WO2010115734A1 - Process for the manufacture of etched items - Google Patents

Process for the manufacture of etched items Download PDF

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Publication number
WO2010115734A1
WO2010115734A1 PCT/EP2010/054024 EP2010054024W WO2010115734A1 WO 2010115734 A1 WO2010115734 A1 WO 2010115734A1 EP 2010054024 W EP2010054024 W EP 2010054024W WO 2010115734 A1 WO2010115734 A1 WO 2010115734A1
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WO
WIPO (PCT)
Prior art keywords
ccl
chcl
group
hydrochlorofluoroalkene
plasma
Prior art date
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PCT/EP2010/054024
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French (fr)
Inventor
Marcello Riva
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Solvay Fluor Gmbh
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Publication date
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Publication of WO2010115734A1 publication Critical patent/WO2010115734A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
    • H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases

Definitions

  • the invention concerns a process for the preparation of etched items, e.g. semiconductors, solar cells, and flat panels.
  • etching etching the material to be etched is silicon, silicon oxide, silicon nitride, or low-k dielectrics, for example, FSG (fluorosilicate glass), or C-doped silicon dioxide, and nitrides of titanium, zirconium and tantalum, shortly TiN, ZrN and TaN (sometimes denoted asTaN x ).
  • a preferred method of etching the items is performed using plasma in the presence of an etchant.
  • WO 97/24750 discloses etching of silicon dioxide using unsaturated fluorocarbon gases of formula C n F 2n , especially C 2 F 4 and C 3 F 6 .
  • US 2002/0045353 discloses the use of partially or perfluorinated olefmes as etching agent in the manufacture of semiconductors.
  • US 4581101 discloses the use of partially or perhalogenated fluorine- substituted ethers as dry etching agent. If desired, saturated and unsaturated (hydro)halocarbons can be used as co-etchant.
  • US 4,920,071 discloses semiconductor devices containing barrier layers which are intended to prevent silicon transport from a doped silicon junction to a refractory metal contact.
  • US 5,668,053 discloses a multilayer semiconductor device.
  • One of the layers is a barrier layer made of TiN, TaN or ZrN.
  • One process step concerns the partial removal of the barrier layer using oxygen and a fluorocarbon gas according to the dry etching technique. The manufacture and purpose of TaN layers is described in detail in
  • US-A 6,508,948 discloses a method for etching features into a substrate by removing substrate material from selected areas.
  • a patterned mask is provided and the item is placed in a plasma chamber.
  • Halogenated heterocyclic hydrocarbons for example, perfluoropyridine, are introduced into the chamber, and etching is started.
  • Additional etching agents e.g. CHF 3 , C 3 F 6 or C 4 F 6 or carrier gases, e.g. nitrogen or argon, can be added.
  • the process can be applied to perform micro fabrication of semi-conductor-based logic, memory and optoelectronic devices and micromechanical systems using anisotropic etching.
  • WO 2008/001844 describes a process for the purification of hexafluoropropylene which in high-purity form, is said to be useful as cleaning gas for removing deposits in a semiconductor manufacturing apparatus or a liquid crystal manufacturing apparatus.
  • CH 2 CClF is said to be present as an impurity. It does not seem to be present in table 1 of said WO publication.
  • WO 2009/089511 discloses the use of HFCO-1233zd as cleaning agent to remove photoresist from articles. It performs its cleaning function as a solvent, e.g. as solvent in a critical state.
  • Problem of the present invention is to provide useful etching agents, especially for etching layers of nitrides, borides and carbides of refractory metals, and for etching of nitrides, borides and carbides of refractory metals which - often in the form of layers - are present as deposits or contaminants in plasma chambers.
  • the invention provides a process for producing an etched item including at least one step of etching the item with an etching agent in a plasma chamber, or for cleaning a plasma chamber containing contaminations or deposits comprising a step of introducing the etching agent into the plasma chamber, starting a direct or remote plasma, terminating the plasma and removing gaseous constituents from the chamber wherein the etching of the item is performed in the presence of at least one etching agent selected from the group consisting of aliphatic C2 to ClO hydrochlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom.
  • the C2 to ClO hydrochlorofluoroalkene etching agent is present in a substantial amount; processes which contain C2 to ClO hydrochlorofluoroalkenes as impurities are not included in this invention.
  • the term "substantial amount" means that the C2 to ClO hydro chlorofluoroalkene etching agent constitutes at least 10 % by weight of the sum of all etching agents applied. Fluorinated compounds which are applicable as etchant, e.g.
  • saturated perfluoroalkanes or saturated hydrofluoroalkanes, unsaturated perfluoroalkenes or perfluoroalkadienes or other unsaturated hydrofluoroalkenes, hydrofluoroalkadienes, or a polymerizing gas, e.g. difluoromethane, are the preferred balance to 100 % by weight.
  • the C2 to ClO etching agent constitutes equal to or more than 50 % by weight of the sum of all etching agents applied. Most preferably, it constitutes equal to or more than 90 % by weight of all etching agents applied. Especially preferably, it constitutes about 100 % by weight of all etching agents applied. In this embodiment, it may include undesired impurities, e.g. up to an amount of 1 % by weight.
  • the hydro chlorofluoroalkenes can be applied diluted by argon or other gases. These gases are not considered in these calculations.
  • the present invention provides for a process for producing an etched item including at least one step of etching the item wherein the etching of the item is performed in the presence of at least one aliphatic C2 to ClO hydro chlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom.
  • an item includes the singular and the plural, especially one item or a plurality of items, e.g. 2, 3, 4, 5 or more items. If only one item or a plurality of items are etched depends on the capacity of the used plasma chamber. If multiple items shall be etched simultaneously, a respective plasma chamber must be applied.
  • hydro chlorofluoroalkene in the present invention includes the singular and the plural, i.e. "hydrochlorofluoroalkene” denotes a single compound or a mixture of 2 or more hydrochlorofluoroalkenes.
  • hydro chlorofluoroalkenes denotes compounds which consist of chlorine, fluorine, hydrogen and carbon.
  • hydrofluoroalkenes includes compounds which have one, two or more C-C double bonds.
  • the hydro chlorofluoroalkenes can be linear or branched.
  • the hydrochlorofluoroalkenes have at least 2 carbon atoms.
  • Preferred hydro chlorofluoroalkenes have equal to or less than 10 carbon atoms. Very preferably, they have equal to 8 or less than 8 carbon atoms. Especially preferably, they have equal to or less than 6 carbon atoms. Very preferably, they have 2 to 6 carbon atoms. Most preferably, they have 3 to 6 carbon atoms.
  • Preferred hydrochlorofluoroalkenes have 1 to 4 chlorine atoms. Very preferably, they have 1 to 3 chlorine atoms, more preferably, 1 or 2 chlorine atoms. 1 chlorine atom is especially preferred.
  • Preferred hydrochlorofluoroalkenes have at least 2 fluorine atoms.
  • hydrochlorofluoroalkenes are those of the general formula (I)
  • CF 2 CHCl
  • CF 2 CHCl
  • CF 3 CH 2 CCl CH 2
  • CF 3 CH CClCH 3
  • CF 3 -CCI CH-CCIFCH 3 (E) and (Z)
  • CF 3 -CC1 CH-CHC1F (E) and (Z)
  • CF 3 -CCI CH-CCIF-CF 3 (E) and (Z)
  • CF 3 -CCl CH 2
  • CF 3 -CH CCl-CF 3 (E) and (Z)
  • CF 3 -CCIF-CH CCI-CH 2 -CF 3
  • CF 3 -CCIF-CH 2 -CCI CH-CF 3 ,
  • CF 3 -CH CCl-CH 3 (E) and (Z)
  • CF 3 -CH 2 -CCl CH 2
  • CF 3 -CH CHCl (E) and (Z)
  • CHCI CCl-CH 2 -CF 3 (E) and (Z)
  • CH 2 Cl-CCl CH-CF 3 (E) and (Z)
  • CCIF CCl-CH 2 -CF 3 (E) and (Z)
  • CH 2 Cl-CCl CH-CF 3 (E) and (Z)
  • CHCI CCI-CHCI-CF 3 (E) and (Z)
  • CH 2 C1-CC1 CC1-CF 3 (E) and (Z)
  • CF 3 -CCl CH- CF 3 (E) and (Z)
  • CH 2 CCI-CHCl-CF 3
  • CHCIF-CCI CCI-CF 3 (E) and (Z)
  • CC1F CC1-CHC1-CF 3 (E) and (Z)
  • CH 2 CI-CCI CCI-CF 3 (E) and (Z)
  • CF 3 -CCl CH-CF 3 (E) and (Z)
  • CCIF CCI-CHCI-CF 3 (E) and (Z)
  • CHC1F-CC1 CC1-CF 3 (E) and (Z)
  • hydrofluoroalkenes are known compounds or can be manufactured from known hydrochlorofluoroalkanes by dehydrochlorination or by dehydrofluorination.
  • the hydrochlorofluoroalkane starting material can be prepared by incomplete fluorination of the respective hydrochloroalkanes.
  • the starting compounds may be incompletely fluorinated side products in fluorination reactions.
  • the starting compounds can also be prepared by chlorine- fluorine exchange reactions in hydrochlorofluoroalkanes which have at least one chlorine atom more and at least one fluorine atom less than the desired fluorination product.
  • the starting compounds can also be prepared by addition of HCl to respective hydrofluoroalkenes or hydrochlorofluoroalkenes.
  • the synthesis of the starting compounds is well known in the art.
  • CH 3 -CCIF-CCIF-CF 3 ⁇ CH 2 CCI-CClF-CF 3
  • CF 3 -CH 2 -CClF-CH 3 is, for example, a side product if pentachlorobutane is fluorinated. This compound and other chlorofluorobutanes are mentioned, for example, in US 5,739,406 and US 7,074,434.
  • hydrochlorofluoroalkenes Another method to prepare hydrochlorofluoroalkenes is to react hydrochlorofluoroalkanes with caustic solutions (e.g. potassium or sodium hydroxide, dissolved in water) to dehydrofluorinate or to dehydrochlorinate them to form hydrochlorofluoroalkenes.
  • caustic solutions e.g. potassium or sodium hydroxide, dissolved in water
  • hydrochlorofluoroalkene or mixtures thereof can be applied for those purposes in etching processes for which halogenated hydrocarbons are generally used.
  • etch dielectric materials for example, silicon dioxide, silicon nitride, low and ultra low-k dielectrics like FSG, carbon doped dielectrics and similar material. They can also be used in silicon oxide etching, in the etching of oxide glasses, e.g. borophosphosilicate glass, or oxide materials, optionally doped by e.g. fluorine (fluorosilicate glass, "FSG") or carbon (e.g. Black Diamond® of Applied Materials), so-called "low-k dielectrics", and “ultra low-k dielectrics", which are principally used for electrically insulating layers.
  • oxide glasses e.g. borophosphosilicate glass
  • oxide materials optionally doped by e.g. fluorine (fluorosilicate glass, "FSG") or carbon (e.g. Black Diamond® of Applied Materials), so-called “low-k dielectrics", and “ultra low-k dielectrics”, which are principally used for electrically insulating layers.
  • FSG flu
  • the hydrochlorofluoroalkenes are very suitable in processes including one or more steps of etching layers of the nitrides, borides or carbides of refractory metals ; such layers are often used to avoid diffusion of dopants or as etch stoppers.
  • the etching of layers of refractory metal nitrides are especially preferred, still more preferably layers containing the nitrides of titanium, zirconium and tantalum, shortly TiN, ZrN and TaN x Such layers often are used as barrier layers.
  • the etching of layers containing the nitrides of titanium, zirconium and tantalum is the preferred field of application.
  • the conditions during etching correspond to those usually applied.
  • direct plasma or indirect plasma can be applied.
  • the etch process can be performed in a high-density plasma, such as an inductively coupled reactor, or a low-density plasma, such as a capacitively coupled reactor which is preferred.
  • the pressure in the plasma chamber is equal to or below 150 Pa.
  • the pressure is from 1 to 120 Pa.
  • the hydrochlorofluoroalkenes are applied together with argon, xenon, nitrogen and/or helium, optionally in the presence of hydrogen. If desired, when used for etching, they can be applied together with fluorinated compounds applicable as etchant, e.g.
  • a polymerizing gas may be added, e.g. difluoromethane.
  • the hydrochlorofluoroalkene is introduced into the plasma reactor, diluted with argon.
  • Mixture of xenon (Xe) and argon (Ar) may be applied to tune the relative selectivity of the etchant chemistry between the dielectrics and the barrier layer, enhancing the selectivity.
  • hydrochlorofluoroalkenes can also be applied in processes in which a hard mask must be etched.
  • the C2 to ClO hydrochlorofluoroalkenes described in detail above are also applicable in another aspect of the present invention, namely chamber cleaning processes.
  • the preferred embodiments described in view of etching, especially the preferred chloro fluoroalkenes are preferably applied in this aspect of the invention, too.
  • residues or deposits form on the walls and construction parts of the plasma reactor. It is possible to remove these residues or deposits by introducing a hydrochlorofluoroalkene into the plasma chamber and applying direct or remote plasma.
  • the hydrochlorofluoroalkene serves as etching agent or, in other words, purifying agent.
  • residues and deposits of metals or metal compounds e.g.
  • the oxides, nitrides, carbides or borides can be removed.
  • metal preferably denotes silicon and refractory metals, especially titanium, tantalum and zirconium.
  • the borides, carbides and especially the nitrides of titanium, tantalum and zirconium can be removed.
  • purifying agent has the same meaning as "etching agent”.
  • the removal of gaseous constituents can be supported by passing clean inert gas, for example nitrogen, through the chamber.
  • a composition of matter which comprises or consists of at least two components, a hydrochlorofluoroalkene and a gas.
  • the advantage of the hydrochlorofluoroalkenes of the present invention is the high etching speed.
  • They can be applied in the manufacture of items in the field of electronics, e.g. microelectronic devices, superconductors, and the manufacture of flat panels and solar cells. They can be applied as etching agent for treating the items and as etching gas for cleaning apparatus used for the manufacture of these items.
  • compositions of matter namely mixtures containing or consisting of at least one hydrochlorofluoroalkene and of at least one gas selected from the group consisting of nitrogen, helium, xenon, and argon.
  • the mixture preferably contains the hydrochlorofluoroalkene and any combinations of two or more of nitrogen and the noble gases mentioned above.
  • additive gases for example one or more hydrogen sources, e.g. hydrocarbons, preferably elemental hydrogen (which serves as fluorine trap in etching) or other passivating gases may be present.
  • Mixtures containing or consisting of xenon, argon, and at least one hydrochlorofluoroalkene, and optionally additionally nitrogen, are especially preferred.
  • one embodiment concerns mixtures of at least one hydrochlorofluoroalkene and at least one gas selected from the group consisting of nitrogen, helium, xenon, argon, and any combinations of two or more thereof, and optionally at least one hydrogen source, preferably hydrogen.
  • Mixtures containing or consisting of CF 3 -CH 2 -CCl CH 2 ,
  • the content of the hydrochlorofluoroalkene or the sum of the hydrochlorofluoroalkenes if two or more of them are contained, is preferably equal to or greater than 10 % by volume. Preferably, it is equal to or lower than 50 % by volume. Preferably, nitrogen, helium, xenon, and/or argon are the balance to 100 % by volume. If hydrogen is present, it is preferably comprised from 2 to 10 % by volume. The percentages given here refer to the gaseous state.
  • the mixtures according to the invention are preferably in the condensed state, especially in the form of a liquid. They can be manufactured, for example, by introducing the respective volumes of gaseous constituents into a storage tank and condensing them therein, or by condensing respective volumes of the constituents and supplying them in liquefied form into the storage tank.
  • EXAMPLE 1 Gas mixtures especially suitable for TaN, ZrN and TiN etching Etching gas mixtures are prepared by condensing the respective unsaturated C4 compound, argon and optionally nitrogen and hydrogen, respectively, in a pressure-resistant storage tank.
  • Chlorotrifluorobutenes can be prepared by dehydrofluorination as described in PCT/EP EP2009/065565 using high-surface aluminium fluoride catalysts as described in EP 1666411 Al and EP 1440939 Al. from chlorotetrafluorobutane, a side product from the preparation of pentafluorobutane from pentachlorobutane and HF over tin halide catalysts. The resulting isomers are separated by distillation.
  • a microelectronic part containing a TaN x barrier layer is manufactured as described in WO 2006/113955.
  • Etching can be performed in an Inductive Coupled Plasma Source (ICP) etch reactor or in a Capacitively Coupled Plasma Source (CCP) reactor which is available from Applied Materials.
  • ICP Inductive Coupled Plasma Source
  • CCP Capacitively Coupled Plasma Source
  • a plasma chamber is contaminated with deposits of TaN layers.
  • the gaseous reaction products can be removed from the chamber by applying a vacuum.
  • a plasma chamber is contaminated with deposits of TaN layers.
  • a plasma chamber is contaminated with deposits of TaN layers.
  • the gaseous reaction products can be removed from the chamber by applying a vacuum.
  • EXAMPLE 6 Cleaning of a plasma chamber to remove TiN deposits using
  • a plasma chamber is contaminated with deposits of TiN layers.
  • EXAMPLE 7 Cleaning of a plasma chamber using C 4 H 4 ClF 3 Chlorotetrafluorobutane is subjected to a dehydrofluorination reaction by passing it at a temperature of about 300 0 C over a high-surface aluminium fluoride catalyst produced as described in EP 1666411 Al.
  • the resulting mixture containing the isomers is mixed with argon so that the resulting etching mixture contains 70 % by volume of argon.
  • the etching mixture is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber.
  • the gaseous reaction products can be removed from the chamber by applying a vacuum.

Abstract

Hydrochlorofluoroalkenes can be used as etching gases for the production of etched items, for example, of semiconductors, flat panels, or solar cells. Preferred compounds are CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2 which can be obtained from hydro chlorofluoroalkanes by thermal, base-induced or catalytic dehydrofluorination. The hydrochlorofluoroalkenes are preferably applied together with nitrogen, argon and/or xenon. The compounds have the especial advantage that they allow fast etching of nitrides, carbides and borides of refractory metals. Nitrides of Ta, Zr and Ti are used for example as barrier layers in microelectronic devices.

Description

Process for the manufacture of etched items
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to European Patent Application No. 09157073.9 filed April 01, 2009 this application being incorporated herein by reference in their entirety for all purposes. DESCRIPTION
The invention concerns a process for the preparation of etched items, e.g. semiconductors, solar cells, and flat panels.
During the manufacture of electronic devices, for example, semiconductor logis and memories, for example, Dynamic Random Access Memories (DRAMs) or Central Processing Units (CPUs), logics or capacitors, often one or more steps of etching must be performed. The material to be etched is silicon, silicon oxide, silicon nitride, or low-k dielectrics, for example, FSG (fluorosilicate glass), or C-doped silicon dioxide, and nitrides of titanium, zirconium and tantalum, shortly TiN, ZrN and TaN (sometimes denoted asTaNx). A preferred method of etching the items is performed using plasma in the presence of an etchant.
WO 97/24750 discloses etching of silicon dioxide using unsaturated fluorocarbon gases of formula CnF2n, especially C2F4 and C3F6.
US 2002/0045353 discloses the use of partially or perfluorinated olefmes as etching agent in the manufacture of semiconductors. US 4581101 discloses the use of partially or perhalogenated fluorine- substituted ethers as dry etching agent. If desired, saturated and unsaturated (hydro)halocarbons can be used as co-etchant.
US 4,920,071 discloses semiconductor devices containing barrier layers which are intended to prevent silicon transport from a doped silicon junction to a refractory metal contact.
US 5,668,053 discloses a multilayer semiconductor device. One of the layers is a barrier layer made of TiN, TaN or ZrN. One process step concerns the partial removal of the barrier layer using oxygen and a fluorocarbon gas according to the dry etching technique. The manufacture and purpose of TaN layers is described in detail in
WO06113955. In that document, the material forming the layer is denoted as "TaNx" with x being 0.5 to 1.67. This indicates that the terms "TaN" and, analogously, "TiN", "ZrN", do not refer to exactly stoechiometric compounds but rather indicate a layer which contains the metal cations and nitrogen anions in an atomic ratio which is more or less close to the stoechiometric one.
US-A 6,508,948 discloses a method for etching features into a substrate by removing substrate material from selected areas. A patterned mask is provided and the item is placed in a plasma chamber. Halogenated heterocyclic hydrocarbons, for example, perfluoropyridine, are introduced into the chamber, and etching is started. Additional etching agents, e.g. CHF3, C3F6 or C4F6 or carrier gases, e.g. nitrogen or argon, can be added. The process can be applied to perform micro fabrication of semi-conductor-based logic, memory and optoelectronic devices and micromechanical systems using anisotropic etching.
WO 2008/001844 describes a process for the purification of hexafluoropropylene which in high-purity form, is said to be useful as cleaning gas for removing deposits in a semiconductor manufacturing apparatus or a liquid crystal manufacturing apparatus. Among others, CH2=CClF is said to be present as an impurity. It does not seem to be present in table 1 of said WO publication.
WO 2009/089511 discloses the use of HFCO-1233zd as cleaning agent to remove photoresist from articles. It performs its cleaning function as a solvent, e.g. as solvent in a critical state.
Problem of the present invention is to provide useful etching agents, especially for etching layers of nitrides, borides and carbides of refractory metals, and for etching of nitrides, borides and carbides of refractory metals which - often in the form of layers - are present as deposits or contaminants in plasma chambers.
The invention provides a process for producing an etched item including at least one step of etching the item with an etching agent in a plasma chamber, or for cleaning a plasma chamber containing contaminations or deposits comprising a step of introducing the etching agent into the plasma chamber, starting a direct or remote plasma, terminating the plasma and removing gaseous constituents from the chamber wherein the etching of the item is performed in the presence of at least one etching agent selected from the group consisting of aliphatic C2 to ClO hydrochlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom. The C2 to ClO hydrochlorofluoroalkene etching agent is present in a substantial amount; processes which contain C2 to ClO hydrochlorofluoroalkenes as impurities are not included in this invention. The term "substantial amount" means that the C2 to ClO hydro chlorofluoroalkene etching agent constitutes at least 10 % by weight of the sum of all etching agents applied. Fluorinated compounds which are applicable as etchant, e.g. saturated perfluoroalkanes or saturated hydrofluoroalkanes, unsaturated perfluoroalkenes or perfluoroalkadienes or other unsaturated hydrofluoroalkenes, hydrofluoroalkadienes, or a polymerizing gas, e.g. difluoromethane, are the preferred balance to 100 % by weight.
Preferably, the C2 to ClO etching agent constitutes equal to or more than 50 % by weight of the sum of all etching agents applied. Most preferably, it constitutes equal to or more than 90 % by weight of all etching agents applied. Especially preferably, it constitutes about 100 % by weight of all etching agents applied. In this embodiment, it may include undesired impurities, e.g. up to an amount of 1 % by weight. As is explained below, the hydro chlorofluoroalkenes can be applied diluted by argon or other gases. These gases are not considered in these calculations. If, for example, a mixture consisting of 10 % by weight of a C2 to ClO hydro chlorofluoroalkene and 90 % by weight of argon is considered, then the content of the hydro chlorofluoroalkene is calculated as being 100 % by weight. According to one embodiment, the present invention provides for a process for producing an etched item including at least one step of etching the item wherein the etching of the item is performed in the presence of at least one aliphatic C2 to ClO hydro chlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom. The term "an item" includes the singular and the plural, especially one item or a plurality of items, e.g. 2, 3, 4, 5 or more items. If only one item or a plurality of items are etched depends on the capacity of the used plasma chamber. If multiple items shall be etched simultaneously, a respective plasma chamber must be applied.
In the present invention, the term "comprising" includes the meaning "consisting of.
The term "hydro chlorofluoroalkene" in the present invention includes the singular and the plural, i.e. "hydrochlorofluoroalkene" denotes a single compound or a mixture of 2 or more hydrochlorofluoroalkenes.
Compounds of this kind are known as being useful starting compounds for producing saturated hydro(chloro)fluorocarbons, see for example WO 89/12614 and WO 89/12615. Hydrochlorofluoropropenes are for example disclosed in WO 2008/121785.
The term "hydro chlorofluoroalkenes" denotes compounds which consist of chlorine, fluorine, hydrogen and carbon. The term "hydrofluoroalkenes" includes compounds which have one, two or more C-C double bonds. The hydro chlorofluoroalkenes can be linear or branched.
The hydrochlorofluoroalkenes have at least 2 carbon atoms. Preferred hydro chlorofluoroalkenes have equal to or less than 10 carbon atoms. Very preferably, they have equal to 8 or less than 8 carbon atoms. Especially preferably, they have equal to or less than 6 carbon atoms. Very preferably, they have 2 to 6 carbon atoms. Most preferably, they have 3 to 6 carbon atoms. Preferred hydrochlorofluoroalkenes have 1 to 4 chlorine atoms. Very preferably, they have 1 to 3 chlorine atoms, more preferably, 1 or 2 chlorine atoms. 1 chlorine atom is especially preferred. Preferred hydrochlorofluoroalkenes have at least 2 fluorine atoms.
Especially preferred hydrochlorofluoroalkenes are those of the general formula (I)
CmClFnH2m-n-1 (I) wherein m is 2 to 6, and n is 1 to (2m-2), or of formula (II) CmCl2FnH2m.n.2 (II) wherein m is 2 to 6, n is 1 to (2m-3), or of formula (III)
CmCl3FnH2m.n.3 (III) wherein m is 2 to 6, n is 1 to (2m-4), with the proviso that the sum of chlorine atoms, fluorine atoms and hydrogen atoms in the compounds of formulae (I), (II) and (III) is 2m.
CF2=CHCl, CF2=CHCl, CF3CH2CCl=CH2, CF3CH=CClCH3,
CF3-CCI=CH-CCIF-CF3 (E) and (Z), CF3-CC1F-CH=CHC1 (E) and (Z),
CF3-CCI=CH-CCIFCH3 (E) and (Z), CF3-CC1=CH-CHC1F (E) and (Z),
CF3-CCI=CH-CCIF-CF3 (E) and (Z), CF3-CCl=CH2, CF3-CH=CCl-CF3 (E) and (Z), CF3-CCIF-CH=CCI-CH2-CF3, CF3-CCIF-CH2-CCI=CH-CF3,
CF3-CH=CCl-CH3 (E) and (Z), CF3-CH2-CCl=CH2, CF3-CH=CHCl (E) and (Z), CF3-CCl=CH2 CF3-CCI=CH-CCIF-CH2-CF3,
CF3-CH=CCl-CH2-CF3 (E) and (Z), CF3-CH2-CCl=CH-CF3 (E) and (Z),
CHCI=CCl-CH2-CF3 (E) and (Z), CH2Cl-CCl=CH-CF3 (E) and (Z), CCIF=CCl-CH2-CF3 (E) and (Z), CH2Cl-CCl=CH-CF3 (E) and (Z),
CHCI=CCI-CHCI-CF3 (E) and (Z), CH2C1-CC1=CC1-CF3 (E) and (Z), CF3-CCl=CH- CF3 (E) and (Z), CH2=CCI-CHCl-CF3, CHCIF-CCI=CCI-CF3 (E) and (Z), CC1F=CC1-CHC1-CF3 (E) and (Z), CH2CI-CCI=CCI-CF3 (E) and (Z), CF3-CCl=CH-CF3 (E) and (Z), CCIF=CCI-CHCI-CF3 (E) and (Z), CHC1F-CC1=CC1-CF3 (E) and (Z), CH2=CCI-CHCl-CF3, CH3-CCl=CCl-CF3 (E) and (Z), CH2=CCI-CClF-CF3, CF3-CCI=CCI-CH2-CF3 (E) and (Z), CF3-CHC1-CC1=CH-CF3 (E) and (Z), CF3-CCIF-CCI=CH-CF3 (E) and (Z), CF3-CHC1-CC1=CC1-CF3 (E) and (Z). Among the compounds listed, the respective hydrochlorofluoroethenes, hydrochlorofluoropropenes, hydrochlorofluorobutenes and hydrochlorofluoropentenes are especially preferred alkenes.
The hydrofluoroalkenes are known compounds or can be manufactured from known hydrochlorofluoroalkanes by dehydrochlorination or by dehydrofluorination.
The hydrochlorofluoroalkane starting material can be prepared by incomplete fluorination of the respective hydrochloroalkanes. For example, the starting compounds may be incompletely fluorinated side products in fluorination reactions. The starting compounds can also be prepared by chlorine- fluorine exchange reactions in hydrochlorofluoroalkanes which have at least one chlorine atom more and at least one fluorine atom less than the desired fluorination product. The starting compounds can also be prepared by addition of HCl to respective hydrofluoroalkenes or hydrochlorofluoroalkenes. In general, the synthesis of the starting compounds is well known in the art. Preferred starting compounds and reaction products are the following : CF3CHCl2 -> CF2=CHCl + HF CF3CHClF -> CF2=CHCl + HF
CF3CH2CClFCH3 -> CF3CH2CCl=CH2
+
CF3CH=CClCH3
CF3-CCIF-CH2-CCIF-CH3 -> CF3-CCI=CH-CCIFCH3 (E) and (Z) CF3-CCIF-CH2-CHCIF -> CF3-CCI=CH-CHCIF (E) and (Z)
+
CF3-CCIF-CH=CHCI (E) and (Z)
CF3-CCIF-CH2-CCIF-CF3 -> CF3-CCI=CH-CCIF-CF3 (E) and (Z)
CF3-CCIF-CH2-CCIF-CH2-CF3 -> CF3-CCI=CH-CCIF-CH2-CF3 +
CF3-CCIF-CH=CCI-CH2-CF3 +
CF3-CCIF-CH2-CCI=CH-CF3
CF3-CH2-CClF-CH3 ^ CF3-CH=CCl-CH3 (E) and (Z)
+
CF3-CH2-CCl=CH2
CF3-CH2-CHClF -> CF3-CH=CHCl (E) and (Z)
CF3-CHCl-CH2F ^ CF3-CCl=CH2
CF3-CFCl-CH3 -> CF3-CCl=CH2
CF3-CH2-CClF-CF3 ^ CF3-CH=CCl-CF3 (E) and (Z)
CF3-CH2-CCIF-CH2-CF3 -> CF3-CH=CCl-CH2-CF3 (E) and (Z)
+
CF3-CH2-CCl=CH-CF3 (E) and (Z)
CH2CI-CCIF-CH2-CF3 -» CHCI=CCl-CH2-CF3 (E) and (Z)
+
CH2Cl-CCl=CH-CF3 (E) and (Z)
CHCIF-CCIF-CH2-CF3 CCIF=CCl-CH2-CF3 (E) and (Z)
+
CH2Cl-CCl=CH-CF3 (E) and (Z)
CH2CI-CCIF-CHCI-CF3 -» CHCI=CCI-CHCI-CF3 (E) and (Z)
+
CH2CI-CCI=CCI-CF3 (E) and (Z)
CF3-CClF-CH2-CF3 ■* CF3-CCl=CH- CF3 (E) and (Z)
CHCIF-CCIF-CHCI-CF3 ■* CCIF=CCI-CHCI-CF3 (E) and (Z)
+
CHCIF-CCI=CCI-CF3 (E) and (Z)
CH3-CCIF-CHCI-CF3 CH2=CCI-CHCl-CF3
+
CH3-CCl=CCl-CF3 (E) and (Z)
CH3-CCIF-CCIF-CF3 ^ CH2=CCI-CClF-CF3
CF3-CHCI-CCIF-CH2-CF3 ■* CF3-CCI=CCI-CH2-CF3 (E) and (Z)
+
CF3-CHCI-CCI=CH-CF3 (E) and (Z)
CF3-CCIF-CCIF-CH2-CF3 ^ CF3-CCIF-CCI=CH-CF3 (E) and (Z)
CF3-CHCI-CCIF-CHCI-CF3 ■* CF3-CHCI-CCI=CCI-CF3 (E) and (Z)
This process is described in co-pending international patent application PCT/EP EP2009/065565 (which claims the priority of EP patent application 08169859.9) in the presence of high-surface aluminium fluoride catalysts which themselves are described in EP 1666411 Al and EP 1440939 Al.
They can also be prepared by other methods, for example, by catalytic dehydrochlorination, addition of HCl or HF to respective alkynes, or they are side products in chlorine- fluorine reactions. CF3-CH2-CClF-CH3 is, for example, a side product if pentachlorobutane is fluorinated. This compound and other chlorofluorobutanes are mentioned, for example, in US 5,739,406 and US 7,074,434.
CF3-CH2-CClF-CH3 can be dehydrofluorinated to form CF3-CH=CCl-CH3 (E) and CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2.
Another method to prepare hydrochlorofluoroalkenes is to react hydrochlorofluoroalkanes with caustic solutions (e.g. potassium or sodium hydroxide, dissolved in water) to dehydrofluorinate or to dehydrochlorinate them to form hydrochlorofluoroalkenes. Such a process is, for example, described in WO 2005/0122212.
Structural and geometric isomers, e.g. the isomers CF3-CH=CCl-CH3 (E) and CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2.can be separated in a known manner, e.g. by distillation.
The hydrochlorofluoroalkene or mixtures thereof can be applied for those purposes in etching processes for which halogenated hydrocarbons are generally used.
They can be used in etching processes, preferably for the manufacture of semiconductor memories and logics, like e.g., DRAMs and CPUs.
They are applicable to etch dielectric materials, for example, silicon dioxide, silicon nitride, low and ultra low-k dielectrics like FSG, carbon doped dielectrics and similar material. They can also be used in silicon oxide etching, in the etching of oxide glasses, e.g. borophosphosilicate glass, or oxide materials, optionally doped by e.g. fluorine (fluorosilicate glass, "FSG") or carbon (e.g. Black Diamond® of Applied Materials), so-called "low-k dielectrics", and "ultra low-k dielectrics", which are principally used for electrically insulating layers.
The hydrochlorofluoroalkenes are very suitable in processes including one or more steps of etching layers of the nitrides, borides or carbides of refractory metals ; such layers are often used to avoid diffusion of dopants or as etch stoppers. The etching of layers of refractory metal nitrides are especially preferred, still more preferably layers containing the nitrides of titanium, zirconium and tantalum, shortly TiN, ZrN and TaNx Such layers often are used as barrier layers. The etching of layers containing the nitrides of titanium, zirconium and tantalum is the preferred field of application.
The conditions during etching correspond to those usually applied. For example, direct plasma or indirect plasma can be applied. The etch process can be performed in a high-density plasma, such as an inductively coupled reactor, or a low-density plasma, such as a capacitively coupled reactor which is preferred. Often, the pressure in the plasma chamber is equal to or below 150 Pa. Preferably, the pressure is from 1 to 120 Pa. Often, the hydrochlorofluoroalkenes are applied together with argon, xenon, nitrogen and/or helium, optionally in the presence of hydrogen. If desired, when used for etching, they can be applied together with fluorinated compounds applicable as etchant, e.g. saturated perfluoroalkanes or saturated hydrofluoroalkanes, unsaturated perfluoroalkenes or perfluoroalkadienes or other unsaturated hydro fluoroalkenes or hydro fluoroalkadienes. For example, a polymerizing gas may be added, e.g. difluoromethane.
Preferably, the hydrochlorofluoroalkene is introduced into the plasma reactor, diluted with argon.
Mixture of xenon (Xe) and argon (Ar) may be applied to tune the relative selectivity of the etchant chemistry between the dielectrics and the barrier layer, enhancing the selectivity.
The hydrochlorofluoroalkenes can also be applied in processes in which a hard mask must be etched.
The C2 to ClO hydrochlorofluoroalkenes described in detail above are also applicable in another aspect of the present invention, namely chamber cleaning processes. The preferred embodiments described in view of etching, especially the preferred chloro fluoroalkenes are preferably applied in this aspect of the invention, too. During plasma etching, residues or deposits form on the walls and construction parts of the plasma reactor. It is possible to remove these residues or deposits by introducing a hydrochlorofluoroalkene into the plasma chamber and applying direct or remote plasma. The hydrochlorofluoroalkene serves as etching agent or, in other words, purifying agent. For example, residues and deposits of metals or metal compounds, e.g. the oxides, nitrides, carbides or borides, can be removed. The term "metal" preferably denotes silicon and refractory metals, especially titanium, tantalum and zirconium. For example, the borides, carbides and especially the nitrides of titanium, tantalum and zirconium can be removed. Thus, a process for cleaning a plasma chamber containing contaminations or deposits of nitrides, carbides or borides of refractory metals is provided comprising a step of introducing a purifying agent containing at least one C2 to ClO hydrochlorofluoroalkene into the plasma chamber, starting a direct or remote plasma, terminating the plasma and removing gaseous constituents from the chamber. The term "purifying agent" has the same meaning as "etching agent". After switching off the plasma, the removal of gaseous constituents can be supported by passing clean inert gas, for example nitrogen, through the chamber. Preferably, the contamination or deposits contain TaN, TiN or ZrN, and as purifying agent, or, in other words, etching agent, a composition of matter comprising or consisting of at least one hydrochlorofluoroalkene selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2, and at least one gas selected from the group consisting of nitrogen, xenon, helium, argon, and any combinations of two or more thereof is introduced into the plasma chamber. Thus, in this preferred embodiment, a composition of matter is applied which comprises or consists of at least two components, a hydrochlorofluoroalkene and a gas. The advantage of the hydrochlorofluoroalkenes of the present invention is the high etching speed.
They can be applied in the manufacture of items in the field of electronics, e.g. microelectronic devices, superconductors, and the manufacture of flat panels and solar cells. They can be applied as etching agent for treating the items and as etching gas for cleaning apparatus used for the manufacture of these items.
Another aspect of the present invention concerns a composition of matter, namely mixtures containing or consisting of at least one hydrochlorofluoroalkene and of at least one gas selected from the group consisting of nitrogen, helium, xenon, and argon. The mixture preferably contains the hydrochlorofluoroalkene and any combinations of two or more of nitrogen and the noble gases mentioned above. Optionally, additive gases, for example one or more hydrogen sources, e.g. hydrocarbons, preferably elemental hydrogen (which serves as fluorine trap in etching) or other passivating gases may be present. Mixtures containing or consisting of xenon, argon, and at least one hydrochlorofluoroalkene, and optionally additionally nitrogen, are especially preferred. Thus, one embodiment concerns mixtures of at least one hydrochlorofluoroalkene and at least one gas selected from the group consisting of nitrogen, helium, xenon, argon, and any combinations of two or more thereof, and optionally at least one hydrogen source, preferably hydrogen. Preferred mixtures comprise or consist of at last one compound selected from the group consisting OfCF3-CCl=CH2, CF3-CH2-CCl=CH2, CF3-CH=CHCl (E) and CF3-CH=CHCl (Z), CF3-CH=CCl-CH3 (E) and CF3-CH=CCl-CH3 (Z), and at least one gas selected from the group consisting of nitrogen, helium, xenon, and argon ; optionally, additionally hydrogen can be contained. Mixtures containing or consisting of CF3-CH2-CCl=CH2,
CF3-CH=CCl-CH3 (E) and CF3-CH=CCl-CH3 (Z) at least one gas selected from the group consisting of nitrogen, helium, xenon, and argon are especially preferred.
The content of the hydrochlorofluoroalkene or the sum of the hydrochlorofluoroalkenes if two or more of them are contained, is preferably equal to or greater than 10 % by volume. Preferably, it is equal to or lower than 50 % by volume. Preferably, nitrogen, helium, xenon, and/or argon are the balance to 100 % by volume. If hydrogen is present, it is preferably comprised from 2 to 10 % by volume. The percentages given here refer to the gaseous state.
The mixtures according to the invention are preferably in the condensed state, especially in the form of a liquid. They can be manufactured, for example, by introducing the respective volumes of gaseous constituents into a storage tank and condensing them therein, or by condensing respective volumes of the constituents and supplying them in liquefied form into the storage tank.
The following examples are intended to explain the invention in further detail without the intention to limit it.
EXAMPLE 1 : Gas mixtures especially suitable for TaN, ZrN and TiN etching Etching gas mixtures are prepared by condensing the respective unsaturated C4 compound, argon and optionally nitrogen and hydrogen, respectively, in a pressure-resistant storage tank.
Chlorotrifluorobutenes can be prepared by dehydrofluorination as described in PCT/EP EP2009/065565 using high-surface aluminium fluoride catalysts as described in EP 1666411 Al and EP 1440939 Al. from chlorotetrafluorobutane, a side product from the preparation of pentafluorobutane from pentachlorobutane and HF over tin halide catalysts. The resulting isomers are separated by distillation.
Table 1 : Etching gas mixtures (amounts given in % by volume)
Figure imgf000012_0001
* CF3-CCl=CH2
The gas mixtures mentioned above are prepared by filling, pressing and/or condensing the respective liquids or gases in a pressure resistant storage tank. EXAMPLE 2 : Etching of barrier layers made of TaN in a process for the manufacture of a semiconductor
A microelectronic part containing a TaNx barrier layer is manufactured as described in WO 2006/113955. A part of the barrier layer is then etched using a mixture containing 30 % by volume Of CF3-CH=CCl-CH3 (E) and 70 % by volume of argon.
Etching can be performed in an Inductive Coupled Plasma Source (ICP) etch reactor or in a Capacitively Coupled Plasma Source (CCP) reactor which is available from Applied Materials.
EXAMPLE 3 : Cleaning of a plasma chamber
A plasma chamber is contaminated with deposits of TaN layers. A mixture containing 30 % by volume OfCF3-CH=CCl-CH3 (E) and 70 % by volume of argon is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber. The gaseous reaction products can be removed from the chamber by applying a vacuum.
EXAMPLE 4 : Cleaning of a plasma chamber using CF3-CH=CCl-CH3 (Z)
A plasma chamber is contaminated with deposits of TaN layers. A mixture containing 30 % by volume of CF3-CH=CCl-CH3 (E) and 70 % by volume of argon is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber. The gaseous reaction products can be removed from the chamber by applying a vacuum. EXAMPLE 5 : Cleaning of a plasma chamber using CF3-CH2-CCl=CH2
A plasma chamber is contaminated with deposits of TaN layers. A mixture containing 30 % by volume OfCF3-CH2-CCl=CH2 and 70 % by volume of argon is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber. The gaseous reaction products can be removed from the chamber by applying a vacuum.
EXAMPLE 6 : Cleaning of a plasma chamber to remove TiN deposits using
CF3-CH2-CCl=CH2
A plasma chamber is contaminated with deposits of TiN layers. A mixture containing 30 % by volume of CF3-CH2-CCl=CH2 and 70 % by volume of argon is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber. The gaseous reaction products can be removed from the chamber by applying a vacuum. EXAMPLE 7 : Cleaning of a plasma chamber using C4H4ClF3 Chlorotetrafluorobutane is subjected to a dehydrofluorination reaction by passing it at a temperature of about 300 0C over a high-surface aluminium fluoride catalyst produced as described in EP 1666411 Al. The resulting mixture of the three isomers with the formula C4H4CIF3 (the E and Z isomers of CF3-CH=CCl-CH3 and CF3-CH2-CCl=CH2) are distilled to remove them from impurities, but they are not subjected to a fine distillation. The resulting mixture containing the isomers is mixed with argon so that the resulting etching mixture contains 70 % by volume of argon. The etching mixture is introduced into the chamber and plasma is started. Plasma conditions are maintained until the deposits are removed from the interior walls of the chamber. The gaseous reaction products can be removed from the chamber by applying a vacuum.
Should the disclosure of any of the patents, patent applications, and publications that are incorporated herein by reference conflict with the present description to the extent that it might render a term unclear, the present description shall take precedence.

Claims

C L A I M S
1. A process for producing an etched item including at least one step of etching the item with an etching agent in a plasma chamber, or for cleaning a plasma chamber containing contaminations or deposits comprising a step of introducing the etching agent into the plasma chamber, starting a direct or remote plasma, terminating the plasma and removing gaseous constituents from the chamber wherein the etching of the item is performed in the presence of at least one etching agent selected from the group consisting of aliphatic C2 to ClO hydrochlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom.
2. The process of claim 1 for producing an etched item wherein the item is a microelectronic device.
3. The process of claim 1 wherein a layer of a nitride, carbide or boride of a refractory metal is etched.
4. The process of claim 1 for cleaning a plasma chamber containing contaminations or deposits of nitrides, carbides or borides or refractory metals.
5. The process of claim 3 or claim 4 wherein the refractory metal is selected from the group consisting of tantalum, zirconium and titanium.
6. The process according to claim 5 wherein TaN, ZrN or TiN layers are at least partially etched.
7. The process of claim 1 wherein the hydrochlorofluoroalkene is applied together with at least one gas selected from the group consisting of nitrogen, xenon, helium, argon, and any combinations of two or more thereof.
8. The process of claim 7 wherein the hydrochlorofluoroalkene is applied together with xenon and argon.
9. The process of claim 6 for cleaning a plasma chamber containing deposits or contaminations wherein the deposits or contaminations contain TaN, TiN or ZrN, and wherein as etching agent, a composition of matter comprising or consisting of at least one hydrochlorofluoroalkene selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2, and at least one gas selected from the group consisting of nitrogen, xenon, helium, argon, and any combinations of two or more thereof is introduced into the plasma chamber.
10. The process of claim 1 wherein the hydro fluoroalkene is selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2.
11. A composition of matter comprising or consisting of at least one hydrochlorofluoroalkene selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2, and at least one gas selected from the group consisting of nitrogen, xenon, helium, argon, and any combinations of two or more thereof.
12. The composition of matter of claiml 1 consisting of at least one hydrochlorofluoroalkene selected from the group consisting of
CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2 and argon, or consisting of at least one hydrochlorofluoroalkene selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2 and xenon, or consisting of at least one hydrochlorofluoroalkene selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2 and argon and xenon.
13. The composition of matter of claim 12 further comprising up to 10 % by volume of nitrogen.
14. The composition of matter of claims 11, 12 or 13 wherein the hydrochlorofluoroalkene is selected from the group consisting of CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2.
15. The composition of matter of claim 11 which is in the liquid state.
16. A process for cleaning a plasma chamber containing contaminations or deposits of nitrides, carbides or borides or refractory metals comprising a step of introducing as purifying agent containing at least one C2 to ClO hydrochlorofluoroalkene containing at least 1 chlorine atom and at least 1 fluorine atom into the plasma chamber, starting a direct or remote plasma, terminating the plasma and removing gaseous constituents from the chamber.
17. The process of claim 14 wherein the contamination or deposits contain TaN, TiN or ZrN, and as purifying agent, a composition of matter comprising or consisting of at least one hydro chlorofluoro carbon selected from the group consisting of CF3-CH=CHCl (E), CF3-CH=CHCl (Z), CF3-CCl=CH2, CF3-CH=CCl-CH3 (E), CF3-CH=CCl-CH3 (Z) and CF3-CH2-CCl=CH2, and at least one gas selected from the group consisting of nitrogen, xenon, helium, argon, and any combinations of two or more thereof is introduced into the plasma chamber.
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