WO2023066847A1 - Selective thermal atomic layer etching - Google Patents

Selective thermal atomic layer etching Download PDF

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Publication number
WO2023066847A1
WO2023066847A1 PCT/EP2022/078797 EP2022078797W WO2023066847A1 WO 2023066847 A1 WO2023066847 A1 WO 2023066847A1 EP 2022078797 W EP2022078797 W EP 2022078797W WO 2023066847 A1 WO2023066847 A1 WO 2023066847A1
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Prior art keywords
torr
acid
total pressure
metal
seconds
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PCT/EP2022/078797
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English (en)
French (fr)
Inventor
Ravindra Kanjolia
Jean-Sébastien LEHN
Martin E. McBRIARTY
Ronald PEARLSTEIN
Jared Leith McWILLIAMS
Nguyen Minh VU
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Merck Patent GmbH
Versum Materials US LLC
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Merck Patent GmbH
Versum Materials US LLC
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Application filed by Merck Patent GmbH, Versum Materials US LLC filed Critical Merck Patent GmbH
Priority to EP22808619.5A priority Critical patent/EP4419732A1/en
Priority to KR1020247015988A priority patent/KR20240089749A/ko
Priority to IL311977A priority patent/IL311977A/en
Priority to JP2024523453A priority patent/JP2024539676A/ja
Priority to CN202280070446.4A priority patent/CN118119734A/zh
Priority to US18/693,555 priority patent/US12590374B2/en
Publication of WO2023066847A1 publication Critical patent/WO2023066847A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/12—Gaseous compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/02—Local etching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/26—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials
    • H10P50/264—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means
    • H10P50/266—Dry etching; Plasma etching; Reactive-ion etching of conductive or resistive materials by chemical means by vapour etching only

Definitions

  • the disclosed and claimed subject matter relates to selective thermal atomic layer etching with a novel series of halogen-free organic acids cycled with an oxidant as a co-reactant to etch metals. Selectivity was shown by thermal etching of copper, cobalt, molybdenum, tungsten in conditions where nickel, platinum, ruthenium, zirconium oxide and SiO2were not etched.
  • Atomic Layer Deposition is one technique finding increased application in the semiconductor industry and it currently is the deposition method allowing the best control on the amount of material deposited.
  • ALD atomic Layer Deposition
  • a layer of atoms is deposited on all surfaces that are exposed to a precursor in the gas phase - this layer is at most as thick as the thickness of one atomic layer.
  • a layer of material with the desired thickness will be deposited.
  • the archetypical example of such a process is the deposition of aluminum oxide (AI2O3) from trimethylaluminum (TMA, A1(CH3)3) and water (H2O), where methane (CH4) is eliminated from the two reacting species.
  • AI2O3 aluminum oxide
  • TMA trimethylaluminum
  • H2O water
  • Atomic Layer Etching can be viewed as the layer-by-layer subtraction of material when ALD is the layer-by-layer addition of material.
  • ALE Atomic Layer Etching
  • a layer of atoms is removed from all surfaces that are exposed to a precursor in the gas phase - this layer is ideally also at most as thick as the thickness of one atomic layer.
  • ALE is performed by sequentially exposing the surfaces to at least two different precursors, a 1 st precursor that activates a layer of surface atoms and a 2 nd precursor that promotes the sublimation of this activated layer of atoms; sometimes a 3 rd precursor is used to regenerate the surface to the condition where the 1 st precursor will be active.
  • tungsten could be etched (between 128 °C and 207 °C) by sequentially exposing a tungsten surface having a native oxide layer to:
  • acetylacetone such as 1,1, 1,5, 5, 5-hexafluoro-2, 4, -pentanedione (HF AC), which reacts with the copper oxide surface species to generate volatile copper acetylacetonate species (sublimation).
  • An alternative method was used to etch copper and cobalt films by cycling alcohols, aldehydes, or esters in one step and an oxidizing gas in another step. See, e.g., International Publication WO 2022050099. In one of these procedures, a cobalt oxide film was etched using tertbutyl alcohol and ozone at 275 °C. In another of these procedures, a copper oxide film was etched using tert-butyl alcohol and ozone at 275 °C.
  • acetylacetone such as 1,1, 1,5, 5, 5-hexafluoro-2, 4, -pentanedione (HF AC), which react with the cobalt chloride surface species to generate volatile cobalt chloro-acetylacetonate species (sublimation).
  • etching reagents such as those used in the disclosed and claimed subject matter (including, but not limited to, pivalic acid, isobutyric acid, and/or propionic acid as volatilizing agents, and water, oxygen, and/or hydrogen peroxide as oxidants) — do not require a plasma and do not contain halogens.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more halogen-free organic acid volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant to etch metals.
  • the one or more halogen-free organic acid volatilizer includes one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2- methylbutanoic acid, 3 -methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2//)-but-2-enoic acid, (Z)-2-butenoic acid and combinations thereof.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with pivalic acid as a volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant to selectively etch copper, cobalt, molybdenum and/or tungsten in conditions where nickel, platinum, ruthenium, zirconium oxide and/or and S i Oz are not etched.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with isobutyric acid as a volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant to selectively etch copper, cobalt, molybdenum and/or tungsten.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with propionic acid as a volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant to selectively etch copper, cobalt, molybdenum, and/or tungsten.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid, each of which is halogen-free, as a volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant.
  • the disclosed and claimed process avoids all risk of contaminating the substrates with halogen atoms.
  • the method is free of 1 ,1 ,1 ,5, 5, 5-hexafluoro-2, 4, -pentanedione (HF AC) and similar materials.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid as a volatizer together with one or more of water, oxygen and a water/oxygen mixture as an oxidizing co-reactant that does not include or does not necessarily require the use of plasma.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid as a volatizer together with water as an oxidizing co-reactant and that further includes employs strong oxidizers (e.g., ozone, hydrogen peroxide, nitrous oxide, and oxygen).
  • the water co-reactant functions as a mild oxidizer.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid as a volatizer together with hydrogen peroxide as an oxidizing co-reactant.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid as a volatizer together with a plasma containing oxygen as an oxidizing co-reactant.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching with one or more of pivalic acid, isobutyric acid and propionic acid as a volatizer together with water, oxygen and a water/oxygen mixture as an oxidizing co-reactant that can be performed at low temperatures.
  • etching can proceed at temperatures as low as 110 °C depending on the metal to be etched.
  • etching of copper can proceed at temperatures between about 110 °C to about 300 °C.
  • cobalt etching is slower at about 300 °C and faster at about 335 °C.
  • tungsten etching proceeds slowly at about 335 °C.
  • molybdenum etching proceeds slowly at about 335 °C.
  • FIG. 1 illustrates a conventional art etching process
  • FIG. 2 illustrates a conventional art etching process
  • FIG. 3 illustrates an embodiment of the disclosed and claimed selective etching process.
  • metal-containing complex (or more simply, “complex”) and “precursor” are used interchangeably and refer to metal-containing molecule or compound which can be used to prepare a metal-containing film by a vapor deposition process such as, for example, ALD or CVD.
  • the metal-containing complex may be deposited on, adsorbed to, decomposed on, delivered to, and/or passed over a substrate or surface thereof, as to form a metal-containing film.
  • metal-containing film includes not only an elemental metal film as more fully defined below, but also a film which includes a metal along with one or more elements, for example a metal oxide film, metal nitride film, metal silicide film, a metal carbide film and the like.
  • the terms “elemental metal film” and “pure metal film” are used interchangeably and refer to a film which consists of, or consists essentially of, pure metal.
  • the elemental metal film may include 100% pure metal or the elemental metal film may include 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% pure metal along with one or more impurities.
  • the term “metal film” shall be interpreted to mean an elemental metal film.
  • 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 a pulsed technique, i.e., pulsed CVD.
  • ALD is used to form a metal-containing film by vaporizing and/or passing at least one metal complex disclosed herein over a substrate surface. For conventional ALD processes see, for example, George S. M., el al. J. Phys. Chem., 1996, 100, 13121-13131.
  • ALD may take the form of conventional (i.e., pulsed injection) ALD, liquid injection ALD, photo-assisted ALD, plasma-assisted ALD, or plasma- enhanced ALD.
  • vapor deposition process further includes various vapor deposition techniques described in Chemical Vapour Deposition: Precursors, Processes, and Applications,' Jones, A. C.; Hitchman, M. L., Eds., The Royal Society of Chemistry: Cambridge, 2009; Chapter 1, pp. 1-36.
  • the term “feature” refers to an opening in a substrate which may be defined by one or more sidewalls, a bottom surface, and upper corners. In various aspects, the feature may be a via, a trench, contact, dual damascene, etc.
  • the materials used in the disclosed and claimed processes are preferably substantially free of water.
  • the term “substantially free” as it relates to water means less than 5000 ppm (by weight) measured by proton NMR or Karl Fischer titration, preferably less than 3000 ppm measured by proton NMR or Karl Fischer titration, and more preferably less than 1000 ppm measured by proton NMR or Karl Fischer titration, and most preferably less than 100 ppm measured by proton NMR or Karl Fischer titration.
  • the materials used in the disclosed and claimed processes are also preferably substantially free of metal ions or metals such as, Li + (Li), Na + (Na), K + (K), Mg 2+ (Mg), Ca 2+ (Ca), Al 3+ (Al), Fe 2+ (Fe), Fe 3+ (Fe), Ni 2+ (Ni), Cr’ (Cr), titanium (Ti), vanadium (V), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) or zinc (Zn).
  • metal ions or metals are potentially present from the starting materials/reactor employed to synthesize the precursors.
  • the term “substantially free” as it relates to 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, and more preferably less than 1 ppm, and most preferably 0.1 ppm as measured by ICP-MS (inductively coupled plasma mass spectrometry).
  • alkyl refers to Ci to C20 hydrocarbon groups which can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl and the like) or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl and the like). These alkyl moieties may be substituted or unsubstituted as described below.
  • alkyl refers to such moieties with Ci to C20 carbons. It is understood that for structural reasons linear alkyls start with Ci, while branched alkyls and cyclic alkyls start with C3.
  • moieties derived from alkyls described below such as alkyloxy and perfluoroalkyl, have the same carbon number ranges unless otherwise indicated. If the length of the alkyl group is specified as other than described above, the above-described definition of alkyl still stands with respect to it encompassing all types of alkyl moieties as described above and that the structural consideration with regards to minimum number of carbons for a given type of alkyl group still apply.
  • Halo or halide refers to a halogen, F, Cl, Br or I which is linked by one bond to an organic moiety.
  • the halogen is F.
  • the halogen is Cl.
  • Halogenated alkyl refers to a Ci to C20 alkyl which is fully or partially halogenated.
  • Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which the hydrogens have all been replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoroisopropyl, perfluorocyclohexyl and the like).
  • fluorine e.g., trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoroisopropyl, perfluorocyclohexyl and the like.
  • the materials used in the disclosed and claimed processes are preferably substantially free of organic impurities which are from either starting materials employed during synthesis or byproducts generated during synthesis. Examples include, but not limited to, alkanes, alkenes, alkynes, dienes, ethers, esters, acetates, amines, ketones, amides, aromatic compounds.
  • the term “free of’ organic impurities means 1000 ppm or less as measured by GC, (gas chromatography) preferably 500 ppm or less (by weight) as measured by GC, most preferably 100 ppm or less (by weight) as measured by GC or other analytical method for assay.
  • the precursors preferably have purity of 98 wt. % or higher, more preferably 99 wt. % or higher as measured by GC when used as precursor to deposit the ruthenium-containing films.
  • the disclosed and claimed subject matter relates to processes for the isotropic thermal ALE of metals, including copper, cobalt, molybdenum, and/or tungsten.
  • the processes include, consist essentially of or consist of the steps of:
  • an oxidation that includes exposing the surface of the metal to one or more oxidizing and/or hydroxylating co-reactant (or “oxidizer” or “surface modifier”) to produce an oxidized and/or hydroxylated surface;
  • volatilization that includes exposing the oxidized and/or hydroxylated surface to one or more volatilizing agents (or “volatizers”) to produce a volatile metalorganic species; and
  • the method consists essentially of steps (i), (ii), (iii) and (iv). In a further aspect of this embodiment, the method consists of steps (i), (ii), (iii) and (iv). The steps in the processes can be cycled as many times as needed to remove a desired thickness of metal oxide. In a further aspect, any of the forgoing embodiments can further include, consist essentially of or consist of a step (v) post-treatment may be added to remove impurities remaining on the surface following a desired number of cycles.
  • the disclosed and claimed subject matter relates to a method for the selective thermal atomic layer etching that includes etching cycles that include, consist essentially of or consist of exposing a metal surface to one or more halogen-free organic acid and one or more an oxidizing co-reactant in cycles.
  • a single cycle of the disclosed and claimed method includes, consists essentially of or consists of:
  • Step l n + (Step 2) m
  • Step 1 includes sequentially exposing a metal surface to one or more oxidizing coreactant (Step 1 A) and purging with an inert gas (Step IB); and
  • Step 2 includes sequentially exposing a metal surface to one or more halogen-free organic acid (Step 2A) and purging with an inert gas (Step 2B).
  • n also equals the number of times steps 1A and IB are sequentially performed within in Step 1 and m also equals the number of times steps 2A and 2B are sequentially performed within Step 2.
  • the disclosed and claimed subject matter relates to a thermal atomic layer etching (ALE) process performed in a reactor for selectively etching a metal substrate including the steps of:
  • Step 1 including sequentially performing:
  • Step 1 A including exposing a metal surface to an oxidizing vapor including one or more of water vapor, oxygen, ozone, nitrous oxide, hydrogen peroxide, oxygen plasma, and combinations thereof, and
  • Step IB including purging the oxidizing vapor with an inert gas
  • Step 2 including sequentially performing:
  • Step 2A including exposing the metal surface to one or more halogen-free organic acid volatizer
  • each iteration of Step 1 alternates with an iteration of Step 2 within each cycle.
  • all iterations of Step 1 are begun and completed before the iterations of Step 2 are begun and completed within in each cycle.
  • n is the same as m. In one embodiment, n is different from m.
  • FIG. 3 illustrates an embodiment of the disclosed and claimed selective etching process using water vapor.
  • the disclosed and claimed process can include any number of desired cycles.
  • the number of cycles is from about 20 to about 5000 cycles. In one embodiment, the number of cycles is from about 20 to about 2200 cycles. In one embodiment, the number of cycles is from about 50 to about 5000. In one embodiment, the number of cycles is from about 50 to about 2500. In one embodiment, the number of cycles is from about 50 to about 1500. In one embodiment, the number of cycles is from about 50 to about 1000. In one embodiment, the number of cycles is from about 50 to about 750. In one embodiment, the number of cycles is from about 50 to about 500. In one embodiment, the number of cycles is from about 50 to about 300. In one embodiment, the number of cycles is from about 50 to about 200.
  • the number of cycles is from about 150 to about 4000. In one embodiment, the number of cycles is from about 200 to about 3000. In one embodiment, the number of cycles is from about 250 to about 2500. In one embodiment, the number of cycles is from about 350 to about 2000. In one embodiment, the number of cycles is from about 450 to about 1700. In one embodiment, the number of cycles is from about 500 to about 1500. In one embodiment, the number of cycles is from about 750 to about 1250. In one embodiment, the number of cycles is from about 250 to about 1000. In one embodiment, the number of cycles is from about 500 to about 1000. In one embodiment, the number of cycles is from about 750 to about 1000.
  • the number of cycles is about 50. In one embodiment, the number of cycles is about 100. In one embodiment, the number of cycles is about 125. In one embodiment, the number of cycles is about 150. In one embodiment, the number of cycles is about 175. In one embodiment, the number of cycles is about 200. In one embodiment, the number of cycles is about 250. In one embodiment, the number of cycles is about 300. In one embodiment, the number of cycles is about 350. In one embodiment, the number of cycles is about 400. In one embodiment, the number of cycles is about 450. In one embodiment, the number of cycles is about 500. In one embodiment, the number of cycles is about 750. In one embodiment, the number of cycles is about 1000. In one embodiment, the number of cycles is about 1250.
  • the number of cycles is about 1500. In one embodiment, the number of cycles is about 1750. In one embodiment, the number of cycles is about 2000. In one embodiment, the number of cycles is about 2250. In one embodiment, the number of cycles is about 2500. In one embodiment, the number of cycles is about 2750. In one embodiment, the number of cycles is about 3000. In one embodiment, the number of cycles is about 3250. In one embodiment, the number of cycles is about 3500. In one embodiment, the number of cycles is about 4000. In one embodiment, the number of cycles is about 4500. In one embodiment, the number of cycles is about 5000.
  • the reactor includes a reactor chamber that includes a body and a heatable lid, an outer heater and an inner heater (pedestal).
  • the chamber outer heater is set at from about 100 °C to about 400 °C. In one embodiment, the chamber outer heater is set at about 140 °C. In one embodiment, the chamber outer heater is set at about 160 °C. In one embodiment, the chamber outer heater is set at about 200 °C. In one embodiment, the chamber outer heater is set at about 225 °C. In one embodiment, the chamber outer heater is set at about 250 °C. In one embodiment, the chamber outer heater is set at about 280 °C. In one embodiment, the chamber outer heater is set at about 300 °C. In one embodiment, the chamber outer heater is set at about 325 °C. In one embodiment, the chamber outer heater is set at about 350 °C.
  • the chamber outer heater is set at about 375 °C. In one embodiment, the chamber outer heater is set at about 400 °C. In one embodiment, the reactor chamber includes an outer heater heated to a temperature of about 100 °C to about 300 °C and an inner heater heated to a temperature of about 100 °C to about 350 °C.
  • the chamber lid heater is set from about 100 °C to about 200 °C. In one embodiment, the chamber lid heater is set at about 100 °C. In one embodiment, the chamber lid heater is set at about 130 °C. In one embodiment, the chamber lid heater is set at about 150 °C. In one embodiment, the chamber lid heater is set at about 200 °C.
  • the chamber inner heater is set at from about 100 °C to about 350 °C. In one embodiment, the chamber inner heater is set at about 140 °C. In one embodiment, the chamber inner heater is set at about 150 °C. In one embodiment, the chamber inner heater is set at about 160 °C. In one embodiment, the chamber inner heater is set at about 170 °C. In one embodiment, the chamber inner heater is set at about 180 °C. In one embodiment, the chamber inner heater is set at about 190 °C. In one embodiment, the chamber inner heater is set at about 200 °C. In one embodiment, the chamber inner heater is set at about 225 °C. In one embodiment, the chamber inner heater is set at about 250 °C.
  • the chamber inner heater is set at about 275 °C. In one embodiment, the chamber inner heater is set at about 300 °C. In one embodiment, the chamber inner heater is set at about 325 °C. In one embodiment, the chamber inner heater is set at about 335 °C.
  • the disclosed and claimed process provides selective thermal etching on certain metal substrates.
  • the disclosed and claimed process selectively etches a substrate including one or more of copper, cobalt, molybdenum and tungsten preferentially instead of nickel, platinum, ruthenium, zirconium oxide and/or and SiCh.
  • the disclosed and claimed process selectively etches a substrate including copper.
  • the disclosed and claimed process selectively etches a substrate including cobalt.
  • the disclosed and claimed process selectively etches a substrate including molybdenum.
  • the disclosed and claimed process selectively etches a substrate including tungsten.
  • the disclosed and claim process does not etch or does not substantially etch a substrate including one or more of nickel, platinum, ruthenium, zirconium oxide and/or SiCh.
  • Step 1 Oxidizing Sequence
  • Step 1 includes, consists essentially of or consists of sequentially exposing a metal surface to one or more oxidizing co-reactant (Step 1 A) and purging with an inert gas (step IB).
  • the one or more oxidizing co-reactant is preferably delivered as a vapor
  • Step 1A Oxidizing Co-Reactant Exposure
  • a metal surface is exposed to one or more oxidizing co-reactant.
  • the one or more oxidizing co-reactant is preferably delivered as a vapor (z.e. , an “oxidizing vapor”), such as water vapor, water vapor co-flowed with an oxidizer such as oxygen, ozone, nitrous oxide, nitric oxide, or hydrogen peroxide, or an oxidizing vapor composed of oxygen, ozone, nitric oxide, oxygen plasma or hydrogen peroxide without co-flowed water vapor, for a suitable time period and at a temperature sufficient to oxidize the surface of a metal substrate.
  • an oxidizing vapor such as water vapor, water vapor co-flowed with an oxidizer such as oxygen, ozone, nitrous oxide, nitric oxide, or hydrogen peroxide
  • an oxidizing vapor composed of oxygen, ozone, nitric oxide, oxygen plasma or hydrogen peroxide without co-flowed water vapor
  • the oxidizing vapor includes one or more of water vapor, oxygen, ozone, nitrous oxide, nitric oxide, hydrogen peroxide, and oxygen plasma and combinations thereof.
  • the oxidizing vapor includes water vapor.
  • the oxidizing vapor includes oxygen.
  • the oxidizing vapor includes ozone.
  • the oxidizing vapor includes nitrous oxide.
  • the oxidizing vapor includes oxygen plasma.
  • the oxidizing vapor includes hydrogen peroxide.
  • the oxidizing vapor includes water vapor and one or more of oxygen, ozone, nitrous oxide, hydrogen peroxide, and oxygen plasma. In one aspect of this embodiment, the oxidizing vapor includes water vapor and oxygen. In one aspect of this embodiment, the oxidizing vapor includes water vapor and ozone. In one aspect of this embodiment, the oxidizing vapor includes water vapor and nitrous oxide. In one aspect of this embodiment, the oxidizing vapor includes water vapor and oxygen plasma. In one aspect of this embodiment, the oxidizing vapor includes water vapor and hydrogen peroxide. In one aspect of this embodiment, the oxidizing vapor includes water vapor and two or more of oxygen, ozone, nitrous oxide hydrogen peroxide.
  • the Step 1A oxidizing vapor exposure is from about 0.25 seconds to about 6 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is from about 0.25 seconds to about 2 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is from about 0.5 seconds to about 5 seconds. In one embodiment, the Step 1 A oxidizing vapor exposure is from about 5 seconds to about 15 seconds. In one embodiment, the Step 1 A oxidizing vapor exposure is about 0.25 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 0.5 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 1 second. In one embodiment, the Step 1 A oxidizing vapor exposure is about 2 seconds.
  • the Step 1 A oxidizing vapor exposure is about 4 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 5 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 6 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 7 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 10 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 12 seconds. In one embodiment, the Step 1A oxidizing vapor exposure is about 15 seconds.
  • the oxidizing vapor source in Step 1A is not actively heated and is maintained at an ambient temperature of about 20 °C to about 35 °C. In one embodiment, in Step 1A the oxidizing vapor source is heated to and held at from about 20 °C to about 30 °C. In one embodiment, in Step 1 A the oxidizing vapor source is heated to and held at from about 30 °C to about 35 °C. In one embodiment, in Step 1 A the oxidizing vapor source is heated to and held at about 25 °C. In one embodiment, in Step 1 A the oxidizing vapor source is heated to and held at about 30 °C. In one embodiment, in Step 1 A the oxidizing vapor source is heated to and held at about 35 °C.
  • the water source in Step 1A is chilled to and held at from about 0 °C to about 5 °C. In one embodiment, in Step 1 A the water source is chilled to and held at from about 5 °C to about 10 °C. In one embodiment, in Step 1 A the water source is chilled to and held at from about 10 °C to about 15 °C. In one embodiment, in Step 1A the water source is chilled to and held at from about 15 °C to about 20 °C. In one embodiment, in Step 1 A the water source is chilled to and held at from about 20 °C to about 25 °C. In one embodiment, in Step 1A the water vapor source is heated to and held at from about 20 °C to about 25 °C.
  • the Step 1 A water vapor is heated to and held at from about 25 °C to about 30 °C. In one embodiment, the Step 1A water vapor source is heated to and held at from about 30 °C to about 35 °C. In one embodiment, in Step 1 A the water vapor source is heated to and held at from about 35 °C to about 40 °C. In one embodiment, in Step 1 A the water vapor source is heated to and held at from about 40 °C to about 45 °C.
  • Step 1 A the water vapor source is chilled to and held at about 0 °C. In one embodiment, in Step 1 A the water vapor source is chilled to and held at about 5 °C. In one embodiment, in Step 1A the water vapor source is chilled to and held at about 10 °C. In one embodiment, in Step 1A the water vapor source is chilled to and held at about 15 °C. In one embodiment, in Step 1A the water vapor source is chilled to and held at about 20 °C. In one embodiment, in Step 1A the water vapor source is heated to and held at about 20 °C. In one embodiment, in Step 1A the water vapor source is heated to and held at about 25 °C.
  • Step 1A the water vapor source is heated to and held at about 30 °C. In one embodiment, in Step 1A the water vapor source is heated to and held at about 40 °C. In one embodiment, in Step 1 A the water vapor source is heated to and held at about 45 °C.
  • the water vapor source temperature is held substantially constant. In one embodiment, the water vapor source temperature is varied.
  • Step 1 A the hydrogen peroxide source is chilled to and held at from about 0 °C to about 5 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at from about 5 °C to about 10 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at from about 10 °C to about 15 °C. In one embodiment, in Step 1A the hydrogen peroxide source is chilled to and held at from about 15 °C to about 20 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at from about 20 °C to about 25 °C.
  • Step 1A the hydrogen peroxide source is heated to and held at from about 20 °C to about 25 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is heated to and held at from about 25 °C to about 30 °C. In one embodiment, in Step 1A the hydrogen peroxide source is heated to and held at from about 30 °C to about 40 °C.
  • the hydrogen peroxide source is chilled to and held at about 0 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at about 5 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at about 10 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at about 15 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is chilled to and held at about 20 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is heated to and held at about 20 °C. In one embodiment, in Step 1A the hydrogen peroxide source is heated to and held at about 25 °C. In one embodiment, in Step 1A the hydrogen peroxide source is heated to and held at about 30 °C. In one embodiment, in Step 1 A the hydrogen peroxide source is heated to and held at about 40 °C.
  • the hydrogen peroxide source temperature is held substantially constant. In one embodiment, the hydrogen peroxide source temperature is varied.
  • oxidizing vapor is delivered into the chamber from one port while an inert gas is delivered into the chamber from another port. In one embodiment, the oxidizing vapor is delivered into the chamber from one port while an additional oxidizing gas is delivered into the chamber from another port and an inert gas is delivered into the chamber from a third port. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.1 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 2.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 0.75 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 2.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 25.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 50.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 25.0 Torr to about 50.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 50.0 Torr to about 75.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 75.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 100.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is about 0.1 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.25 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.5 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.75 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 1.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 2.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 3.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is about 4.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 15.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 20.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 50.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 75.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 100.0 Torr.
  • water vapor is delivered into the chamber from one port while an inert gas is delivered into the chamber from another port.
  • the total pressure in the chamber during the water vapor delivery is from about 0.1 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 0.5 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 0.5 Torr to about 2.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 0.5 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 0.5 Torr to about 0.75 Torr.
  • the total pressure in the chamber during the water vapor delivery is from about 1.0 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 1.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 2.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 10.0 Torr to about 25.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 10.0 Torr to about 50.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 25.0 Torr to about 50.0 Torr.
  • the total pressure in the chamber during the water vapor delivery is from about 50.0 Torr to about 75.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 75.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 1.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is from about 10.0 Torr to about 100.0 Torr.
  • the total pressure in the chamber during the water vapor delivery is about 0.1 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 0.25 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 0.5 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 0.75 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 1.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 2.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 3.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 4.0 Torr.
  • the total pressure in the chamber during the water vapor delivery is about 5.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 10.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 15.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 20.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 50.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 75.0 Torr. In one embodiment, the total pressure in the chamber during the water vapor delivery is about 100.0 Torr.
  • water vapor is delivered into the chamber from one port while an additional oxidizing gas is delivered into the chamber from another port to form a mixed or combined oxidizing vapor and an inert gas is delivered into the chamber from a third port.
  • the total pressure in the chamber during the oxidizing vapor delivery is from about 0.1 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 2.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 1.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is from about 0.5 Torr to about 0.75 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 2.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 25.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 50.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is from about 25.0 Torr to about 50.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 50.0 Torr to about 75.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 75.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 1.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is from about 10.0 Torr to about 100.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is about 0.1 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.25 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.5 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 0.75 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 1.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 2.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 3.0 Torr.
  • the total pressure in the chamber during the oxidizing vapor delivery is about 4.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 5.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 10.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 15.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 20.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 50.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 75.0 Torr. In one embodiment, the total pressure in the chamber during the oxidizing vapor delivery is about 100.0 Torr.
  • the additional oxidizing gas includes one or more of oxygen, ozone, nitrous oxide and hydrogen peroxide. In a further aspect of the forgoing embodiments and aspects thereof, the additional oxidizing gas includes oxygen. In a further aspect of the forgoing embodiments and aspects thereof, the additional oxidizing gas includes ozone. In a further aspect of the forgoing embodiments and aspects thereof, the additional oxidizing gas includes nitrous oxide. In a further aspect of the forgoing embodiments and aspects thereof, the additional oxidizing gas includes hydrogen peroxide.
  • the oxidizing vapor is delivered by vapor-draw. In one embodiment, the oxidizing vapor is delivered with the aid of a carrier gas. In one embodiment, the oxidizing vapor is delivered by bubbling an inert gas through water. In one embodiment, the oxidizing vapor is delivered as a gas (i.e., without bubbling through water). In one embodiment, the oxidizing vapor is delivered simultaneously with an additional oxidizing vapor.
  • Step IB Inert Gas Purge
  • any suitable inert purge gas can be used.
  • the purge gas includes argon.
  • the purge gas includes nitrogen.
  • the Step IB purge time is from about 0.5 seconds to about 30 seconds. In one embodiment, the Step IB purge time is from about 1 second to about 5 seconds. In one embodiment, the Step IB purge time is from about 10 seconds to about 30 seconds. In one embodiment, the Step IB purge time is from about 0.5 seconds to about 10 seconds. In one embodiment, the Step IB purge time exposure is from about 1 second to about 7 seconds. In one embodiment, the Step IB purge time exposure is from about 7 seconds to about 10 seconds. In one embodiment, the Step IB purge time exposure is from about 10 seconds to about 20 seconds. In one embodiment, the Step IB purge time exposure is from about 20 seconds to about 30 seconds.
  • the Step IB purge time exposure is about 0.25 seconds. In one embodiment, the Step IB purge time exposure is about 0.5 seconds. In one embodiment, the Step IB purge time exposure is about 1 second. In one embodiment, the Step IB purge time exposure is about 2 seconds. In one embodiment, the Step IB purge time exposure is about 3 seconds. In one embodiment, the Step IB purge time exposure is about 4 seconds. In one embodiment, the Step IB purge time exposure is about 5 seconds. In one embodiment, the Step IB purge time exposure is about 6 seconds. In one embodiment, the Step IB purge time exposure is about 7 seconds. In one embodiment, the Step IB purge time exposure is about 8 seconds. In one embodiment, the Step IB purge time exposure is about 9 seconds.
  • the Step IB purge time exposure is about 10 seconds. In one embodiment, the Step IB purge time exposure is about 12 seconds. In one embodiment, the Step IB purge time exposure is about 15 seconds. In one embodiment, the Step IB purge time exposure is about 17 seconds. In one embodiment, the Step IB purge time exposure is about 20 seconds. In one embodiment, the Step IB purge time exposure is about 25 seconds. In one embodiment, the Step IB purge time exposure is about 30 seconds.
  • the purge gas is flowed at between about 1 seem to about 2000 seem. In one embodiment, the purge gas is flowed at between about 3 seem to about 8 seem. In one embodiment, the purge gas is flowed at between about 100 seem to about 2000 seem. In one embodiment, the purge gas is flowed at between about 50 seem to about 500 seem. In one embodiment, the purge gas is flowed at between about 500 seem to about 2000 seem. In one embodiment, the purge gas is flowed at about 1 seem. In one embodiment, the purge gas is flowed at about 2 seem. In one embodiment, the purge gas is flowed at about 3 seem. In one embodiment, the purge gas is flowed at about 4 seem.
  • the purge gas is flowed at about 5 seem. In one embodiment, the purge gas is flowed at about 6 seem. In one embodiment, the purge gas is flowed at about 7 seem. In one embodiment, the purge gas is flowed at about 8 seem. In one embodiment, the purge gas is flowed at about 9 seem. In one embodiment, the purge gas is flowed at about 10 seem. In one embodiment, the purge gas is flowed at about 9 seem. In one embodiment, the purge gas is flowed at about 10 seem. In one embodiment, the purge gas is flowed at about 50 seem. In one embodiment, the purge gas is flowed at about 100 seem. In one embodiment, the purge gas is flowed at about 200 seem.
  • the purge gas is flowed at about 300 seem. In one embodiment, the purge gas is flowed at about 500 seem. In one embodiment, the purge gas is flowed at about 750 seem. In one embodiment, the purge gas is flowed at about 1000 seem. In one embodiment, the purge gas is flowed at about 1250 seem. In one embodiment, the purge gas is flowed at about 1500 seem. In one embodiment, the purge gas is flowed at about 1750 seem. In one embodiment, the purge gas is flowed at about 2000 seem.
  • Step 2 Volatilizer Exposure Sequence
  • Step 2 includes, consists essentially of or consists of sequentially exposing a modified metal surface to one or more volatilizer (Step 2A) and purging with an inert gas (step 2B).
  • the one or more volatilizer includes, consists essentially of, or consists of a halogen-free organic acid or mixture of halogen-free organic acids.
  • the one or more volatilizer includes one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3 -methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2E)-but-2- enoic acid, (Z)-2-butenoic acid and combinations thereof.
  • the one or more volatilizer includes one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3 -methylbutanoic acid, 3-butenoic acid and combinations thereof.
  • the one or more volatilizer includes one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid and combinations thereof.
  • the one or more volatilizer includes one or more of propionic acid, isobutyric acid, pivalic acid and combinations thereof.
  • the one or more volatilizer includes propionic acid.
  • the one or more volatilizer includes isobutyric acid. In one aspect of this embodiment, the one or more volatilizer includes pivalic acid. In one aspect of this embodiment, the one or more volatilizer includes acetic acid. In one aspect of this embodiment, the one or more volatilizer includes butanoic acid. In one aspect of this embodiment, the one or more volatilizer includes acrylic acid. In one aspect of this embodiment, the one or more volatilizer includes methacrylic acid. In one aspect of this embodiment, the one or more volatilizer includes 2-methylbutanoic acid. In one aspect of this embodiment, the one or more volatilizer includes 3 -methylbutanoic acid.
  • the one or more volatilizer includes 3-butenoic acid. In one aspect of this embodiment, the one or more volatilizer includes cyclopropanecarboxylic acid. In one aspect of this embodiment, the one or more volatilizer includes pentanoic acid. In one aspect of this embodiment, the one or more volatilizer includes (2£)-but-2-enoic acid. In one aspect of this embodiment, the one or more volatilizer includes (Z)-2-butenoic acid. In one aspect of this embodiment, the one or more volatilizer includes a mixture of one or more of propionic acid, isobutyric acid and pivalic acid.
  • the one or more volatilizer includes a mixture of two or more of propionic acid, isobutyric acid and pivalic acid. In one aspect of this embodiment, the one or more volatilizer includes a mixture of halogen-free organic acids including one or more of propionic acid, isobutyric acid and pivalic acid.
  • Step 2A Volatilizer Exposure
  • the Step 2A one or more volatilizer exposure is from about 0.25 seconds to about 15 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is from about 0.25 seconds to about 1 second. In one embodiment, the Step 2 A one or more volatilizer exposure is from about 0.5 seconds to about 2 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is from about 2 seconds to about 15 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 0.25 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 0.5 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 1 second.
  • the Step 2A one or more volatilizer exposure is about 2 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 3 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 4 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 5 seconds. In one embodiment, the Step 2 A one or more volatilizer exposure is about 6 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 8 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 10 seconds. In one embodiment, the Step 2A volatilizer exposure is about 12 seconds. In one embodiment, the Step 2A one or more volatilizer exposure is about 15 seconds.
  • Step 2A the one or more volatilizer is heated to and held at from about 50 °C to about 100 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at from about 55 °C to about 95 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at from about 60 °C to about 90 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at from about 65 °C to about 85 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at from about 70 °C to about 80 °C.
  • Step 2A the one or more volatilizer is heated to and held at about 50 °C. In one embodiment, the Step 2A one or more volatilizer exposure is about 55 °C. In one embodiment, in Step 2 A the one or more volatilizer is heated to and held at about 60 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 65 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 70 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 75 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 80 °C.
  • Step 2A the one or more volatilizer is heated to and held at about 85 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 90 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 95 °C. In one embodiment, in Step 2A the one or more volatilizer is heated to and held at about 100 °C.
  • the one or more volatilizer is delivered by a flow-through mode without the assistance of a carrier gas as discussed below. In another embodiment, the one or more volatilizer is delivered by a flow-through mode with the assistance of a carrier gas as discussed below. [0123] In one embodiment, the one or more volatilizer is delivered and “trapped” in which the reactor chamber is closed and the one or more volatilizer is “trapped” in the reactor. In one aspect of this embodiment, the one or more volatilizer is delivered using carrier gas (e.g., nitrogen or argon) as discussed below. In one aspect of this embodiment, the deposition chamber outlet is closed prior to the delivery of the one or more volatilizer, so as to keep it trapped in the chamber. In one aspect of this embodiment, the reactor outlet is kept closed for a time of approximately 0.1 second to a time of approximately 10 seconds to keep the one or more volatilizer trapped in the reactor in order to maximize its impact before opening the reactor to evacuate the gases.
  • carrier gas e.g., nitrogen
  • the total pressure in the chamber during the one or more volatilizer delivery is from about 0.1 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 0.5 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 0.5 Torr to about 2.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 0.5 Torr to about 1.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 0.5 Torr to about 0.75 Torr.
  • the total pressure in the chamber during the one or more volatilizer delivery is from about 1.0 Torr to about 5.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 1.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 2.0 Torr to about 10.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 10.0 Torr to about 25.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 10.0 Torr to about 50.0 Torr.
  • the total pressure in the chamber during the one or more volatilizer delivery is from about 25.0 Torr to about 50.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 50.0 Torr to about 75.0 Torr. In one embodiment, the total pressure in the chamber during the pivalic acid delivery is from about 75.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 1.0 Torr to about 100.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is from about 10.0 Torr to about 100.0 Torr.
  • the total pressure in the chamber during the one or more volatilizer delivery is about 0.1 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 0.25 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 0.5 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 0.75 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 1.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 2.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 3.0 Torr.
  • the total pressure in the chamber during the one or more volatilizer delivery is about 4.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 5.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 10.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 15.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 20.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 50.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 75.0 Torr. In one embodiment, the total pressure in the chamber during the one or more volatilizer delivery is about 100.0 Torr.
  • any suitable inert carrier gas can be used if desired.
  • the carrier gas includes argon.
  • the carrier gas includes nitrogen.
  • Step 2B Inert Gas Purge
  • any suitable inert purge gas can be used.
  • the purge gas includes argon.
  • the purge gas includes nitrogen.
  • the Step 2B purge time is from about 0.5 seconds to about 75 seconds. In one embodiment, the Step 2B purge time is from about 0.5 seconds to about 10 seconds. In one embodiment, the Step 2B purge time exposure is from about 1 second to about 7 seconds. In one embodiment, the Step 2B purge time exposure is from about 1 second to about 5 seconds. In one embodiment, the Step 2B purge time is from about 10 seconds to about 75 seconds. In one embodiment, the Step 2B purge time exposure is about 0.25 seconds. In one embodiment, the Step 2B purge time exposure is about 0.5 seconds. In one embodiment, the Step 2B purge time exposure is about 1 second. In one embodiment, the Step 2B purge time exposure is about 2 seconds.
  • the Step 2B purge time exposure is about 3 seconds. In one embodiment, the Step 2B purge time exposure is about 4 seconds. In one embodiment, the Step 2B purge time exposure is about 5 seconds. In one embodiment, the Step 2B purge time exposure is about 6 seconds. In one embodiment, the Step 2B purge time exposure is about 7 seconds. In one embodiment, the Step 2B purge time exposure is about 8 seconds. In one embodiment, the Step 2B purge time exposure is about 9 seconds. In one embodiment, the Step 2B purge time exposure is about 10 seconds. In one embodiment, the Step 2B purge time exposure is about 15 seconds. In one embodiment, the Step 2B purge time exposure is about 20 seconds. In one embodiment, the Step 2B purge time exposure is about 25 seconds.
  • the Step 2B purge time exposure is about 30 seconds. In one embodiment, the Step 2B purge time exposure is about 40 seconds. In one embodiment, the Step 2B purge time exposure is about 50 seconds. In one embodiment, the Step 2B purge time exposure is about 60 seconds. In one embodiment, the Step 2B purge time exposure is about 75 seconds.
  • the last purge time before a new cycle begins is extended (i.e., an extended purge).
  • the extended purge time is from about 30 seconds to 60 seconds. In one embodiment, the extended purge time is from about 30 seconds to 45 seconds. In one embodiment, the extended purge time is about 30 seconds. In one embodiment, the extended purge time is about 45 seconds. In one embodiment, the extended purge time is about 60 seconds.
  • the purge gas is flowed at between about 1 seem to about 2000 seem. In one embodiment, the purge gas is flowed at between about 3 seem to about 8 seem. In one embodiment, the purge gas is flowed at between about 100 seem to about 2000 seem. In one embodiment, the purge gas is flowed at between about 50 seem to about 500 seem. In one embodiment, the purge gas is flowed at between about 500 seem to about 2000 seem. In one embodiment, the purge gas is flowed at about 1 seem. In one embodiment, the purge gas is flowed at about 2 seem. In one embodiment, the purge gas is flowed at about 3 seem. In one embodiment, the purge gas is flowed at about 4 seem.
  • the purge gas is flowed at about 5 seem. In one embodiment, the purge gas is flowed at about 6 seem. In one embodiment, the purge gas is flowed at about 7 seem. In one embodiment, the purge gas is flowed at about 8 seem. In one embodiment, the purge gas is flowed at about 9 seem. In one embodiment, the purge gas is flowed at about 10 seem. In one embodiment, the purge gas is flowed at about 9 seem. In one embodiment, the purge gas is flowed at about 10 seem. In one embodiment, the purge gas is flowed at about 50 seem. In one embodiment, the purge gas is flowed at about 100 seem. In one embodiment, the purge gas is flowed at about 200 seem.
  • the purge gas is flowed at about 300 seem. In one embodiment, the purge gas is flowed at about 500 seem. In one embodiment, the purge gas is flowed at about 750 seem. In one embodiment, the purge gas is flowed at about 1000 seem. In one embodiment, the purge gas is flowed at about 1250 seem. In one embodiment, the purge gas is flowed at about 1500 seem. In one embodiment, the purge gas is flowed at about 1750 seem. In one embodiment, the purge gas is flowed at about 2000 seem.
  • the disclosed and claimed subject matter further includes films prepared by the methods described herein.
  • the films etched by the methods described herein have trenches, vias or other topographical features with an aspect ratio of about 0 to about 60.
  • the aspect ratio is about 0 to about 0.5.
  • the aspect ratio is about 0.5 to about 1.
  • the aspect ratio is about 1 to about 50.
  • the aspect ratio is about 1 to about 40.
  • the aspect ratio is about 1 to about 30.
  • the aspect ratio is about 1 to about 20.
  • the aspect ratio is about 1 to about 10.
  • the aspect ratio is about 0.1. In a further aspect of this embodiment, the aspect ratio is about 0.2. In a further aspect of this embodiment, the aspect ratio is about 0.3. In a further aspect of this embodiment, the aspect ratio is about 0.4. In a further aspect of this embodiment, the aspect ratio is about 0.5. In a further aspect of this embodiment, the aspect ratio is about 0.6. In a further aspect of this embodiment, the aspect ratio is about 0.8. In a further aspect of this embodiment, the aspect ratio is about 1. In a further aspect of this embodiment, the aspect ratio is greater than about 1. In a further aspect of this embodiment, the aspect ratio is greater than about 2. In a further aspect of this embodiment, the aspect ratio is greater than about 5.
  • the aspect ratio is greater than about 10. In a further aspect of this embodiment, the aspect ratio is greater than about 15. In a further aspect of this embodiment, the aspect ratio is greater than about 20. In a further aspect of this embodiment, the aspect ratio is greater than about 30. In a further aspect of this embodiment, the aspect ratio is greater than about 40. In a further aspect of this embodiment, the aspect ratio is greater than about 50.
  • the metal includes copper, cobalt, molybdenum and tungsten. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes copper. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes cobalt. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes molybdenum. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes tungsten.
  • the films etched by the methods described herein have a resistivity of between about 1 pQ.cm to about 250 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 1 pQ.cm to about 5 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 3 pQ.cm to about 4 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 5 pQ.cm to about 10 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 10 pQ.cm to about 50 pQ.cm.
  • the films have a resistivity of about 50 pQ.cm to about 100 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 100 pQ.cm to about 250 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 1 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 2 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 3 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 4 pQ.cm.
  • the films have a resistivity of about 5 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 7.5 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 10 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 15 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 20 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 30 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 40 pQ.cm.
  • the films have a resistivity of about 50 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 60 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 80 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 100 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 150 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 200 pQ.cm. In a further aspect of this embodiment, the films have a resistivity of about 250 pQ.cm.
  • the metal includes copper, cobalt, molybdenum and tungsten. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes copper. In a further aspect of the forgoing embodiments and aspects thereof the metal includes cobalt. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes molybdenum. In a further aspect of the forgoing embodiments and aspects thereof, the metal includes tungsten.
  • Another aspect of the disclosed and claimed subject matter is the use of one or more of propionic acid, isobutyric acid, pivalic acid, acetic acid, butanoic acid, acrylic acid, methacrylic acid, 2-methylbutanoic acid, 3 -methylbutanoic acid, 3-butenoic acid, cyclopropanecarboxylic acid, pentanoic acid, (2£)-but-2-enoic acid, (Z)-2-butenoic acid and combinations thereof as halogen-free organic volatalizer together with one or more of water vapor, oxygen, ozone, nitrous oxide, hydrogen peroxide, and oxygen plasma and combinations thereof as oxidizing vapor for selective thermal atomic layer etching of a metal substrate comprising one or more of copper, cobalt, molybdenum and tungsten.
  • Etching Conditions I through XIV and Examples 1 through 18 were performed in a cross flow ALD system capable of accommodating up to 8” diameter wafer sizes.
  • Etching Conditions XV through XVII and Examples 19 through 24 were performed in an ALD system with a funnel lid (detailed below).
  • Pivalic acid, isobutyric acid and propionic acid were obtained from MilliporeSigma.
  • Etching Conditions I One dose of pivalic acid and one dose of water.
  • Etching Conditions II One dose of pivalic acid.
  • Etching Conditions III Three doses of pivalic acid and three doses of water.
  • Etching Conditions IV Three doses of pivalic acid and one dose of water.
  • Etching Conditions V One dose of pivalic acid and three doses of water.
  • Etching Conditions VI Three doses of pivalic acid (at a higher temperature, 85 °C) and three doses of water.
  • Etching Conditions VII Two doses of water.
  • Etching Conditions VIII Three doses of pivalic acid (at a higher temperature, 85 °C) and one dose of water.
  • Etching Conditions IX Three doses of pivalic acid (at a lower temperature, 60 °C; trapped mode; delivered with nitrogen carrier gas) and two doses of water.
  • Etching Conditions X Three doses of pivalic acid (at a lower temperature, 60 °C; trapped mode; delivered with nitrogen carrier gas) and one dose of water.
  • Etching Conditions XI Thermal Treatment (at either 120 °C or 170 °C) without pivalic acid and water.
  • Etching Conditions XII Thermal Treatment (at 120 °C) with water.
  • Etching Conditions XIII Thermal Treatment (at 120 °C) with pivalic acid.
  • Etching Conditions XIV One dose of pivalic acid (at 75 °C; delivered with nitrogen carrier gas) and one dose of water.
  • Etching Conditions XV One dose of pivalic acid only at a lower temperature of pivalic acid (50 °C).
  • Etching Conditions XVI One dose of pivalic acid and one dose of water + oxygen.
  • Etching Conditions XVII One dose of pivalic acid and either one, two, or three doses of water + oxygen.
  • Etching Conditions XVIH One dose of pivalic acid and three doses of hydrogen peroxide.
  • Etching Conditions XIX One dose of isobutyric acid and two or four doses of oxygen.
  • Etching Conditions XX One dose of isobutyric acid and four doses of water + oxygen.
  • Etching Conditions XXI One dose of propionic acid and two or four doses of oxygen.
  • Etching Conditions XXII One dose of propionic acid and two doses of water + oxygen.
  • Example 1 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions I with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 350 cycles with each cycle including one dose of pivalic acid and one dose of water as follows:
  • Example 2 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions II with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 350 cycles.
  • Each etching cycle included:
  • Example 3 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions I with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 500 cycles with each cycle including one dose of pivalic acid and one dose of water as follows:
  • ALE was performed under Etching Conditions III with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 500 cycles with each cycle including three doses of pivalic acid and three doses of water as follows:
  • Example 5 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions III with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including three doses of pivalic acid and three doses of water as follows:
  • ALE was performed under Etching Conditions IV with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including three doses of pivalic acid and one dose of water as follows:
  • Example 7 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions IV with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including one dose of pivalic acid and three doses of water as follows:
  • Example 8 Series of Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions VI with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of between 60-1000 cycles with each cycle including three doses of pivalic acid (at an elevated temperature of 85 °C) and three doses of water as follows:
  • ALE was performed under Etching Conditions IV with the process chamber outer heater set at 300 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including three doses of pivalic acid and one dose of water as follows:
  • Example 10 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions III with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including three doses of pivalic acid (with differing pre-heated temperatures) and three doses of water as follows:
  • Example 11 Cobalt Heat-Treatment under Standard Conditions
  • ALE was performed under Etching Conditions VII with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including two doses of water as follows:
  • Example 12 Tungsten, Copper, Cobalt, Polished Molybdenum and Non-Polished Molybdenum ALE Under Standard Conditions
  • ALE was performed under Etching Conditions VIII with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 1,000 cycles with each cycle including three doses of pivalic acid (pre-heated to 85 °C) and one dose of water as follows:
  • Example 13 Tungsten, Copper, Cobalt, Polished Molybdenum and Non-Polished Molybdenum ALE Under Standard Conditions
  • ALE was performed under Etching Conditions IX with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250 cycles with each cycle including three doses of pivalic acid (pre-heated to 60 °C, used in a trapped mode and delivered with nitrogen carrier gas) and two doses of water as follows:
  • Example 14 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions X with the process chamber outer heater set at 280 °C and the process chamber inner heater set at 335 °C over the course of 250, 175, 320, 350 or 700 cycles with each cycle including three doses of pivalic acid (pre-heated to 60 °C, used in a trapped mode and delivered with nitrogen carrier gas) and one dose of water as follows:
  • the RMS of the copper samples for this example before any etching treatment was 0.73 nm (roughness) as measured by AFM.
  • Table 2 also shows that the copper films etched at 200 °C, 180 °C, and 160 °C became insulating while the copper films etched at temperatures equal to or lower than 140 °C remained electrically conducting.
  • Example 15 Copper Heat-Treated Under Standard Conditions
  • ALE was performed under Etching Conditions XI with the process chamber outer heater sand the process chamber inner heater each set at the same temperature (either 120 °C or 170 °C).
  • the copper sample was heated to 3.5 hours at 120 °C. After this treatment, extremely few pinholes, and no tall island formation were observed, but the surface morphology became rougher; the copper film had an RMS of 1.49 nm (roughness) as measured by AFM. No copper was etched.
  • ALE was performed under Etching Conditions XII with the process chamber outer heater set at 120 °C and the process chamber inner heater set at 120 °C over the course of 350 cycles with each cycle including one dose of water as follows: (a) a 0.5-second exposure of water vapor, H2O (delivered by vapor-draw, while held at a temperature slightly higher than room temperature (about 30 °C), which resulted in a pressure spike of 0.650-0.700 Torr); and
  • ALE was performed under Etching Conditions XII with the process chamber outer heater set at 120 °C and the process chamber inner heater set at 120 °C over the course of 350 cycles with each cycle including one dose of pivalic acid as follows:
  • the copper film had an RMS of 1.54 nm (roughness) as measured by AFM - smoother than a film exposed to pulses of water alone. Between 8 A and 24 A of copper was etched.
  • ALE was performed under Etching Conditions XIV with the process chamber outer heater set at 140 °C and the process chamber inner heater set at 140 °C over the course of 700, 1750, or 3000 cycles with each cycle including one dose of pivalic acid (pre-heated at 75 °C) and one dose of water as follows:
  • the RMS of the copper samples, before any etching treatment, was 0.73 nm (roughness) as measured by AFM.
  • the normal temperature of pivalic acid in Etching Condition XV is 50 °C.
  • the normal temperature of pivalic acid in Etching Condition XVI through XVH is 60 °C.
  • the pedestal was heated to a temperature 25 degrees C higher than the intended sample temperature to accommodate for a temperature gradient across the carrier wafer.
  • argon purge flows of 140 seem, 140 seem, and 200 seem were continuously run to protect sensitive interior parts of the chamber.
  • ALE was performed under Etching Conditions XV with the process chamber pedestal heater set at 225 °C (corresponding to an estimated sample temperature of 200 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of pivalic acid (pre-heated at 50 °C) as follows:
  • the RMS roughness of the copper sample before any etching treatment was 1.3 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.3 pQ.cm prior to etch.
  • Example 20 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVI with the process chamber pedestal heater set at 165 °C, 245 °C, or 325 °C (corresponding to an estimated sample temperature of 140 °C, 220 °C, or 300 °C) and the process chamber lid heaters set at 130 °C over the course of 200 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and one dose of water co-flowed with oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 1.3 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.3 pQ.cm prior to etch.
  • Example 21 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVI with the process chamber pedestal heater set at 195 °C (corresponding to an estimated sample temperature of 170 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and one dose of water co-flowed with oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 1.3 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.3 pQ.cm prior to etch.
  • ALE was performed under Etching Conditions XVII with the process chamber pedestal heater set at 195 °C (corresponding to an estimated sample temperature of 170 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and one, two, or three doses of water coflowed with oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 1.3 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.3 pQ.cm prior to etch.
  • step (a) After 100 cycles with one dose of 800 seem O2 per cycle in step (a), 8-12 A of copper was etched, the film resistivity was 3.7 pQ.cm post-etch.
  • step (a) After 100 cycles with one dose of H2O vapor + 800 seem O2 per cycle in step (a), 12-16 A of copper was etched, the film resistivity was 3.5 pQ.cm post-etch. Pinholes could be detected, but no tall islands of crystalline copper could be detected. The roughness of the copper film post-etch was 1.6 nm.
  • step (a) After 100 cycles with two doses of H2O vapor + 800 seem O2 per cycle in step (a), 13- 17 A of copper was etched, the film resistivity was 3.5 pQ.cm post-etch.
  • step (a) After 100 cycles with three doses of H2O vapor + 800 seem O2 per cycle in step (a), 13-17 A of copper was etched, the film resistivity was 3.5 pQ.cm post-etch.
  • Example 23 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVI with the process chamber pedestal heater set at 195 °C (corresponding to an estimated sample temperature of 170 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and one dose of water co-flowed with 800 seem oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 1.3 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.3 pQ.cm prior to etch.
  • Example 24 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVII with the process chamber pedestal heater set at 195 °C (corresponding to an estimated sample temperature of 170 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and two doses of water co-flowed with oxygen as follows:
  • the copper films prior to etch, had been thinned by chemicalmechanical planarization from the original as-received thickness of about 500 A to a thickness of about 400 A.
  • the RMS roughness of the copper samples before any etching treatment was 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, and some sparse particles with a width of approx. 40 nm could be detected prior to etch. No tall islands of copper could be detected prior to etch.
  • the typical resistivity across the test substrate surface was 3.4-3.5 pQ.cm prior to etch.
  • Example 25 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVIII with the process chamber pedestal heater set at 165 °C, 195 °C, or 225 °C (corresponding to an estimated sample temperature of 140 °C, 170 °C, or 200 °C) and the process chamber lid heaters set at 130 °C over the course of 200 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and three doses of hydrogen peroxide as follows:
  • the RMS roughness of the copper samples before any etching treatment was approximately 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.7 pQ.cm prior to etch.
  • Example 26 Cobalt ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XVIII with the process chamber pedestal heater set at 375 °C (corresponding to an estimated sample temperature of 350 °C) and the process chamber lid heaters set at 130 °C over the course of 180 cycles with each cycle including one dose of pivalic acid (pre-heated at 60 °C) and three doses of hydrogen peroxide as follows:
  • the RMS roughness of an example cobalt sample before any etching treatment was 0.5 nm as measured by AFM. A grainy surface could be detected, but no tall islands of crystalline cobalt could be detected on the cobalt samples before any etching treatment.
  • the thickness of the cobalt on the sample was 190 A prior to etch.
  • the resistivity across the test substrate surface was 24.8 pQ.cm prior to etch.
  • ALE was performed under Etching Conditions XIX with the process chamber pedestal heater set at 165 °C (corresponding to an estimated sample temperature of 140 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of isobutyric acid (pre-heated at 50 °C) and two or four doses of oxygen gas as follows:
  • the RMS roughness of the copper samples before any etching treatment was 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.7 pQ.cm prior to etch.
  • Example 28 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XX with the process chamber pedestal heater set at 165 °C (corresponding to an estimated sample temperature of 140 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of isobutyric acid (pre-heated at 50 °C) and four doses of water co-flowed with oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.7 pQ.cm prior to etch.
  • ALE was performed under Etching Conditions XXI with the process chamber pedestal heater set at 165 °C (corresponding to an estimated sample temperature of 140 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of propionic acid (pre-heated at 40 °C) and two or four doses of oxygen gas as follows:
  • the RMS roughness of the copper samples before any etching treatment was 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.7 pQ.cm prior to etch.
  • Example 30 Copper ALE Under Standard Conditions
  • ALE was performed under Etching Conditions XXH with the process chamber pedestal heater set at 165 °C (corresponding to an estimated sample temperature of 140 °C) and the process chamber lid heaters set at 130 °C over the course of 100 cycles with each cycle including one dose of propionic acid (pre-heated at 40 °C) and two doses of water co-flowed with oxygen as follows:
  • the RMS roughness of the copper samples before any etching treatment was 0.7 nm (roughness) as measured by AFM. Pinholes could be detected, but no tall islands of crystalline copper could be detected on the copper samples before any etching treatment.
  • the typical resistivity across the test substrate surface was 3.7 pQ.cm prior to etch.
  • metals like Cu, Co, Mo, and W can be etched in the temperature range of about 100 °C to less than 400 °C.
  • a halogen-free organic acid alone may induce some, but limited, etching. This may be attributed to the removal of a native oxide layer on the metal surface.
  • Etching of copper at temperatures at or below 200 °C is demonstrated by cycling pivalic acid, isobutyric acid, or propionic acid with an oxidant.
  • the oxidant may be water, oxygen, water coflowed with oxygen, or a different oxidizing and hydroxylating agent such as hydrogen peroxide.
  • the oxidant may be chosen to modify the etch behavior, such as to improve etch selectivity. After etching, the films are only slightly rougher than before etch, and the film resistivity is similar the resistivity before etch.
  • Cycling pivalic acid, isobutyric acid, or propionic acid with water, oxygen, water coflowed with oxygen, or hydrogen peroxide has been demonstrated as effective vapor-phase etch processes for metals.

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