approximately 350°C. As described above, the ALE cycle was modified in step (iii) to dose dimethyl aluminum chloride (DMAC) instead of SOCl2.

[0169] After 30 ALE cycles, approximately 8±2 Å of HfO2 was removed.

[0170] Example 9: ALE of ZrO2 and HfO2 using difluoride salt, chlorinator, and ozone

[0171] In a predictive example, the test substrate can be prepared by ALD of a thin film of HfO2 or ZrO2 on a silicon substrate. 5 to 100 ALE cycles can be performed using the sample at a temperature of approximately 200°C to approximately 400°C. The ALE cycle may include the following six steps: (i) a first dose of anhydrous HF vapor from a container containing a difluoride salt, (ii) a first purge, (iii) a second dose of chlorinator, (iv) a second purge, (v) a third dose of oxidizing agent, and (vi) a third purge. The difluoride salt may include ammonium difluoride (NH4HF2), sodium difluoride (NaHF2), potassium difluoride (KHF2), or a mixture thereof. The chlorinator may include thionyl chloride or dimethylaluminum chloride. The oxidizing agent may include ozone and oxygen gas. An etching rate of approximately 0.5 Å / cycle to approximately 5.0 Å / cycle is expected per cycle.

[0172] Example 10: ALE of ZrO2 and HfO2 using anhydrous HF, chlorinator, and ozone liquid sources

[0173] In a predictive example, the test substrate can be prepared by ALD of a thin film of HfO2 or ZrO2 on a silicon substrate. 5 to 100 ALE cycles can be performed using the sample at a temperature of approximately 200°C to approximately 400°C. The ALE cycle may include the following six steps: (i) a first dose of vapor from a container containing a liquid fluorinator, (ii) a first purge, (iii) a second dose of chlorinator, (iv) a second purge, (v) a third dose of oxidizing agent, and (vi) a third purge. The liquid fluorinator may include triethylamine trishydrofluoride (TREAT-HF), pyridine hydrogen fluoride (HF-pyridine), or a mixture thereof. The chlorinator may include thionyl chloride or dimethylaluminum chloride. The oxidizing agent may include ozone and / or oxygen gas. An etching rate of approximately 0.5 Å / cycle to approximately 5.0 Å / cycle is expected per cycle.

[0174] Example 11: Hot vapor phase etching of native Co, Mo, and W oxides using a chlorinator

[0175] The test substrates were prepared by physical vapor deposition (PVD) of Co, Mo, or W. For Co, approximately 165-180 Å of Co was deposited as a blanket film on approximately 3000 Å of thermally grown SiO2 on a 200 mm silicon wafer, and then cut into 44 mm × 44 mm test substrates. For Mo, a circular spot of approximately 200 Å with a diameter of approximately 45 mm was deposited on approximately 3000 Å of thermally grown SiO2 on a 300 mm silicon wafer, and then cut into 44 mm × 44 mm test substrates, with each test substrate centered on one Mo spot. For W, a circular spot of approximately 200 Å with a diameter of approximately 45 mm was deposited on approximately 3000 Å of thermally grown SiO2 on a 300 mm silicon wafer, and then cut into 44 mm × 44 mm test substrates, with each test substrate centered on one W spot. All substrates were exposed to ambient air at room temperature for over 1000 hours to allow native oxides to form. The process chamber pedestal heater was set to 325°C, and 20, 40, or 60 vapor-phase etching cycles were performed. This corresponds to a calibrated sample temperature of approximately 310°C. The results are shown in Table 3 below. The results reported are measured using X-ray fluorescence calibrated to the metal thickness; i.e., the actual thickness of the removed native oxide is greater than the thickness reported below as the density of metal atoms is lower than that of the metal. The greatest etching was observed with Mo, followed by W. The effect on Co was minimal under the test conditions. Etching was limited to the surface layer, as suggested by the stable amount of material etched with increasing number of etching cycles. No increase in metal resistivity was observed. [Table 8]

[0176] As shown in Examples 1-10 above, the ALE process can be easily controlled (i.e., tuned) to provide a specific amount of etching for a desired application. The selection of surface modifiers, volatiles, and oxidizers is expected to affect etching characteristics, including etching per cycle and selectivity. This flexibility enables etching of metal oxides for several applications, particularly in semiconductor devices, such as thinning of high-k oxides in high-aspect-ratio structures, or thinning of oxide ferroelectrics with stringent requirements for composition and crystallinity.

[0177] Surface modifiers are proposed that are either metal-free or that yield metal-free surface modifier vapors through the decomposition of the original agent (e.g., KHF2(s) → KF(s) + HF(g)). Some of these agents are liquid or solid at standard temperature and pressure and can be packaged in containers such as ampoules. Storage and delivery of this form of chemical are safer and easier to deploy compared to agents that are gaseous at standard temperature and pressure.

[0178] As shown in Example 11 above, the volatile agents disclosed and claimed herein can selectively remove oxides formed on metal surfaces. These oxides may be by-products potentially formed by the exposure of metals to air. Such oxides can cause undesirable effects, such as high contact resistance between the oxidized metal and a second metal deposited in contact with the oxidized metal. Selective gas-phase volatilization of surface compounds, such as native oxides, may be a convenient method for reintegrating unfinished semiconductor device wafers exposed to air.

[0179] 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 modifications 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) A volatilization step comprising exposing a metal oxide-containing surface or a metal fluoride-containing surface to one or more chlorine-supplying volatile agents to generate one or more chlorine-containing volatile by-products containing one or more metals from the metal oxide-containing surface or the metal fluoride-containing surface, and (b) Optional purging process, A vapor phase etching process, including

2. (i) A surface modification step comprising exposing a metal oxide surface to one or more fluorinated surface modifiers to generate one or more fluorinated metal compounds on the surface, (ii) Purge process, (iii) A volatilization step comprising exposing the fluorinated metal compound to one or more chlorine-supplying volatile agents to produce one or more chlorine-containing volatile by-products containing one or more metals of the fluorinated metal compound, (iv) Purge process, (v) A surface cleaning step comprising exposing the surface to one or more oxidizing agents to remove contaminants and converting at least a portion of the surface to a metal oxide, (vi) Purge process, A vapor phase etching process, including

3. The process according to claim 2, further comprising step (vii) an oxidative post-treatment step for removing impurities remaining on the surface.

4. The process according to claim 1 or 2, wherein the metal oxide-containing surface, the metal fluoride-containing surface, or the metal oxide surface contains one or more of zirconium (Zr), hafnium (Hf), aluminum (Al), titanium (Ti), cobalt (Co), nickel (Ni), molybdenum (Mo), ruthenium (Ru), tungsten (W), and combinations thereof.

5. The process according to claim 1, wherein the metal oxide-containing surface or the metal fluoride-containing surface contains cobalt (Co).

6. The process according to claim 1, wherein the metal oxide-containing surface or the metal fluoride-containing surface contains nickel (Ni).

7. The process according to claim 1, wherein the metal oxide-containing surface or the metal fluoride-containing surface contains molybdenum (Mo).

8. The process according to claim 1, wherein the metal oxide-containing surface or the metal fluoride-containing surface contains ruthenium (Ru).

9. The process according to claim 1, wherein the metal oxide-containing surface or the metal fluoride-containing surface contains tungsten (W).

10. The process according to claim 2, wherein the metal oxide surface contains cobalt (Co).

11. The process according to claim 2, wherein the metal oxide surface contains nickel (Ni).

12. The process according to claim 2, wherein the metal oxide surface contains molybdenum (Mo).

13. The process according to claim 2, wherein the metal oxide surface contains ruthenium (Ru).

14. The process according to claim 2, wherein the metal oxide surface contains tungsten (W).

15. The aforementioned metal oxide is ZrO ２ , HfO ２ , Hf ｘ Zr １－ｘ O ２ (In the formula, x is a value between 0 and 1), TiO ２ Al ２ O ３ The process according to claim 2, comprising one or more of the following:

16. The surface of the metal oxide contains ZrO ２ The process according to claim 2, wherein the surface of the metal oxide contains ZrO

17. The metal oxide surface is HfO ２ The process according to claim 2, including the process described in claim 2.

18. The metal oxide surface is Hf ｘ Zr １－ｘ O ２ The process according to claim 2, comprising (wherein x is a value between 0 and 1).

19. The metal oxide surface is TiO ２ The process according to claim 2, including the process described in claim 2.

20. The metal oxide surface is Al ２ O ３ The process according to claim 2, including the process described in claim 2.

21. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include one or more metal-free fluorides.

22. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include one or more of Ishikawa reagent, ammonium difluoride, sodium difluoride, potassium difluoride, pyridine hydrogen fluoride, triethylamine trishydrofluoride, hydrogen fluoride, and combinations thereof.

23. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include two or more of the following: Ishikawa reagent, ammonium difluoride, sodium difluoride, potassium difluoride, pyridine hydrogen fluoride, triethylamine trishydrofluoride, and hydrogen fluoride.

24. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include Ishikawa reagent.

25. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include ammonium difluoride.

26. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include sodium difluoride.

27. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include potassium difluoride.

28. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include pyridine hydrogen fluoride.

29. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include triethylamine trishydrofluoride.

30. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers include hydrogen fluoride.

31. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 0.5 seconds to about 30 seconds.

32. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 0.5 seconds.

33. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 1 second.

34. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 5 seconds.

35. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 10 seconds.

36. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is approximately 15 seconds.

37. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is about 20 seconds.

38. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is approximately 25 seconds.

39. The process according to claim 2, wherein in step (i), the exposure time of the one or more fluorinated surface modifiers to the surface of the metal oxide is approximately 30 seconds.

40. The process according to claim 2, wherein in step (i), one or more fluorinated surface modifiers are flowed at a rate of about 0.5 sccm to about 500 sccm.

41. The process according to claim 2, wherein step (i) is performed at a pressure of about 0.5 tor to about 100 tor.

42. In step (a) above, one or more chlorine supply volatile agents are dimethylaluminum chloride (DMAC, Al(CH)). ３ ) ２ Cl), diethylaluminum chloride (DEAC, Al(C) ２ H ５ ) ２ Cl), Titanium tetrachloride (TiCl) ４ ), boron trichloride (BCl ３ ), thionyl chloride (SOCl ２ ), chlorine (Cl ２ The process according to claim 1, comprising one or more of the following:

43. In step (a) above, one or more chlorine supply volatile agents are dimethylaluminum chloride (DMAC, Al(CH)). ３ ) ２ The process according to claim 1, comprising Cl).

44. In step (a) above, one or more chlorine supply volatile agents are diethylaluminum chloride (DEAC, Al(C)). ２ H ５ ) ２ The process according to claim 1, comprising Cl).

45. In step (a) above, one or more chlorine supply volatile agents are provided, such as titanium tetrachloride (TiCl ４ The process according to claim 1, including )

46. In step (a) above, one or more chlorine supply volatile agents are provided with boron trichloride (BCl ３ The process according to claim 1, including )

47. In step (a) above, one or more chlorine supply volatile agents are provided, thionyl chloride (SOCl ２ The process according to claim 1, including )

48. In step (a) above, one or more chlorine-supplying volatile agents are used to supply chlorine (Cl ２ The process according to claim 1, including )

49. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 0.5 seconds to about 30 seconds.

50. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 0.5 seconds.

51. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 1 second.

52. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 5 seconds.

53. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 10 seconds.

54. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 15 seconds.

55. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 20 seconds.

56. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 55 seconds.

57. The process according to claim 1, wherein in step (a), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 30 seconds.

58. The process according to claim 1, wherein in step (a), one or more chlorine-supplying volatile agents are flowed at a rate of about 1 sccm to about 500 sccm.

59. The process according to claim 1, wherein step (a) is performed at a pressure of about 0.5 tor to about 100 tor.

60. In step (iii) above, one or more chlorine supply volatile agents are dimethylaluminum chloride (DMAC, Al(CH)). ３ ) ２ Cl), diethylaluminum chloride (DEAC, Al(C) ２ H ５ ) ２ Cl), Titanium tetrachloride (TiCl) ４ ), boron trichloride (BCl ３ ), thionyl chloride (SOCl ２ ), chlorine (Cl ２ The process according to claim 2, comprising one or more of the following:

61. In step (iii) above, one or more chlorine supply volatile agents are dimethylaluminum chloride (DMAC, Al(CH)). ３ ) ２ The process according to claim 2, comprising Cl).

62. In the above step (iii), one or more chlorine supply volatile agents are diethylaluminum chloride (DEAC, Al(C)). ２ H ５ ) ２ The process according to claim 2, comprising Cl).

63. In the above step (iii), one or more chlorine supply volatile agents are titanium tetrachloride (TiCl ４ The process according to claim 2, including )

64. In the above step (iii), one or more chlorine supply volatile agents are provided with boron trichloride (BCl ３ The process according to claim 2, including )

65. In the above step (iii), one or more chlorine supply volatile agents are provided, thionyl chloride (SOCl ２ The process according to claim 2, including )

66. In the above step (iii), one or more chlorine-supplying volatile agents are used to provide chlorine (Cl ２ The process according to claim 2, including )

67. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 0.5 seconds to about 30 seconds.

68. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 0.5 seconds.

69. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 1 second.

70. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 5 seconds.

71. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 10 seconds.

72. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 15 seconds.

73. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is about 20 seconds.

74. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 55 seconds.

75. The process according to claim 2, wherein in step (iii), the exposure time of the one or more chlorine-supplying volatile agents to the surface of the metal oxide is approximately 30 seconds.

76. The process according to claim 2, wherein in step (iii), one or more chlorine-supplying volatile agents are flowed at a rate of about 1 sccm to about 500 sccm.

77. The process according to claim 2, wherein step (iii) is performed at a pressure of about 0.5 tor to about 100 tor.

78. In step (v) above, one or more oxidizing agents are oxygen (O ２ ), ozone (O ３ ), water (H ２ O) vapor, hydrogen peroxide (H ２ O ２ ), oxygen plasma (O ＊ ), N ｘ O ｙ The process according to claim 2, comprising nitric oxide (NO) and one or more combinations thereof (wherein x = 1 or 2 and y = 1, 2, 3, or 4).

79. In step (v) above, one or more oxidizing agents are used to deliver oxygen (O ２ The process according to claim 2, including )

80. In step (v) above, one or more oxidizing agents are used to produce ozone (O ３ The process according to claim 2, including )

81. The process according to claim 2, wherein in step (v), one or more oxidizing agents include nitric oxide (NO).

82. In step (v) above, one or more oxidizing agents are added to water (H ２ O) The process according to claim 2, comprising steam.

83. In step (v) above, one or more oxidizing agents are hydrogen peroxide (H ２ O ２ The process according to claim 2, including )

84. In step (v) above, one or more oxidizing agents are used to form an oxygen plasma (O ＊ The process according to claim 2, including )

85. In step (v) above, one or more oxidizing agents are N ｘ O ｙ The process according to claim 2, comprising (wherein x = 1 or 2 and y = 1, 2, 3, or 4).

86. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is about 1 second to about 60 seconds.

87. The process according to claim 2, wherein in step (v), the exposure time of the one or more oxidizing agents is approximately 1 second.

88. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 5 seconds.

89. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 10 seconds.

90. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 15 seconds.

91. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 20 seconds.

92. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 30 seconds.

93. The process according to claim 2, wherein in step (v), the exposure time to the one or more oxidizing agents is approximately 60 seconds.

94. The process according to claim 2, wherein in step (v), one or more oxidizing agents are flowed at a rate of about 10 sccm to about 1000 sccm.

95. The process according to claim 2, wherein step (v) is performed at a pressure of about 0.5 tor to about 100 tor.

96. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of approximately 100°C to approximately 450°C.

97. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of about 100°C.

98. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of about 150°C.

99. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of about 200°C.

100. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of approximately 250°C.

101. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of approximately 300°C.

102. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of approximately 350°C.

103. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of about 400°C.

104. The process according to claim 1 or 2, wherein the substrate is heated to a temperature of approximately 450°C.

105. The process according to claim 1 or 2, comprising approximately 100 to approximately 1000 cycles.

106. The process according to claim 1 or 2, comprising approximately 25 to approximately 250 cycles.

107. The process according to claim 1 or 2, comprising approximately 5 to approximately 50 cycles.

108. The process according to claim 1 or 2, comprising approximately 5 cycles.

109. The process according to claim 1 or 2, comprising approximately 10 cycles.

110. The process according to claim 1 or 2, comprising approximately 20 cycles.

111. The process according to claim 1 or 2, comprising approximately 25 cycles.

112. The process according to claim 1 or 2, comprising approximately 35 cycles.

113. The process according to claim 1 or 2, comprising approximately 50 cycles.

114. The process according to claim 1 or 2, comprising approximately 75 cycles.

115. The process according to claim 1 or 2, comprising approximately 100 cycles.

116. The process according to claim 1 or 2, comprising approximately 200 cycles.

117. The process according to claim 1 or 2, comprising approximately 250 cycles.

118. The process according to claim 1 or 2, comprising approximately 300 cycles.

119. The process according to claim 1 or 2, comprising approximately 325 cycles.

120. The process according to claim 1 or 2, comprising approximately 400 cycles.

121. The process according to claim 1 or 2, comprising approximately 500 cycles.

122. The process according to claim 1 or 2, comprising approximately 750 cycles.

123. The process according to claim 1 or 2, comprising approximately 1,000 cycles.

124. A metal-containing film etched by a process according to any one of claims 1 to 123, comprising topographic features having an aspect ratio of approximately 0 to approximately 60.

125. A metal-containing film etched by a process according to any one of claims 1 to 123, comprising topographic features having an aspect ratio of approximately 1 to approximately 10.

126. A metal-containing film etched by a process according to any one of claims 1 to 123, comprising topographic features having an aspect ratio of approximately 10 to approximately 100.

127. A metal-containing film etched by a process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 0.

128. A metal-containing film etched by a process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 1.

129. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 2.

130. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 5.

131. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 10.

132. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 20.

133. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 30.

134. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 40.

135. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 50.

136. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 60.

137. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 80.

138. A metal-containing film etched by the process according to any one of claims 1 to 123, comprising a topographic feature having an aspect ratio of approximately 100.

139. A metal-containing film having a dielectric constant of approximately 5 to approximately 10, etched by the process described in any one of claims 1 to 123.

140. A metal-containing film having a dielectric constant of approximately 10 to approximately 30, etched by the process described in any one of claims 1 to 123.

141. A metal-containing film having a dielectric constant of approximately 30 to approximately 50, etched by the process described in any one of claims 1 to 123.

142. A metal-containing film having a dielectric constant of approximately 50 to approximately 80, etched by the process described in any one of claims 1 to 123.

143. A metal-containing film having a dielectric constant of approximately 1.5, etched by the process described in any one of claims 1 to 123.

144. A metal-containing film having a dielectric constant of approximately 2, etched by the process described in any one of claims 1 to 123.

145. A metal-containing film having a dielectric constant of approximately 3, etched by the process described in any one of claims 1 to 123.

146. A metal-containing film having a dielectric constant of approximately 4, etched by the process described in any one of claims 1 to 123.

147. A metal-containing film having a dielectric constant of approximately 5, etched by the process described in any one of claims 1 to 123.

148. A metal-containing film having a dielectric constant of approximately 6, etched by the process described in any one of claims 1 to 123.

149. A metal-containing film having a dielectric constant of approximately 7, etched by the process described in any one of claims 1 to 123.

150. A metal-containing film having a dielectric constant of approximately 8, etched by the process described in any one of claims 1 to 123.

151. A metal-containing film having a dielectric constant of approximately 9, etched by the process described in any one of claims 1 to 123.

152. A metal-containing film having a dielectric constant of approximately 10, etched by the process described in any one of claims 1 to 123.

153. A metal-containing film having a dielectric constant of approximately 12, etched by the process described in any one of claims 1 to 123.

154. A metal-containing film having a dielectric constant of approximately 14, etched by the process described in any one of claims 1 to 123.

155. A metal-containing film having a dielectric constant of approximately 16, etched by the process described in any one of claims 1 to 123.

156. A metal-containing film having a dielectric constant of approximately 18, etched by the process described in any one of claims 1 to 123.

157. A metal-containing film having a dielectric constant of approximately 20, etched by the process described in any one of claims 1 to 123.

158. A metal-containing film having a dielectric constant of approximately 25, etched by the process described in any one of claims 1 to 123.

159. A metal-containing film having a dielectric constant of approximately 30, etched by the process described in any one of claims 1 to 123.

160. A metal-containing film having a dielectric constant of approximately 35, etched by the process described in any one of claims 1 to 123.

161. A metal-containing film having a dielectric constant of approximately 40, etched by the process described in any one of claims 1 to 123.

162. A metal-containing film having a dielectric constant of approximately 55, etched by the process described in any one of claims 1 to 123.

163. A metal-containing film having a dielectric constant of approximately 60, etched by the process described in any one of claims 1 to 123.

164. A metal-containing film having a dielectric constant of approximately 65, etched by the process described in any one of claims 1 to 123.

165. A metal-containing film having a dielectric constant of approximately 70, etched by the process described in any one of claims 1 to 123.

166. A metal-containing film having a dielectric constant of approximately 75, etched by the process described in any one of claims 1 to 123.

167. A metal-containing film having a dielectric constant of approximately 80, etched by the process described in any one of claims 1 to 123.

168. A metal-containing film etched by the process described in any one of claims 1 to 123, having a predominantly cubic crystal structure.

169. A metal-containing film etched by the process described in any one of claims 1 to 123, having a predominantly tetragonal structure.

170. A metal-containing film etched by the process described in any one of claims 1 to 123, having a predominantly orthorhombic structure.

171. A metal-containing film etched by the process described in any one of claims 1 to 123, having a mostly non-centrosymmetric crystalline structure.

172. A metal-insulator-metal capacitor ("MIMcap") device comprising a first electrode, a fabricated dielectric layer, and a second electrode, wherein the dielectric layer is fabricated using a process described in any one of claims 1 to 123.

173. The metal-insulator-metal capacitor ("MIMcap") device according to claim 172, wherein the dielectric layer has a thickness of about 5 nm to about 10 nm before etching using the process described in any one of claims 1 to 123.

174. The metal-insulator-metal capacitor ("MIMcap") device according to claim 172, wherein the dielectric layer has a thickness of about 1 nm to about 6 nm after being etched using the process described in any one of claims 1 to 123.

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