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WO2009058275A1 - Procédés de nettoyage de plaquettes après polissage mécano-chimique au moyen de compositions à base d'amidoxime - Google Patents

Procédés de nettoyage de plaquettes après polissage mécano-chimique au moyen de compositions à base d'amidoxime Download PDF

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Publication number
WO2009058275A1
WO2009058275A1 PCT/US2008/012238 US2008012238W WO2009058275A1 WO 2009058275 A1 WO2009058275 A1 WO 2009058275A1 US 2008012238 W US2008012238 W US 2008012238W WO 2009058275 A1 WO2009058275 A1 WO 2009058275A1
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WIPO (PCT)
Prior art keywords
acid
group
amidoxime
cleaning
compounds
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PCT/US2008/012238
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English (en)
Inventor
Wai Mun Lee
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EKC Technology Inc
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EKC Technology Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3263—Amides or imides
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Definitions

  • the present invention relates to compositions and methods for removal of chemical residues from metal or dielectric surfaces or for chemical mechanical polishing of a copper or aluminum surface including an aqueous solution comprising an amidoxime complex applied for a time sufficient to remove the chemical residues.
  • the DRAM chip will have a memory of 1 gigabit, and typical CPU will have 13 million transistors per cm 2 (currently they only contain about 4 million).
  • the number of metal layers (the "wires") will increase from the current 2-3 to 5-6 and the operating frequency, which is currently 200 MHZ, will increase, for example, to 500 MHZ. This will increase the need for a three dimensional construction on the wafer chip to reduce delays of the electrical signals.
  • the typical chip would need 10,000 or more meters of wire.
  • the manufacturing of electronic wafer chips involves a step wherein semiconductor work-pieces are cleaned with a liquid solution during or after Chemical Mechanical Planarization (CMP).
  • CMP Chemical Mechanical Planarization
  • a "semiconductor work-piece” is a microelectronic device, which has not completed the fabrication process, typically a silicon wafer with active regions formed in or on the surface of the silicon wafer. Connections to the active regions are made using multiple layers of metal, typically copper and tungsten, which has been deposited on the silicon substrate.
  • a damascene process is used whereby the copper is deposited into lines etched into the inter-layer dielectric and then the excess copper is removed and the surface planarized using a CMP process, followed by a cleaning step.
  • the goal of the cleaning process (“Post-CMP cleaning”) is to remove residues left by the CMP step from the semiconductor work-piece surface without significantly etching the metal, leaving deposits on the surface, or imparting significant organic (such as carbon) contamination to the semiconductor work-piece.
  • Acidic cleaning solutions are often quite efficient at removing organic contamination from the wafer surface and complexing residual copper. Thus, it is desirable to have a cleaning solution that is effective in the moderate to low pH regime. Acidic chemistries are typically utilized in a brush scrubber or megasonic cleaning unit for Post-CMP cleaning.
  • a cleaning solution may contain various chemicals that perform different functions during the cleaning process.
  • a cleaning solution must contain a "cleaning agent.”
  • a “cleaning agent” is the component of solution that removes residual CMP slurry particles, typically particles of metal, from the surface of the semiconductor work-piece.
  • a cleaning solution may also contain "chelating agents,” “corrosion- inhibiting compounds,” and/or “surface-active agents.”
  • a “chelating agent” helps prevent re-deposition of removed metal onto the semiconductor work-piece by complexing the metal in the cleaning solution.
  • a “corrosion-inhibiting compound” is the component of the cleaning solution that protects the metal surface from attack by mechanisms such as the aggressive nature of the cleaning solution, oxidation, post cleaning corrosion, galvanic attack, or photo-induced attack.
  • a "surface-active agent” is a component of the cleaning solution that modifies the wetting characteristics and prevents watermark formation.
  • Any oxidation or corrosion on the surface or recess of the metal causes thinning of the lines (dissolution) and results in poor performance or failure of the semiconductor device. Therefore, it is important to protect the metal surfaces from corrosion by forming a suitable corrosion resistant film on the surface of the metal.
  • Many cleaning solutions available in the art do not provide a film forming agent, and thus suffer from a high static etch rate and/or high RMS value.
  • the cleaning solution's corrosion preventing abilities are quantified by measuring the static etch rate or the surface roughness (quantified by RMS, root mean square, value) of a metal surface that has been cleaned with the subject solution.
  • a high static etch rate indicates dissolution of the metal surface is occurring.
  • a high RMS value indicates a rough surface caused by attack of the metal.
  • An effective protective film reduces the corrosion of the metal as indicated by static etch rate and RMS values after cleaning.
  • the corrosion resistance of a cleaning solution can also be directly measured using electrochemical means known to those skilled in the art.
  • One preferred method of protecting the metal surface from oxidation corrosion is by passivating the metal surface after or during cleaning. Some existing acidic cleaning chemistries do not passivate the metal, resulting in corrosion during and after the cleaning step by oxidation of the metal surface.
  • Planarizing a wafer surface usually includes a cleaning step followed by an additional step of rinsing with water or an inhibitor solution. Some rinsing agents can leave deposits on the surface of the work-piece, thus contaminating the wafer.
  • Adding a second step is also a drawback due to the fact that it lengthens the manufacturing process, complicates the process by having to handle more chemicals and more steps, and provides one more possible source of contamination or other quality control problems.
  • a process that cleans and protects the surface of the semiconductor work-piece is desirable.
  • the ability of the cleaning chemistry to remove residual metals and retain them in the cleaning solution is also an important characteristic of a Post-CMP cleaning solution.
  • Chemicals that can complex the residual metals in the cleaning solution are effective cleaning solutions because the residual metals are not re-deposited on the semiconductor work-piece after they are removed. These complexing chemicals are referred to as "chelating agents.”
  • Cleaning solutions using chemistry that cannot complex the residual metals typically perform poorly at the desired cleaning task. Thus, it is desirable to have a cleaning solution capable of removing and complexing the dissolved metal in the cleaning solution.
  • a surface wetting agent in the cleaning solution.
  • Surface wetting agents prevent contamination of the semiconductor work-piece by helping to stop spotting of the surface caused by droplets clinging to the surface.
  • Spotting also called watermarks
  • the available cleaning solutions do not adequately meet all of the requirements of post-CMP cleaning.
  • the chemistry of the current invention makes use of multiple additives to provide a solution that is not sensitive to oxygen, removes particles efficiently, removes metal from the dielectric surface, is in the neutral to low pH range, protects the metal from corrosion and dissolution, and does not contaminate the semi conductor surface.
  • the biodegradability is also unsatisfactory.
  • EDTA proves to have inadequate biodegradability in conventional tests, as does PDTA or HPDTA and corresponding aminomethylenephosphonates which, moreover, are often undesirable because of their phosphorus content.
  • Phosphorus is also a dopant in semiconductor devices, therefore it is desirable to have CMP and post-CMP cleaning solutions with non-phosphor containing compounds.
  • complexing agents sometimes called chelating agents.
  • Much metal-chelating functionality is known, a metal ion being attached by coordination links to two or more nonmetal atoms (ligands) in the same molecule. Heterocyclic rings are formed with the central (metal) atom as part of each ring.
  • the complex becomes more soluble in the solution, it functions as a cleaning process. If the complexed product is not soluble in the solution, it becomes a passivating agent by forming an insoluble film on top of the metal surface.
  • the current complexing agents in use such as, glycolic acid, glyoxylic acid, lactic acid, phosphonic acid, are acidic in nature and have a tendency to attack the residue and remove both metals and metal oxides, such as copper and copper oxide.
  • complexing agents that are not aggressive toward metal substrates, while effectively providing for the chelation of metal ions residue created during the manufacturing processes.
  • the present invention provides a method of solving one or more of the following problems common with prior art compositions and methods: reducing or eliminating corrosion problems; eliminating substantial use of flammable solvents; eliminating SARA Title HI chemistries; and lowering mobile and transition metal ions.
  • One embodiment, in accordance with the present invention is a method for the removal of residues from metal or dielectric surfaces after chemical mechanical polishing (commonly refers to post CMP clean or PCMP) of a copper or aluminum surface using an aqueous solution comprising at least one compound with one or more amidoxime functional groups. Such compound is believed to act as a chelating compound.
  • the composition optionally contains a basic compound, and optionally an acid.
  • Another embodiment, in accordance with the present invention is a method of chemical mechanical polishing a copper or aluminum surface by applying the above composition to the copper or aluminum surface, and polishing the surface in the presence of the composition.
  • the copper or aluminum surface is chemical mechanical polished by applying an aqueous composition having a pH between about 3 and about 10 to the copper or aluminum surface, and polishing the surface in the presence of the composition.
  • the invention also relates to a method for removal of chemical residues from a metal or dielectric surface after chemical mechanical polishing, by contacting the metal or dielectric surface with an aqueous composition having a pH between about 2 and about 11 for a time sufficient to remove the chemical residues.
  • the invention relates to a method for chemical mechanical polishing of a copper surface by applying an aqueous composition having a pH between about 3.7 and about 7 to the copper surface, and polishing the surface in the presence of the composition.
  • the formulations of the present invention are effective in both an acidic and basic pH range, allowing for customization of the pH based on the needs of the application, not on the effectiveness of the CMP or post-CMP cleaning compositions.
  • the invention relates to method for the chemical mechanical polishing of an aluminum surface by applying an aqueous composition having a pH between about 3.7 and about 7 to the aluminum surface, and polishing the surface in the presence of the composition.
  • the aqueous composition may include: a) a monofunctional, difunctional or trifunctional organic acid; and/or b) a buffering amount of one or more basic compounds selected from quaternary amines, hydroxylamine, hydroxylamine derivatives (including salts), hydrazine or hydrazine salt base, ammonium compounds, and one or more alkanolamines.
  • the composition contains at least one alkaline
  • alkanolamines are monoethanolamine, 2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N- tris(2-hydroxyethyl)-ammonia, isopropanolamine, 3-amino-l-propanol, 2-amino-l- propanol, 2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane and mixtures thereof.
  • Suitable organic acids include methanesulfonic acid, oxalic acid, lactic acid, citric acid, xylenesulfonic acid, toluenesulfonic acid, formic acid, tartaric acid, propionic acid, benzoic acid, ascorbic acid, gluconic acid, malic acid, malonic acid, succinic acid, gallic acid, butyric acid, trifluoracetic acid, glycolic, and mixtures thereof.
  • the aqueous composition can include a chelation agent that will complex with transition metal ions and mobile ions.
  • the chelation agent includes ethylene diamine tetraacetic acid (EDTA), an oxime, 8-hydroxy quinoline, a polyalkylenepolyamine or crown ether.
  • the aqueous composition can include an oxidizing agent that will maintain metal film oxide layers.
  • the oxidizing agent includes ammonium peroxydisulfate, peracetic acid, urea hydroperoxide, sodium percarbonate or sodium perborate.
  • the cleaning agents of the current invention are also chelating agents.
  • the cleaning action of the current invention efficiently removes residual particles from the surface of the semiconductor work-piece and also complexes the metal that is removed in solution.
  • the cleaning efficiency is improved by presenting metal from re-depositing on the semiconductor work-piece surface.
  • the corrosion-inhibiting compound of the current invention protects the metal of the semiconductor work-piece from oxidation, and corrosion.
  • the corrosion- inhibiting compounds are effective at forming a film on the metal of the semiconductor work-piece that protects metal surfaces from chemical, galvanic and photo-induced attack during and after the cleaning step.
  • One preferred embodiment forms a protective film by reducing the surface of the metal. By protecting the metal surface from attack, the metal retains its desired thickness and electrical carrying capacity.
  • the cleaning solution of the current invention is not highly sensitive to oxygen because it does not contain any oxygen sensitive compounds. Because the cleaning solution is not highly sensitive to oxygen, the performance of the cleaning solution is not affected by the presence of air in the cleaning equipment. Thus, the cleaning solution of the current invention can be used without extra precautions to purge the storage, transfer and cleaning equipment of essentially all air.
  • the cleaning solution of the current invention cleans the semiconductor work-piece and forms a corrosion-inhibiting film on the metal surfaces in the same step. Because the cleaning and corrosion inhibiting is accomplished in a single step, there is less likelihood of accidental contamination by handling a completely separate solution. Furthermore, valuable processing time is saved by not having to add an additional inhibiting step.
  • Some preferred embodiments of the cleaning solution include a surface-active agent, also referred to as a surface-wetting agent. The surface-active agent helps prevent spotting (watermarks) on the surface that can be a source of contamination or hide defects in the semiconductor work-piece.
  • One embodiment of the present invention involves the use of an aqueous composition comprising an amidoxime compound containing one or more amidoxime functional group in a semiconductor application wherein the amidoxime compound complexes with metal (or metal oxide) on a surface, in a residue, or both.
  • the composition contains one or more organic solvents.
  • the composition contains one or more surfactants.
  • the composition contains one or more additional compounds that contain functional groups which complex or chelate with metals or metal oxides.
  • the composition contains a compound which has oxidation and reduction potentials, such as a hydoxylamine or hydroxylamine derivative, such as a salt, and hydrogen peroxide.
  • the composition may contain from about 0.1% to about 99.9% water and from about 0.01% to about 99.9% of one or more compounds with one or more amidoxime functional groups. [0040]
  • the composition may also include a surfactant.
  • compositions that are substantially free from fluoride-containing compounds, acid compounds, organic solvents, alkanolamines, quaternary ammonium compounds, hydroxylamine and hydroxylamine derivatives, non-hydroxyl-containing amines, alkanolamines, non- amidoxime group chelating agents, and surfactants.
  • compositions herein may contain substantially no additional components.
  • a preferred source of the amidoxime group is from a nitrile compound that is derived from the cyanoethylation of a compound selected from the group consisting of sugar alcohols, hydroxy acids, sugar acids, monomelic polyols, polyhydric alcohols, glycol ethers, polymeric polyols, polyethylene glycols, polypropylene glycols, amines, amides, imides, amino alcohols, and synthetic polymers.
  • amidoxime structure can be represented in their resonance form as illustrated below
  • Amidoximes are made by the reaction of hydroxylamine with nitrile compounds.
  • the most preferred compounds which undergo cyanoethylation include the following:
  • Ketones or aldehydes possessing a -CH-, -CH2-, or -CH3 group adjacent to the carbonyl group • Ketones or aldehydes possessing a -CH-, -CH2-, or -CH3 group adjacent to the carbonyl group.
  • Formulations containing amidoximes may optionally include other complexing agents and the amidoxime compound could have other functional groups that have a chelate functionality within the molecule itself.
  • compositions of the present application include semiconductor processing compositions comprising water and at least one. compound containing at least one amidoxime functional group. It a preferred embodiment the at least one amidoxime functional groups are derived from a nitrile compound.
  • the nitrile compound is derived from the cyanoethylation of a compound selected from the group consisting of sugar alcohols, hydroxy acids, sugar acids, monomelic polyols, polyhydric alcohols, glycol ethers, polymeric polyols, polyethylene glycols, polypropylene glycols, amines, amides, imides, amino alcohols, and synthetic polymers.
  • One embodiment of the present invention is a method for removal of chemical residues from a metal or dielectric surface, which comprises: providing a semiconductor surface, wherein said surface comprises at least one metal or metal oxide and has undergone chemical mechanical polishing by contacting the metal or dielectric surface with a cleaning composition comprising: at least about 10% by weight of a mixture of water and optionally an organic solvent; from about 0.1% to about 35% by weight of at least one compound containing at least one amidoxime functional group; optionally one or more other organic acid compounds.
  • the composition includes between 0.1% to
  • the cleaning composition may contain a buffering amount of at least one basic compounds such as e.g., an ammonium compound, hydroxylamine, a hydroxylamine derivative, an alkanolamine and mixtures thereof.
  • the cleaning composition contains at least at least hydroxylamine or a hydroxlyamine derivative as a basic component, which may be present in an amount from about 0.3% to about 15% by weight.
  • the composition contains ammonium component (such as e.g. tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH (Tris(2- hydroxyethyl)methyl ammonium hydroxide)), preferably present in an amount from about 0.1% to about 50% by weight.
  • ammonium component such as e.g. tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH (Tris(2- hydroxyethyl)methyl ammonium hydroxide)
  • the composition contains an alkanolamine component including but not limited to monoethanolamine, 2-(2- hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)- ammonia, isopropanolamine, 3-amino-l-propanol, 2-amino-l-propanol, 2-(N- methylamino)ethanol, 2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane, or mixtures thereof.
  • alkanolamine component including but not limited to monoethanolamine, 2-(2- hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)- ammonia, isopropanolamine, 3-amino-l-propanol, 2-amino-l-propanol, 2-(N- methylamino)ethanol, 2-(2-
  • the cleaning composition neutralizes and removes amines and/or hydroxylamines in the residual processing formulation and wherein said contacting removes metal or metal oxide of the semiconductor surface at a rate less than about 17 Angstroms/min.
  • the cleaning composition includes a buffering amount of at least one basic compound selected from the group consisting of: an ammonium compound; hydroxylamine; a hydroxylamine derivative; and one or more alkanolamines.
  • a buffering amount is, for example, from about 0.1% to about 5% by weight of the basic compound.
  • One preferred basic compound is choline.
  • the cleaning ⁇ e.g. post-CMP) composition incudes one or more organic acid compounds, which can be, for example methanesulfonic acid, oxalic acid, lactic acid, citric acid, xylenesulfonic acid, toluenesulfonic acid, formic acid, tartaric acid, propionic acid, benzoic acid, ascorbic acid, gluconic acid, malic acid, malonic acid, succinic acid, gallic acid, butyric acid, trifluoracetic acid, glycolic acid, methanesulfonic acid, oxalic acid, lactic acid, citric acid, and mixtures thereof.
  • the one or more organic acid compounds may be present in an amount from about 0.2% to about 45% by weight.
  • composition may furhter contain an organic solvent or surface active agent.
  • the organic solvent which is miscible with water, is in an amount from about 5% to about 15% by weight.
  • a surface active agent such as:
  • Another embodiment of the present invention is a method for the cleaning of a semiconductor work-piece after the Chemical-Mechanical Planarization (CMP) of the wafer during the manufacturing of semiconductor devices; the method comprising the steps of: (a) providing a semiconductor work-piece, wherein said semiconductor workpiece comprises: (i) a metal line, wherein said metal line comprises copper or aluminum; (ii) a barrier material, wherein said barrier materials can be selected from the group consisting of a), tantalum (Ta), b). tantalum nitride (TaN), c). titanium (Ti), d). Titanium nitride (TiN), e) tungsten (W), and f).
  • CMP Chemical-Mechanical Planarization
  • tungsten nitride WN
  • a dielectric contacting said semiconductor work-piece with a cleaning solution comprising a cleaning agent, wherein said cleaning agent comprises: (i) water; and (ii) one or more amidoxime compounds.
  • the cleaning agent further comprises a surface- active agent which can be selected from the group consisting of: (a) non-ionic; (b) anionic; (c) cationic; (d) zwitterionic; (e) amphoteric surfactants; (f) and mixtures thereof.
  • a surface- active agent which can be selected from the group consisting of: (a) non-ionic; (b) anionic; (c) cationic; (d) zwitterionic; (e) amphoteric surfactants; (f) and mixtures thereof.
  • the cleaning agent contains at least one basic compound which includes one or more alkanolamines selected from the group consisting of monoethanolamine, 2-(2- hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)- ammonia, isopropanolamine, 3-amino-l-propanol, 2-amino-l-propanol, 2-(N- methylamino)ethanol, 2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane and mixtures thereof.
  • the cleaning agent may be present in an amount from about 0.5% to about 50% by weight.
  • the cleaning agent is substantially free from fluoride-containing compounds, acid compounds, organic solvents, alkanolamines, quaternary ammonium compounds, hydroxylamine and hydroxylamine derivatives, non-hydroxyl-containing amines, alkanolamines, non-amidoxime group chelating agents, and surfactants.
  • the amidoxime group is derived from a nitrile compound that is derived from the cyanoethylation of a compound selected from the group consisting of sugar alcohols, hydroxy acids, sugar acids, monomelic polyols, polyhydric alcohols, glycol ethers, polymeric polyols, polyethylene glycols, polypropylene glycols, amines, amides, imides, amino alcohols, and synthetic polymers.
  • the cleaning agent may be further diluted with e.g. water prior to contacting the semiconductor work-piece.
  • the cleaning agent or compositions are diluted before use or replenished during or after use where up to 500 parts water is added to said composition within about one day prior to contacting the resulting mixture to a substrate. At some times the up to 500 parts water is added to the composition within about one hour prior to contacting the resulting mixture to a substrate. In one embodiment, the dilution factor is from about 10 to about 500.
  • the cleaning solution may have (1) another chelating agent which does not contain an amidoxime functional group, such as e.g.
  • ethylene diamine tetraacetic acid hydroxamic acid, an oxime, 8-hydroxy quinoline, a polyalkylenepolyamine, triazole, a crown ether, and mixtures thereof and/or (2) an oxidizing agent, such as e.g. ammonium peroxydisulfate, peracetic acid, urea hydroperoxide, sodium percarbonate, organic peroxide, sodium perborate and mixtures thereof.
  • an oxidizing agent such as e.g. ammonium peroxydisulfate, peracetic acid, urea hydroperoxide, sodium percarbonate, organic peroxide, sodium perborate and mixtures thereof.
  • Another embodiment of the invention is a method for the removal of residues and contaminants from a metal or dielectric surface.
  • the method has at least the steps of (1) providing a semiconductor surface, wherein said surface comprises at least one metal or metal oxide and has thereon a cleaning formulation comprising amines, hydroxyl amines, or mixtures thereof; (2) contacting the metal or dielectric surface with a post-cleaning composition containing one or more amidoxime compounds, water, between 1% to 25% by weight of one or more organic acids selected from the group consisting of monofunctional, difunctional and trifunctional organic acids, and between 0.5% and 30% by weight of an oxidizing agent, for a time sufficient to remove the residual cleaning formulation.
  • the post cleaning (post-clean) composition has a pH between about 3.5 and about 7, and the contacting removes metal or metal oxide of the semiconductor surface at a rate less than about 17 Angstroms/min.
  • the semiconductor surface comprises a metal comprising Al, an Al/(0.5%)Cu alloy, Ti, W, Ta, or alloys thereof, and wherein the contacting step removes less than about 1 Angstrom/min of metal or metal oxide from the semiconductor surface.
  • the contacting step of the method removes less than about 17 Angstroms/min of Cu metal or Cu oxide from the semiconductor surface.
  • the post-clean composition may also contain between 0.01% and 10% by weight of a chelator.
  • the post clean composition has a surface tension of approximately 70 dynes/cm or less.
  • the residues are from a liquid residual CMP or etching residue remover formulation comprising, for example amines, hydroxylamines, or mixture thereof.
  • the chemical residues are removed by contacting the metal or dielectric surface with a post-etch cleaning composition comprising: one or more compounds with at least one amidoxime functional group, water, between 1% to 25% by weight of one or more organic acids selected from the group consisting of monofunctional, difunctional or trifunctional organic acid; between 0.5% and 30% by weight of an oxidizing agent; and water, wherein the post clean composition has a pH between about 3.5 and about 7, for a time sufficient to remove the residual processing formulation, wherein the post clean composition neutralizes and removes amines and/or hydroxylamines in the residual processing formulation, wherein said contacting removes copper or copper oxide from the semiconductor surface at a rate less than about 17 Angstroms/min or in other embodiments, the semiconductor surface has a metal comprising Al, an Al/(0.5%)Cu alloy, Ti, W, Ta, or alloys thereof, and
  • the post-CMP cleaning chemistries herein are capable of being used without a rinse step and in some embodiments; the method of post-CMP cleaning is done without a rinse step, unlike many current post-CMP cleaners.
  • the present invention also applies to a method for the chemical mechanical planarization of a semiconductor work-piece; the method comprising the steps of: (a) providing a semiconductor work-piece, wherein said semiconductor workpiece comprises: (i) a metal line, wherein said metal line comprises copper or aluminum; (ii) a barrier material, wherein said barrier materials can be selected from the group consisting of a). Tantalum (Ta), b). Tantalum nitride (TaN), c). Titanium (Ti), d). Titanium nitride (TiN), e). Tungsten (W), and f).
  • Tungsten nitride WN
  • a dielectric contacting said semiconductor work-piece with a cleaning solution comprising a cleaning agent, wherein said cleaning agent comprises: (i) water; (ii) one or more compounds containing at least one amidoxime functional group.
  • the cleaning agent may further include one or more oxidizers and one or more surface- active agents, such as a surfactant in the classes disclosed herein (anionic surfactants, Zweitter-ionic surfactants, multi-ionic surfactants, or combinations thereof).
  • a surfactant in the classes disclosed herein (anionic surfactants, Zweitter-ionic surfactants, multi-ionic surfactants, or combinations thereof).
  • surfactants are: sodium salts of polyacrylic acid, potassium oleate, sulfosuccinates, sulfosuccinate derivatives, sulfonated amines, sulfonated amides, sulfates of alcohols, alkylanyl sulfonates, carboxylated alcohols, alkylamino propionic acids, alkyliminodipropionic acids, and combinations thereof and wherein the surfactant comprises between about 0.001 to about 10 percent by weight of the composition.
  • the pH may be adjusted to between about 2 and about 11.
  • Preferable additives for pH adjustment are acetic acid, phosphoric acid, oxalic acid, and combinations thereof and wherein the composition has a pH between about 2 and about 11.
  • Such chemistries in CMP applications may be slurries including abrasive particles comprising about 35 wt. % or less of the composition and wherein the abrasive particles comprise materials selected from the group of silica, alumina, titanium oxide, zirconium oxide, cerium oxide, and combinations thereof.
  • the chemistries may also comprise one or more corrosion inhibitors, water, and combinations thereof.
  • the one or more compounds containing at least one amidoxime group in situ with a first CMP composition between about 30 seconds and about 300 seconds after the first CMP composition is delivered to the polishing pad.
  • the compositions herein are diluted prior to use in an amount of up to about 1000 parts water by weight to about 1 part of the composition by weight, more preferably up to about 500 parts water by weight to about 1 part of the composition, or up to about 100 parts water by weight to about 1 part of the composition or up to about 10 parts water by weight to about 1 part of the composition, or 1 part water to about 1 part of the composition, including ratios in between.
  • the dilution is done prior to use in some embodiments and after use in another embodiment. When done prior to use, the water is added, for example, within about one week, or about one day, or about one hour. It has been found that the fresh dilution is more effective than if said dilution occurred greater than about one week from use. By use, for example, the mixture is contacted with a substrate.
  • Figure 1 illustrates the surface chemistry concept of a contact angle and its importance in semiconductor cleaning.
  • Figure 2 shows the unexpected results of an amidoxime compound inhibiting copper oxidation in the presence of strong oxidizer, such as hydrogen peroxide.
  • Figure 3 provides ESCA analysis data which show the presence of
  • Figure 4 provides ESCA analysis data which show that all of the
  • Cu(II) oxide has been removed by the amidoxime solution of the invention.
  • the cleaning process also inhibits the oxidation of the copper surface after two hours exposure to an ambient environment.
  • Figure 5 provides ESCA analysis data which show only a small amount of Cu(II) oxide growth after exposure to an ambient environment for 10 days.
  • the cleaning process using a composition comprising an amidoxime compound inhibited the growth of Cu(II) oxide.
  • Figure 6 is the Auger depth profile analysis of the copper surface treated by cleaning; the result suggests that, after exposure to an ambient environment for
  • Figure 7 shows a Copper Pourbaix diagram indicating that copper oxide/hydroxide are insoluble in water at high pH.
  • Figure 8 is a graph depicting amidoxime solution (DS6-10), which effectively removes particles from a thermal oxide surface. It is also effective at a dilution factor of 10.
  • Figure 9 is a graph showing amidoxime solution (DS6-10), which effectively removes particles from a copper surface. It is also effective at a dilution factor of 10.
  • Figure 10 is a graph depicting amidoxime solution (DS6-10). which effectively removes particles from low k dielectrice BlackDiamondTM (BDI) surface. It is also effective at a dilution factor of 10.
  • DS6-10 amidoxime solution
  • BDI BlackDiamondTM
  • Figure 11 shows the zeta potential of conventional CMP slurries at various pH's. Slurry systems are stable above or below its isoelectric point.
  • Figure 12 shows the zeta potential of amidoxime solution (DS6-10) at various pH's. It has a high negative Zeta Potential, which suggests good property for removal slurry particles.
  • Figure 13 provides SEM images using different cleaning chemicals.
  • Amidoxime solution (DS6-10) of the invention effectively removes particles and copper oxide from the surface without damaging the copper surface. It is also effective at a dilution factor of 10.
  • Figure 14 presents SEM images of amidoxime solution (DS6-10) which, after exposure to the solution at 60°C up to 4 hours, effectively remove particles and copper oxide from the surface without damaging the copper surface. The images are compared to those for EKC5510 from EKC Technology under the same conditions.
  • Figure 15 shows there was no k value shift for BlackDiamondTM (BDI) from Applied Materials. This suggests that amidoxime solution (DS6-10) of the invention is compatible with carbon doped low k dielectric.
  • BDI BlackDiamondTM
  • Figure 16 shows the process flow for post CMP clean tool from
  • the wafer After polishing, the wafer is transferred to a brush unit capable of dispensing cleaning chemistries and DI water, and then the wafer is moved to a pencil unit for DI rinse with high pressure jet spray water to the wafer surface.
  • the present invention is a cleaning solution for cleaning a semiconductor work-piece.
  • the composition of the cleaning solution comprises at least one compound containing at least one amidoxime functional group.
  • the CMP and post- CMP cleaning solution may be supplied in concentrated form, or diluted with water or other suitable diluents known to one skilled in the art and in concentrations as provided herein.
  • Amidoxime compound can be used in the invention is derived from the reaction of a nitrile compound with hydroxylamine.
  • the typical silicon surface is terminated (covered) with -OH groups under neutral or basic conditions.
  • the silicon surface is hydrophilic, meaning the surface is "wettable". These groups activate the surface to a number of possible chemical or physioabsorbtion phenomena.
  • the Si-OH groups impair a weak acid effect which allows for the formation of salts and to exchange the proton (H+) for various metals (similar to the ion exchange resins).
  • These SiO- and Si-OH groups can also act as ligands for complexing Al, Fe, Cu, Sn and Ca.
  • the surface is very dipolar and so electrostatic charges can accumulate or be dissipated depending on the bulk solution's pH, ion concentration or charge. This accumulated surface charge can be measured as the Zeta potential.
  • pH in aqueous media the pH of the sample is one of the most important factors that affects its zeta potential.
  • a zeta potential value on its own without defining the solution conditions is a virtually meaningless number.
  • a particle in suspension with a negative zeta potential If more alkali is added to this suspension then the particles tend to acquire more negative charge.
  • acid is added to this suspension then a point will be reached where the charge will be adsorption where they have no effect on the isoelectric point, (ii) specific ion neutralised. Further addition of acid will cause a build up of positive charge. Therefore a zeta potential versus pH curve will be positive at low pH and lower or negative at high pH.
  • the isoelectric point There may be a point where the plot passes through zero zeta potential. This point is called the isoelectric point and is very important from a practical consideration. It is normally the point where the colloidal system is least stable.
  • a typical plot of zeta potential versus pH is shown in figure 8. In this example, the isoelectric point of the sample is at approximately pH 5.5.
  • the plot can be used to predict that the sample should be stable at pH values less than 4 (sufficient positive charge is present) and greater than pH 7.5 (sufficient negative charge is present). Problems with dispersion stability would be expected at pH values between 4 and 7.5 as the zeta potential values are between +30 and -3OmV.
  • the thickness of the double layer depends upon the concentration of ions in solution and can be calculated from the ionic strength of the medium. The higher the ionic strength, the more compressed the double layer becomes. The valency of the ions will also influence double layer thickness.
  • a trivalent ion such as Al 3+ WiIl compress the double layer to a greater extent in comparison with a monovalent ion such as Na + .
  • Inorganic ions can interact with charged surfaces in one of two distinct ways (i) nonspecific ion adsorption, which will lead to a change in the value of the isoelectric point.
  • the effect of the concentration of a formulation component on the zeta potential can give information to assist in formulating a product to give maximum stability.
  • the influence of known contaminants on the zeta potential of a sample can be a powerful tool in formulating the product to resist flocculation for example.
  • Si silicon
  • the oxide layer may become impenetrable to the chemistry and the metal becomes passive, (Vf >Vp) and the metal polishing rate becomes slow.
  • Metal polishing selectively to oxide generally ranges from 20 to 100:1, depending on the metal type. Tungsten metal should have selectivities >50:l for the metal to oxide, and copper could have >140: 1 metal to oxide selectivity. Etch rates can be up to 7000 A/min. The chemical diffusion rate and the type of metal oxide surface are important to the successful planarization process. A detailed mechanism has been proposed by Kaufman, F.; J. Electrochem. Soc; 138 (11), p. 3460, 1991. [00117] Copper films present a difficult problem because copper is a soft metal and is easily damaged by slurry particles. The Post Clean Treatment solutions can be very useful for removing these imperfections.
  • Aluminum is also a soft metal and is easily damaged by slurry particles.
  • Aluminum differs from copper in its ability to self-passivate. Copper in its natural state does not easily form an oxide film on its surface. It is believed that the Post Clean Treatment solution can successfully polish copper in part because copper does not easily form a protective oxide layer. In contrast, Aluminum does self-passivate relatively easily. In spite of this tendency to form a protective oxide layer, we have surprisingly found that the Post Clean Treatment solutions can also be used to successfully polish aluminum films.
  • Contact angle measurement characterizes the interfacial tension between a solid and a liquid drop.
  • the technique provides a simple method to generate a great amount of information for surface analysis. And because the technique is extremely surface sensitive, it can be used in semiconductor cleaning applications
  • Contact angle measurement is a simplified method of characterizing the interfacial tension present between a solid, a liquid, and a vapor.
  • a droplet of a high surface tension liquid rests on a solid of low surface energy
  • the liquid surface tension will cause the droplet to form a spherical shape (lowest energy shape).
  • the solid surface energy exceeds the liquid surface tension, the droplet is a flatter, lower profile shape.
  • x -OH, - NHR, -H, -Halogen, -CO 2 H and -CH 2 COOH, -CH(OH)-COOH
  • R generally aliphatic, H or aromatic
  • Concentrations can vary from 1 to 25 wt %. The important factor is the solubility of the acid and base products with any additional agents in the aqueous solutions.
  • a caustic component can be used to adjust the pH of the buffer Post
  • CMP cleaning composition Although the pH adjustment can be achieved with any common base, i.e. sodium, potassium, magnesium etc. hydroxides, such bases introduce mobile ions into the final formulation. Mobile ions can easily destroy computer chips being produced today in the semiconductor industry. Accordingly, embodiments of the present invention are free of bases that introduce mobile ions. In such embodiments, other bases are used, including organic amines, hydroxylamine, quaternary amines such as tetramethylammonium hydroxide (TMAH) or choline or THEMAH or ammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • THEMAH ammonium hydroxide
  • An added feature for this invention is to add small quantities of metal ion chelators which could include di-, tri-, tetra-functional groups, i.e., EDTA, citric acid, oximes, lactic acid, 8-hydroxy quinoline and other well known agents that will chelate with metal ions under acid conditions.
  • metal ion chelators which could include di-, tri-, tetra-functional groups, i.e., EDTA, citric acid, oximes, lactic acid, 8-hydroxy quinoline and other well known agents that will chelate with metal ions under acid conditions.
  • Other possible agents are polyethylene oxide, polyethyleneimine and crown ethers. These latter two compounds have varying affinity for mobile ions (Li, Na, K, and certain alkaline earth ions). Concentrations preferably vary from 0.01 to 10 wt %.
  • Preferred corrosion-inhibiting compounds are ascorbic acid, benzotriazole, caffeic acid, cinnamic acid, cysteine, glucose, imidazole, mercaptothiazoline, mercaptoethanol, mercaptopropionic acid, mercaptobenzothiazole, mercaptomethylimidazole, tannic acid, thioglycerol, thiosalicylic acid, triazole, vanillin, vanillic acid, or mixtures thereof.
  • One preferred cleaning solution of the present invention includes a surface-active agent to promote even wetting of the semiconductor surface.
  • Preferred embodiments include, but are not limited to, non-ionic, anionic, cationic, zwitterionic or amphoteric surfactants or mixtures thereof.
  • Surfactants nonionics, anionics and cationics
  • the surface tensions for the Post Clean Treatment solutions will be .about.70 dynes/cm, there may be special situations were the surface tension needs to be reduced.
  • a key component of the formulations of the present invention is the presence of one or more compounds with at least one amidoxime functional group.
  • the multidentate complexing agents disclosed above complex with substrate surfaces to remove contaminants on such surfaces.
  • Amidoxime molecule can be designed to function as passivation on metal surface by rendering insoluble metal complex or as cleaning agent by rendering the metal containing residue more soluble.
  • Amidoxime copper complexes have shown to be readily soluble in water under basic condition while less soluble under acidic condition. Accordingly, the passivating/cleaning effect of the amidoxime chemistry can be affected by altering the pH.
  • Amidoximes have been shown to complex with metals, such as copper.
  • Amidoximes of cyanoethylated cellulose have also been shown to complex with copper and other metal ions. (See, Altas H. Basta, International Journal of Polymeric Materials,
  • compositions, and method of use thereof containing a group of higher pH range chelating compounds comprising at least two functional groups where at least one such group is an amidoxime.
  • the other groups or complexing compounds may be selected as may be beneficial for the application, the chemistry, and/or the conditions.
  • Examples of other complexing groups include hydroxamic acid, thiohydroxamic acid, N-hydroxyurea, N-hydroxycarbamate, and
  • N-nitroso-alkyl-hydroxylamine These groups offer synergistic advantages when used with amidoximes of removing metal oxide, such as copper oxide, residue by rendering such oxides soluble in aqueous solutions. As with amidoximes, these functional groups can be formed by reaction with hydroxylamine or hydroxylamine derivatives.
  • complexing agents may be purchased commercially or prepared by known methods. A non-exhaustive list has been previously presented.
  • hydroxamic acid group is a synergistic functional group.
  • Such groups are well known (H. L. Yale, "The Hydroxamic Acids", Chem. Rev., 209-256 (1943)).
  • Polymers containing hydroxamic acid groups are known and can be prepared by addition of hydroxylamine to anhydride groups of anhydride-containing copolymers, such as styrene-maleic anhydride copolymer or poly(vinylmethylether/maleic anhydride) copolymers, or by reaction of hydroxylamine with ester groups.
  • Hydroxamic acid-containing polymers can also be prepared by acid-catalyzed hydrolysis of polymers that contain amidoxime groups (U.S. Pat.No. 3,345,344).
  • United States Patent No. 6,259,353 discusses the formation of high purity oximes from aqueous hydroxylamine and ketones reacted at ambient temperature without addition of impurities such as salts or acids.
  • Thiohydroxamic acids are another synergistic type of functional groups with amidoximes and can be prepared by addition of hydroxylamine to dithiocarboxylic acids (H. L. Yale, Chem. Rev., 33, 209-256 (1943)).
  • N-hydroxyureas are another synergistic type of functional groups with amidoximes and can be prepared by reaction of hydroxylamine with an isocyanate (A. O.
  • N-Hydroxycarbamates are another synergistic type of functional groups with amidoximes and can be prepared by reaction of hydroxylamine with either a linear or cyclic carbonate (A. O. Ilvespaa et al., Chimia (Switz.) 18, 1-16 (1964)).
  • N-Nitroso-alkyl-hydroxylamines are another synergistic type of functional groups with amidoximes and can be prepared by nitrosation of alkyl hydroxylamines (M. Shiino et al., Bioorganic and Medicinal Chemistry 95, 1233-1240
  • One embodiment of the present invention involves methods of precleaning substrates or removing stripping or ashing residues using aqueous cleaning solutions which comprise at least one chelating compound with one or more amidoxime functional group.
  • amidoximes can be prepared by the reaction of nitrile-containing compounds with hydroxylamine.
  • amidoxime chelating compounds A convenient route to the formation of amidoxime chelating compounds is by adding hydroxylamine to the corresponding nitrile compound.
  • cyanide addition reactions such as hydrocyanation, polymerization of nitrile-containing monomers to form polyacrylonitrile or copolymers of acrylonitrile with vinyl monomers, and dehydration of amides.
  • Typical procedures for the syntheses of nitriles may be found in J. March, Advanced Organic Chemistry, 4th ed., John Wiley and Sons, NY, (1992).
  • Nitriles compounds listed in the CRC Handbook can be used in this invention include but are not limited to the followings: Cyanoacetylene, Cyanoacetaldehyde, Acrylonitrile, Fluoroacetonitrile, Acetonitrile (or Cyanomethane), Trichloroacetonitrile, Methacrylonitrile (or ⁇ -Methylacrylonitrile), Proionitrile (or Cyanoethane), Isobutyronitrile, Trimethylacetonitrile (or tert-Butylcyanide), 2- Ethyacrylonitrile, Dichloroacetonitrile, ⁇ Chloroisobutyronitrile, n-Butyronitrile (or 1- Cyanopropane), trans-Crotononitrile, Allycyanide, Methoxyacetonitrile, 2- Hydroxyisobutyronitrile (or Acetone cyanohydrins), 3-Hydroxy
  • Ri is — H, — CH 3 , a C 2 . 24 -alkyl or -alkenyl radical, a substituted C 2 . 24 -alkyl or - alkenyl radical with at least one substituent from the group — Cl, — Br, — OH, — NH 2 , — CN, an alkyl- or alkenylaryl radical with a Cl-24-alkyl group, or is a substituted alkyl- or alkenylaryl radical with a Ci -24 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 independently of one another, are chosen from CH 2 — CN, — CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , — CH(CH 3 )- CH 3 , -CH 2 -OH, -CH 2 - CH 2 -OH, -CH(OH)-CH 3 , -CHCH 3
  • the detergent and cleaner according to the invention comprise cationic nitrites in which Rj is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- tetradecyl, nhexadecyl or n-octadecyl radical.
  • R 2 and R 3 are preferably chosen from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both of the radicals may advantageously also be a cyanomethylene radical.
  • radicals Rl to R3 are identical, for example (CH 3 ) 3 N(+)CH 2 — CN (X-), (CH 3 CH 2 ) 3 N(+)CH 2 — CN X-, (CH 3 CH 2 CH 2 ) 3 N (+)CH 2 — CN X-, (CH 3 CH(CH 3 )) 3 N(+)CH 2 — CN X- or (HO— CH 2 - CH 2 ) 3 N(+)CH 2 — CN X-, where X- is preferably an anion which is chosen from the group consisting of hydroxide, chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate.
  • X- is preferably an anion which is chosen from the group consisting of hydroxide, chloride, bromide, iodide, hydrogensulfate, methosul
  • cyanoethylation A particularly useful route to nitrites is termed "cyanoethylation", in which acrylonitrile undergoes a conjugate addition reaction with protic nucleophiles such as alcohols and amines.
  • protic nucleophiles such as alcohols and amines.
  • Other unsaturated nitrites can also be used in place of acrylonitrile.
  • Preferred amines for the cyanoethylation reaction are primary amines and secondary amines having 1 to 30 carbon atoms, and polyethylene amine. Alcohols can be primary, secondary, or tertiary.
  • the cyanoethylation reaction (or "cyanoalkylation" using an unsaturated nitrile other than acrylonitrile) is preferably carried out in the presence of a cyanoethylation catalyst.
  • Preferred cyanoethylation catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide and metal ion free bases from tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium hydroxide), TBAH, choline, and
  • THEMAH Tris(2-hydroxyethyl)rnethylarnmonium hydroxide.
  • the amount of catalyst used is typically between 0.05 mol % and 15 mol %, based on unsaturated nitrile.
  • the cyanolates are derived from the following groups: arabitol, erythritol, glycerol, isomalt, lactitol, maltitol, mannitol, sorbitol, xylitol, sucrose and hydrogenated starch hydrosylate (HSH).
  • hydroxyphenyl acetic acid mandelic acid
  • 2-hydroxypropionic acid lactic acid
  • glycolic acid glycolic acid
  • hydroxysuccinic acid malic acid
  • 2,3-dihydroxybutanedioic acid
  • tartaric acid 2-hydroxy- 1,2,3- propanetricarboxylic
  • acid citric acid
  • ascorbic acid 2-hydroxybenzoic, acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • sugar acids galactonic acid, mannonic, acid, fructonic acid, arabinonic acid, xylonic acid, ribonic, acid, 2-deoxyribonic acid, and alginic acid.
  • PEGS Polyethylene glycols
  • n can assume values between 1 (ethylene glycol, see below) and about 16.
  • Polyethylene glycols are commercially available, for example under the trade names Carbowax. RTM. PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HOLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone-Poulenc), Lutrol® E300 (BASF), and the corresponding trade names with higher numbers.
  • PPGs Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which satisfy the general formula
  • n can assume values between 1 (propylene glycol) and about 12.
  • n can assume values between 1 (propylene glycol) and about 12.
  • Amines are organic compounds and a type of functional group that contain nitrogen as the key atom. Structurally amines resemble ammonia, wherein one or more hydrogen atoms are replaced by organic substituents such as alkyl, aryl and cyclic groups. Compounds containing one or more -NH- groups of the formula:
  • Amides - an amide is an amine where one of the nitrogen substituent is an acyl group; it is generally represented by the formula: Ri(CO)NR 2 R 3 , where either or both R2 and R3 may be hydrogen.
  • an amide can also be regarded as a derivative of a carboxylic acid in which the hydroxyl group has been replaced by an amine or ammonia, in which a -CH- or -CH 2 - group is situated between -CONH- groups.
  • Imides - imide is a functional group consisting of two carbonyl groups bound to a primary amine or ammonia.
  • the structure of the imide moiety is as shown, which possessing a -CH-, -CH 2 -, Or -CH 3 group adjacent to the carbonyl group.
  • Amino alcohols are organic compounds that contain both an amine functional group and an alcohol functional, where the amine can be primary or secondary amines of the formula, wherein X is independently selected from alkylene, heteroalkylene, arylene, heteroarylene, alkylene-heteroaryl, or alkylene-aryl group.
  • Synthetic polymers such as acetone-formaldehyde condensate, acetone-isobutyraldehyde condensate, methyl ethyl ketone-formaldehyde condensate, poly(allyl alcohol), poly(crotyl alcohol), poly(3- chloroallyl alcohol), ethylene-carbon monoxide copolymers, polyketone from propylene, ethylene and carbon monoxide, poly(methallyl alcohol, poly(methyl vinyl ketone, and poly(vinyl alcohol).
  • Synthetic polymers such as acetone-formaldehyde condensate, acetone-isobutyraldehyde condensate, methyl ethyl ketone-formaldehyde condensate, poly(allyl alcohol), poly(crotyl alcohol), poly(3-chloroallyl alcohol), ethylene-carbon monoxide copolymers, polyketone from propylene, ethylene and carbon monoxide, poly(methallyl alcohol, poly(methyl vinyl ketone, and poly(vinyl alcohol) have also been cyanoethylated and can also serve as platforms for further modification into metal-binding polymers.
  • nitrile groups of these cyanoethylates or cyanoalkylates can be reacted with hydroxylamine to form the amidoxime.
  • hydroxylamine, hydroxylamine hydrochloride, and hydroxylamine sulfate are suitable sources of hydroxylamine.
  • hydroxylamine salt is used instead of hydroxylamine freebase, a base such as sodium hydroxide, sodium carbonate or metal ion free base such ammonium hydroxide, tetraalkylammonium hydroxide should be used to release hydroxylamine as freebase for the reaction.
  • Metal ion freebase such as ammonium hydroxide or a group of tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide, TMAH pentahydrate, BTMAH (benzyltetrarriethylammonium hydroxide), TBAH, choline, and
  • TEMAH Tris(2-hydroxyethyl)methylammonium hydroxide
  • the present invention offers the benefit of binding to the metal oxide surface to create an oxidation barrier, particularly where the amidoxime is derived from functionalized amidoxime polymer, such as from polyvinylalcohol, polyacrylonitriles and its copolymers.
  • functionalized amidoxime polymer such as from polyvinylalcohol, polyacrylonitriles and its copolymers.
  • the present invention utilizes the cyanoethylated compounds referenced in "The Chemistry of Acrylonitrile, 2nd ed.” as starting materials for synthesis of amidoximes, such reference is incorporated herein to the extent of the cyanoethylated compounds disclosed therein.
  • the most preferred staring materials for synthesis of amidoximes are those prepared from cyanoethylated sugar alcohols, like sucrose, or reduced sugar alcohols, like sorbitol.
  • the present invention further offers the benefit of increasing the bulk removal of metal during the CMP process when a chelating agent disclosed herein (e.g.,
  • the present invention further offers the benefit of more efficient and effective binding to metal ions found in semiconductor manufacturing processes, such as residue after plasma etching particularly with leading edge technology where copper is used as conducting metal.
  • Another advantage of the chelating agents disclosed herein is that such chelating agent could be used in dilution as a Post-copper CMP clean because these groups of compounds are less acidic than organic acid and less basic than ammonia, choline hydroxide and THEMAH.
  • the present invention further offers the benefit of more efficient and effective binding to metal ions found in semiconductor manufacturing processes, such as residue after plasma etching particularly with leading edge technology where copper is used as conducting metal.
  • Another advantage of the chelating agents disclosed herein is that such chelating agent could be used in dilution as a Post-copper CMP clean because these groups of compounds are less acidic than organic acid and less basic than ammonia, choline hydroxide and THEMAH.
  • amidoxime chelating compound can also prepare in-situ while blending the cleaning formulation.
  • Silica was activated by heating it above 100 °C in vacuum and was then allowed to cool to room temperature under nitrogen. To the activated silica (10 g) was absorbed aniline (1.86 g, 20 mmol) and acrylonitrile (2.65 g, 50 mmol) and the flask was capped tightly. The contents were then stirred with a magnetic stirrer for 6 days at 60 °C. After this time the mixture was cooled to room temperature and extracted with MeOH.
  • TMAH TMAH (25% in water, 10.95 g, 30.04 mmol) at room temperature. The mixture was stirred for 24 hours, and was then cooled to 0 °C. A mixture of 12M HCl (2.69 cm 3 , 32.1 mmol) and ice (3 g) was added and the mixture was extracted with CH 2 Cl 2 (5x50 cm 3 ).
  • Acetamide (2 g, 33.9 mmol) was mixed with acrylonitrile (2.26 g, 42.7 mmol) at 0 0 C and TMAH (25% in water, 0.06 cm 3 , 0.06 g, 1.7 mmol) was added. The mixture was then stirred overnight, allowing it to warm to room temperature slowly. The mixture was filtered through a pad of silica with the aid of Et 2 O/CH 2 Cl 2 (200 cm 3 ) and the filtrate was concentrated under reduced pressure.
  • the product was heated with spinning in a Kugelrohr at 150 °C/2 mmHg to remove side products and to give N,N-bis(2- cyanoethyl)acetamide (0.89 g, 15.9%) as a viscous oil.
  • Pentaerythritol (2 g, 14.7 mmol) was mixed with acrylonitrile (5 cm 3 ,
  • TMAH tetramethylammonium hydroxide
  • TMAH (25% in water, 0.34 cm 3 , 0.35 g, 9.5 mmol) in dioxane (5 cm 3 ) was added acrylonitrile (3.53 g, 66.1 mmol) dropwise. The mixture was then stirred overnight, and allowed to warm to room temperature. More acrylonitrile (1.51 g, 28 mmol) and TMAH (0.25 cm 3 , 7 mmol) was added and stirring was continued for additional 24 h. The crude mixture was filtered through a pad of silica (Et 2 O/CH 2 Cl 2 as eluent) and evaporated to remove dioxane.
  • Cinnamonitrile (1 g, 7.74 mmol) and hydroxylamine (0.71 cm 3 , 11.6 mmol, 1.5 eq) were reacted in EtOH (7 cm 3 ) as described for AO6 (two chromatographic separations were needed in purification) to give N'-hydroxycinnamimidamide (0.88 g, 70%) as a light orange solid, mp 85-87 °C (lit 93 0 C).
  • the solution was warmed to 42 °C in a water bath and treated with acrylonitrile (42 ml, 633 mmol, 0.96 eq) drop-wise via the addition funnel for * a period of 1 hr. while maintaining the temperature at 42 °C.
  • the second portion of sorbitol (60 g, 329 mmol) and water (50 ml) were added to the flask.
  • the second portion of the acrylonitrile (89.1 ml, 1.344 mol, 2.04 eq) was added in a drop-wise fashion over a period of 1 hr.
  • the solution was warmed to 50-55oC for 4 hr. and then allowed to cool to room temperature.
  • the reaction was neutralized by addition of acetic acid (2.5 ml) and allowed to stand overnight at room temperature.
  • the solution was evaporated under reduced pressure to give the product as a clear, viscous oil (228.23 g).
  • Tetramethylammonium hydroxide can be used to substitiute lithium hydroxide.
  • the first portion of acrylonitrile (100 ml) was then added to the reaction drop-wise via a 500 ml addition funnel over a period of 2 hr.
  • the reaction was slightly exothermic, raising the temperature to 51 0 C.
  • the final portion of sorbitol (32 g) was added for a total of 0.638 moles followed by a final portion of acrylonitrile (190 ml) over 2.5 hr. keeping the reaction temperature below 60°C. (A total of 4.41 moles of acrylonitrile was used.)
  • the reaction solution was then heated to 50-55 0 C for 4 hr.
  • the solution was then allowed to cool to room temperature and the reaction was neutralized by addition of acetic acid (2.5 ml). Removal of the solvent under reduced pressure gave the product as a clear, viscous oil (324 g).
  • Tetramethylammonuium hydroxide can be used to substitute lithium hydroxide.
  • a 1000 mL three-necked round-bottomed flask was equipped with a mechanical stirrer, condenser, and addition funnel under nitrogen.
  • CE-Sorb6 14.77 g, 29.5 mmol
  • water 200 mL
  • hydroxylamine hydrochloride 11.47 g, 165 mmol, 5.6 eq
  • ammonium hydroxide 22.1 mL of 28% solution, 177 mmol, 6.0 eq
  • hydroxylamine solution was then added in one portion directly to the mixture in the round-bottomed flask at room temperature.
  • Hydroxylamine freebase (50%) aqueous solution can be used to replace the solution by blending hydroxylamine chloride and ammonium hydroxide.
  • the IR spectrum indicated loss of most of the nitrile peak at 2250 cm-1 and the appearance of a new peak at 1660 cm-1, indicative of the amidoxime or hydroxamic acid.
  • polyamidoxime Preparation and analysis of polyamidoxime is essentially that described in U.S. 3,345,344, which is incorporated herein by reference in its entirety.
  • 80 parts by weight of polyacrylonitrile of molecular weight of about 130,000 in the form of very fine powder (-300 mesh) was suspended in a solution of 300 parts by weight of hydroxylammonium sulfate, 140 parts by weight of sodium hydroxide and 2500 parts by weight of deionized water.
  • the pH of the solution was 7.6.
  • the mixture was heated to 90° C and held at that temperature for 12 hours, all of the time under vigorous agitation. It was cooled to 35° C and the product filtered off and washed repeatedly with deionized water.
  • the resin remained insoluble throughout the reaction, but was softened somewhat by the chemical and heat. This caused it to grow from a very fine powder to small clusters of 10 to 20 mesh.
  • the product weighed 130 grams. The yield is always considerably more than theoretical because of fumly occluded salt.
  • the product is essentially a poly-amidoxime having the following reoccurring unit
  • Amidoxime chelating agents can substitute for organic carboxylic acids, organic carboxylic ammonium salt or an amine carboxylates being used in cleaning formulations and processes.
  • One embodiment involves a method for removing organometallic and organosilicate residues remaining after a dry etch process from semiconductor substrates.
  • the substrate is exposed to a conditioning solution of phosphoric acid, hydrofluoric acid, and a carboxylic acid, such as acetic acid, which removes the remaining dry etch residues while minimizing removal of material from desired substrate features.
  • the approximate proportions of the conditioning solution are typically 80 to 95 percent by weight amidoxime compound and acetic acid, 1 to 15 percent by weight phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric acid. See, U.S. Patent No. 7,261,835.
  • Another embodiment includes from about 0.5% to about 24% by weight of complexing agents with amidoxime functional groups with an method having a pH between about 1.5 and about 6 and comprising: at least about 75% by weight of a mixture of water and an organic solvent; from about 0.5% to about 10% by weight 'phosphoric acid; optionally one or more other acid compounds; optionally one or more fluoride-containing compounds; and at least one alkaline compound selected from the group consisting of: a trialkylammonium hydroxide and/or a tetraalkylammonium hydroxide; a hydroxylamine derivative; and one or more alkanolamines.
  • Example 2 Example 2
  • Table 1 lists other embodiments of the present invention where the formulations additionally include from about 0.5% to about 24% by weight of compounds with amidoxime functional groups in methods.
  • Such formulations may contain additional components consistent with this application such as surfactants, alkaline components, and organic solvents.
  • compositions for cleaning or etching a , semiconductor substrate and method for using the same.
  • the compositions include from about 0.01% to about 50%, more preferably about 0.5% to about 24% by weight of compounds with amidoxime functional groups may include a fluorine-containing compound as an active agent such as a quaternary ammonium fluoride, a quaternary phosphonium fluoride, sulfonium fluoride, more generally an -onium fluoride or "multi" quaternary -onium fluoride that includes two or more quaternary- onium groups linked together by one or more carbon-containing groups.
  • a fluorine-containing compound as an active agent such as a quaternary ammonium fluoride, a quaternary phosphonium fluoride, sulfonium fluoride, more generally an -onium fluoride or "multi" quaternary -onium fluoride that includes two or more quaternary- onium groups linked together by one or
  • the composition may further include a pH adjusting acid such as a mineral acid, carboxylic acid, dicarboxylic acid, sulfonic acid, or combination thereof to give a pH of about 2 to 9.
  • a pH adjusting acid such as a mineral acid, carboxylic acid, dicarboxylic acid, sulfonic acid, or combination thereof to give a pH of about 2 to 9.
  • the composition can be anhydrous and may further include an organic solvent such as an alcohol, amide, ether, or combination thereof.
  • the composition is useful for obtaining improved etch rate, etch selectivity, etch uniformity and cleaning criteria on a variety of substrates.
  • the present invention can be used with methods and compositions for removing silicon-containing sacrificial layers from Micro Electro Mechanical System (MEMS) and other semiconductor substrates having such sacrificial layers is described.
  • the etching compositions include a supercritical fluid (SCF), an etchant species, a co-solvent, chelating agent containing at least one amidoxime group, and optionally a surfactant.
  • SCF supercritical fluid
  • etchant species e.g., a co-solvent
  • chelating agent containing at least one amidoxime group e.g., the non-polar character of SCFs and their associated inability to solubilize polar species that must be removed from the semiconductor substrate.
  • the resultant etched substrates experience lower incidents of stiction relative to substrates etched using conventional wet etching techniques. See U.S. Patent No. 7,160,815.
  • Example 5 Example 5
  • the invention uses a supercritical fluid (SFC)- based composition, comprising at least one co-solvent, at least one etchant species, and optionally at least one surfactant, wherein said at least one etchant comprises an alkyl phosphonium difluoride and wherein said SFC-based composition is useful for etching sacrificial silicon-containing layers, said compositions containing from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating group, at least one being an amidoxime functional groups.
  • SFC supercritical fluid
  • the surfactant comprises at least one nonionic or anionic surfactant, or a combination thereof, and the surfactant is preferably a nonionic surfactant selected from the group consisting of fluoroalkyl surfactants, polyethylene glycols, polypropylene glycols, polyethylene ethers, polypropylene glycol ethers, carboxylic acid salts, dodecylbenzenesulfonic acid; dodecylbeuzenesulfonic salts, polyaciylate polymers, dinonylphenyl polyoxyethylene, silicone polymers, modified silicone polymers, acetylenic diols, modified acetylenic diols, alkylammonium salts, modified alkylammonium salts, and combinations comprising at least one of the foregoing.
  • a nonionic surfactant selected from the group consisting of fluoroalkyl surfactants, polyethylene glycols, polypropylene glycols, polyethylene ethers, polypropy
  • compositions for use in semiconductor processing wherein the composition comprises water, phosphoric acid, and an organic acid; wherein the organic acid is ascorbic acid or is an organic acid having two or more carboxylic acid groups (e.g., citric acid).
  • the said compositions containing from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and such compounds can be in addition to, part of, or in substitution of the organic acid.
  • the water can be present in about 40 wt. % to about 85 wt. % of the composition
  • the phosphoric acid can be present in about 0.01 wt.
  • Example 7 % to about 10 wt. % of the composition, and the organic acid can be present in about 10 wt. % to about 60 wt. % of the composition.
  • the composition can be used for cleaning various surfaces, such as, for example, patterned metal layers and vias by exposing the surfaces to the composition. See U.S. Patent No. 7,135,444. [00382] Example 7
  • the present invention can also be used with a polishing liquid composition for polishing a surface, with one embodiment comprising an insulating layer and a metal layer, the polishing liquid composition comprising a compound having six or more carbon atoms and a structure in which each of two or more adjacent carbon atoms has a hydroxyl group in a molecule, and water, wherein the compound having a structure in which each of two or more adjacent carbon atoms has a hydroxyl group in a molecule is represented by the formula (I): Rl-X-(CH 2 )q-[CH(OH)] n ⁇ CH 2 OH (I) wherein Rl is a hydrocarbon group having 1 to 12 carbon atoms; X is a group represented by (CH 2 ) m , wherein m is 1, oxygen atom, sulfur atom, COO group, OCO group, a group represented by NR 2 or 0(R 2 O)P(O)O, wherein R 2 is hydrogen atom or a hydrocarbon
  • compositions for use in semiconductor processing wherein the composition comprises water, phosphoric acid, and an organic acid; wherein the organic acid is ascorbic acid or is an organic acid having two or more carboxylic acid groups (e.g., citric acid), further comprising from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and such compounds can be in addition to, part of, or in substitution of the organic acid.
  • the water can be present in about 40 wt. % to about 85 wt. % of the composition
  • the phosphoric acid can be present in about 0.01 wt.
  • Example 9 Example 9
  • from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound can be used with an oxidizing solution and process for the in situ oxidation of contaminants, including hydrocarbon, organic, bacterial, phosphonic acid, and other contaminants, the contaminants being found in various surfaces and media, including soil, sludge, and water.
  • the solution further includes a peroxygen compound, such as hydrogen peroxide, in solution with a pre-mixed solution of a carboxylic acid and a halogen salt, such as glycolic acid and sodium bromide, respectively.
  • from about 0.01% to about 5% by weight, preferably about 0.01 to about 0.1% of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound can be used with a chemical mechanical polishing slurry that is free of heteropolyacid and consisting essentially of about 3 to about 5 percent abrasive, about 3 to about 5 percent , hydrogen peroxide, about 0.05 to about 0.1 percent citric acid, about 0.05 to about 0.5 percent iminodiacetic acid, about 0.005 to about 0.02 percent ammonia, and about 85-90 percent water, wherein the abrasive consists essentially of polymethylmethacrylate. See U.S. Patent No. 7,029,373. [00390] Example 11:
  • the present invention includes a non-corrosive cleaning composition for removing residues from a substrate comprising: (a) water; (b) at least one hydroxyl ammonium compound; (c) at least one basic compound, preferably selected from the group consisting of amines and quaternary ammonium hydroxides; (d) at least one organic carboxylic acid; (e) from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and such compounds can be in addition to, part of, or in substitution of the organic acid; and (f) optionally, a polyhydric compound.
  • the pH of the composition is preferably between about 2 to about 6. See U.S. Patent No. 7.001,874, which is incorporated herein by reference.
  • the present invention may also be used with a cleaning solution where the cleaning solution also contains one of polyvalent carboxylic acid and its salt, such as where the polyvalent carboxylic acid contains at least one selected from the group consisting of oxalic acid, citric acid, malic acid, maleic acid, succinic acid, tartaric acid, and malonic acid, wherein the cleaning solution contains from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and such compounds can be in addition to, part of, or in substitution of the organic acid, which can be used in addition to, as part of, or in substitution of the polyvalent carboxylic acid.
  • the cleaning solution further contains a polyamino carboxylic acid and its salt. See U.S. Patent No. 6,998,352.
  • a further embodiment of the present invention is to a method of chemically-mechanically polishing a substrate, which method comprises: (i) contacting a substrate comprising at least one layer of ruthenium and at least one layer of copper with a polishing pad and a chemical-mechanical polishing composition comprising: (a) an abrasive consisting of ⁇ -alumina treated with a negatively-charged polymer or copolymer, (b) hydrogen peroxide, (c) from about 0.01% to about 50% by weight, preferably about 0.5% to about 24% of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound; (d) at least one heterocyclic compound, wherein the at least one heterocyclic compound comprises at least one nitrogen atom, (e) a phosphonic acid, and (f) water, (ii) moving the polishing pad relative to the substrate, and (iii) abrading at least a portion of the substrate to polish the substrate, wherein the pH
  • Another embodiment of the present invention is to a semiconductor wafer cleaning formulation, including 1-21% wt. fluoride source, 20-55% wt. organic amine(s), 0.5-40% wt. nitrogenous component, e.g., a nitrogen-containing carboxylic acid or an imine, 23-50% wt. water, and 0-21% wt. of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound.
  • the formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures. See U.S. Patent No. 6,967,169.
  • Example 15 Example 15:
  • the present invention also includes a method for chemical mechanical polishing copper, barrier material and dielectric material, the method comprises the steps of: a) providing a first chemical mechanical polishing slurry comprising (i) 1-10 wt. % silica particles, (ii) 1-12 wt. % oxidizing agent, and (iii) 0-2 wt. % corrosion inhibitor and cleaning agent, wherein said first slurry has a higher removal rate on copper relative to a lower removal rate on said barrier material; b) chemical mechanical polishing a semiconductor wafer surface with said first slurry; c) providing a second chemical mechanical polishing slurry comprising (i) 1-10 wt.
  • the present invention further includes a method for cleaning a surface of a substrate, which comprises at least the following steps (1) and (2), wherein the step (2) is carried out after carrying out the step (1): Step (1): A cleaning step of cleaning the surface of the substrate with an alkaline cleaning agent containing a complexing agent, and Step (2): A cleaning step employing a cleaning agent having a hydrofluoric acid content C (wt %) of from 0.03 to 3 wt %, the complexing agent is from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound. See U.S. Patent No. 6,896,744.
  • Another embodiment of the present invention includes a cleaning gas that is obtained by vaporizing a carboxylic acid and/or a compound with one or more chelating groups/agents, at least one being an amidoxime functional group/compound which is supplied into a treatment chamber having an insulating substance adhering to the inside thereof, and the inside of the treatment chamber is evacuated.
  • the cleaning gas supplied into the treatment chamber comes in contact with the insulating substance adhering to an inside wall and a susceptor in the treatment chamber, the insulating substance is turned into a complex, so that the complex of the insulating substance is formed.
  • the complex of the insulating substance is easily vaporized due to its high vapor pressure.
  • the vaporized complex of the insulating substance is discharged out of the treatment chamber by the evacuation. See U.S. Patent No. 6,893,964.
  • the present invention includes a method for rinsing metallized semiconductor substrates following treatment of the substrates with an etch residue removal chemistry, the method comprising the steps of: providing at least one metallized semiconductor substrate, the substrate having etch residue removal chemistry thereon, wherein the etch residue removal chemistry includes N-methylpyrrolidinone; rinsing the etch residue removal chemistry from the substrate and minimizing metal corrosion of the substrate by rinsing the substrate with an aqueous medium comprising an an ti -corrosive agent including an organic acid selected from the group consisting of mono- and polycarboxylic acids in an amount effective to minimize metal corrosion; removing the aqueous medium from the process vessel; and introducing a drying vapor into the process vessel which the substrate remains substantially stationary within the process vessel, wherein the remover includes from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional
  • the present invention may also be used with the compositions of U.S.
  • Patent No. 6,849,200 wherein the iminodiacetic acid component is supplemented by or substituted with compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound.
  • the present invention also includes a method of cleaning a surface of a copper-containing material by exposing the surface to an acidic mixture comprising NO3-,
  • the mixture may also include one or more organic acids to remove at least some of the particles. See U.S. Patent No.
  • the present invention also includes a cleaning composition comprising at least one of fluoride salts and hydrogendifluoride salts; an organic solvent having a hetero atom or atoms; optionally one or more surfactants in an amount of from 0.0001 to
  • the present invention further includes a glycol-free composition for cleaning a semiconductor substrate, the composition consisting essentially of: a. an acidic buffer solution having an acid selected from a carboxylic acid and a polybasic acid and an ammonium salt of the acid in a molar ratio of acid to ammonium salt ranging from 10:1 to
  • Example 23 wherein the acidic buffer solution is present in an amount sufficient to maintain a pH of the composition from about 3 to about 6, b. from 30% by weight to 90% by weight of an organic polar solvent that is miscible in all proportion in water, c. from 0.1% by weight to 20% by weight of fluoride, d. from 0.5% by weight to 40% by weight of water, and e. optionally up to 15% by weight of a corrosion inhibitor.
  • the composition further contains from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound or such compounds may be used in place of the corrosion inhibitor. See U.S. Patent No. 6,828,289. [00414] Example 23:
  • the present invention further includes compositions containing AEEA and or AEEA derivatives which can be present in an amount ranging from about 1% to about 99%, though in most instances the amount ranges from about 10% to about 85%.
  • AEEA range given for various compositions described herein, there is a "high- AEEA” embodiment where the amount of AEEA is in the upper half of the range, and a “low- AEEA” embodiment where AEEA is present in an amount bounded by the lower half of the range.
  • the embodiments further include from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound.
  • these compositions also include other compounds, particularly polar organic solvents, water, alkanolamines, hydroxylamines, additional chelating agents, and/or corrosion inhibitors. See U.S. Patent No. 6,825,156. [00416] Example 24:
  • a composition for the stripping_of photoresist and the cleaning of residues from substrates, and for silicon oxide etch comprising from about 0.01 percent by weight to about 10 percent by weight of one or more fluoride compounds, from about 10 percent by weight to about 95% by weight of a sulfoxide or sulfone solvent, and from about 20 percent by weight to about 50 percent by weight water, further including from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound.
  • the composition may contain corrosion inhibitors, chelating agents, co- solvents, basic amine compounds, surfactants, acids and bases. See U.S. Patent No. 6,777,380.
  • a polishing composition for polishing a semiconductor substrate has a pH of under 5.0 and comprises (a) a carboxylic acid polymer comprising polymerized unsaturated carboxylic acid monomers having a number average molecular weight of about 20,000 to 1,500,000 or blends of high and low number average molecular weight polymers of polymerized unsaturated carboxylic acid monomers, (b) 1 to 15% by weight of an oxidizing agent, (c) up to 3.0% by weight of abrasive particles, (d) 50-5,000 ppm (parts per million) of an inhibitor, (e) up to 3.0% by weight of a complexing agent, such as, malic acid, and (f) 0.1 to 5.0% by weight of a surfactant, from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound. See U.S. Patent No. 6,679,928. [00
  • Particulate and metal ion contamination is removed from a surface, such as a semiconductor wafer containing copper damascene or dual damascene features, employing aqueous composition comprising a fluoride containing compound; a dicarboxylic acid and/or salt thereof; and a hydroxycarboxylic acid and/or salt thereof, the composition contains from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound. See U.S. Patent No. 6,673,757. [00422] Example 27:
  • a semiconductor wafer cleaning formulation including 2-98% wt. organic amine, 0-50% wt. water, 0.1-60% wt. 1,3-dicarbonyl compound chelating agent, 0-25% wt. of additional different chelating agent(s), 0.5-40% wt. nitrogen-containing carboxylic acid or an imine, and 2-98% wt polar organic solvent.
  • the formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.
  • compositions used are aqueous, acidic compositions containing flouride and polar, organic solvents.
  • the compositions are free of glycols and hydroxyl amine and have a low surface tension and viscosity and further include from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound. See U.S. Patent No. 6,656,894.
  • Example 29 Example 29:
  • the invention includes a method of cleaning a surface of a copper- containing material by exposing the surface to an acidic mixture comprising NO3-, F- and from about 0.01% to about 50% by weight, preferably about 0.5% to about 24%, of compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and/or one or more organic acid anions having carboxylate groups.
  • the invention also includes an improved semiconductor processing method of forming an opening to a copper-containing material. A mass is formed over a copper- containing material within an opening in a substrate. The mass contains at least one of an oxide barrier material and a dielectric material.
  • a second opening is etched through the mass into the copper-containing material to form a base surface of the copper-containing material that is at least partially covered by particles comprising at least one of a copper oxide, a silicon oxide or a copper fluoride.
  • the base surface is cleaned with a solution comprising nitric acid, hydrofluoric acid and one or more organic acids to remove at least some of the particles.
  • An exemplary composition includes an acetic acid solution (99.8%, by weight in water), an HF solution (49%, by weight in water), an HNO3 solution (70.4%, by weight in water), and H2O the resulting cleaning mixture being: from about 3% to about 20% compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, by weight; from about 0.1% to about 2.0% HN03 by weight; and from about 0.05% to about 3.0% HF, by weight. See U.S. Patent No. 6,589,882. [00429] Example 30:
  • Another embodiment of the present invention is a composition for selective etching of oxides over a metal.
  • the composition contains water, hydroxylammonium salt, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, a fluorine containing compound, and optionally, a base.
  • the pH of the composition is about 2 to 6. See U.S. Patent No. 6,589,439.
  • Example 31 Another embodiment of the present invention is an etching treatment comprising a combination including hydrofluoric acid of 15 percent by weight to 19 percent by weight, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound of 0.5 percent by weight to 24 percent by weight and ammonium fluoride of 12 percent by weight to 42 percent by weight, said combination having a hydrogen ion concentration of 10-6 mol/L to 10-1.8, further comprising a surfactant of 0.001 percent by weight to 1 percent by weight. See U.S. Patent No. 6,585,910. [00433]
  • Example 32 Example 32:
  • Another embodiment of the present invention includes a semiconductor wafer cleaning formulation, including 2-98% wt. organic amine, 0-50% wt. water, 0.1-60% wt. one or more compounds with one or more chelating groups/agents,, at least one being an amidoxime functional group/compound, 0-25% wt. of additional different chelating agent(s), 0.1-40% wt. nitrogen-containing carboxylic acid or an imine, optionally 1,3-dicarbonyl compound chelating agent, and 2-98% wt polar organic solvent.
  • the formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures. See U.S. Patent No. 6,566,315.
  • Example 33 Example 33:
  • An alternative embodiment of the present invention is a method for removing organpmetallic and organosilicate residues remaining after a dry etch process from semiconductor substrates.
  • the substrate is exposed to a conditioning solution of a fluorine source, a non-aqueous solvent, a complementary acid, and a surface passivation agent.
  • the fluorine source is typically hydrofluoric acid.
  • the non-aqueous solvent is typically a polyhydric alcohol such as propylene glycol.
  • the complementary acid is typically either phosphoric acid or hydrochloric acid.
  • the surface passivation agent is one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and may optionally include a carboxylic acid such as citric acid.
  • Example 34 Another embodiment of the present invention is a stripping and cleaning composition for the removal of residue from metal and dielectric surfaces in the manufacture of semi-conductors and microcircuits.
  • the composition is an aqueous system including organic polar solvents including corrosive inhibitor component from one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and optionally a select group of aromatic carboxylic acids used in effective inhibiting amounts.
  • a method in accordance with this invention for the removal of residues from metal and dielectric surfaces comprises the steps of contacting the metal or dielectric surface with the above inhibited compositions for a time sufficient to remove the residues. See U.S. Patent No. 6,558,879. [00439] Example 35:
  • Another embodiment of the present invention is a homogeneous nonaqueous composition containing a fluorinated solvent, ozone, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally a co-solvent and the use of these compositions for cleaning and oxidizing substrates is described. See U.S. Patent No. 6,537,380. [00441] Example 36:
  • the present invention also includes a chemical mechanical polishing slurry and method for using the slurry for polishing copper, barrier material and dielectric material that comprises a first and second slurry.
  • the first slurry has a high removal rate on copper and a low removal rate on barrier material.
  • the second slurry has a high removal rate on barrier material and a low removal rate on copper and dielectric material.
  • the first and second slurries at least comprise silica particles, an oxidizing agent, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, optionally a corrosion inhibitor, and a cleaning agent. See, U.S. Patent No. 6,527,819. [00443] Example 37:
  • Another embodiment of the present invention also includes a method for removing organometallic and organosihicate residues remaining after a dry etch process from semiconductor substrates.
  • the substrate is exposed to a conditioning solution of phosphoric acid, hydrofluoric acid, and one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally a carboxylic acid, such as acetic acid, which removes the remaining dry etch residues while minimizing removal of material from desired substrate features.
  • the approximate proportions of the conditioning solution are typically 80 to 95 percent by weight one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and carboxylic acid, 1 to 15 percent by weight phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric acid.
  • compositions for use in semiconductor processing wherein the composition comprises water, phosphoric acid, and one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally an organic acid; wherein the organic acid is ascorbic acid or is an organic acid having two or more carboxylic acid groups (e.g., citric acid).
  • the water can be present in about 40 wt. % to about 85 wt. % of the composition, the phosphoric acid can be present in about 0.01 wt. % to about 10 wt.
  • composition can be used for cleaning various surfaces, such as, for example, patterned metal layers and vias by exposing the surfaces to the composition. See U.S. Patent No. 6,486,108.
  • Another embodiment of the present invention is a method for removing organometallic and organosilicate residues remaining after a dry etch process from semiconductor substrates.
  • the substrate is exposed to a conditioning solution of phosphoric acid, hydrofluoric acid, and one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally a carboxylic acid, such as acetic acid, which removes the remaining dry etch residues while minimizing removal of material from desired substrate features.
  • the approximate proportions of the conditioning solution are typically 80 to 95 percent by weight one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and acetic acid, 1 to 15 percent by weight phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric acid. See U.S. Patent No. 6,453,914. [00449] Example 40:
  • Another example of the present invention is show in cleaning a substrate which has a metal material and a semiconductor material both exposed at the surface and which has been subjected to a chemical mechanical polishing treatment, the substrate is first cleaned with a first cleaning solution containing ammonia water, etc. and then with a second cleaning solution containing (a) a first complexing agent capable of easily forming a complex with the oxide of said metal material, etc. and (b) an anionic or cationic surfactant. See U.S. Patent No. 6,444,583. [00451]
  • Example 41 Example 41:
  • the present invention is also exemplified by a cleaning agent for semiconductor parts, which can decrease a load on the environment and has a high cleaning effect on CMP (chemical mechanical polishing) abrasive particles, metallic impurities and other impurities left on the semiconductor parts such as semiconductor substrates after the CMP, comprising a (co)polymer having one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally at least one kind of group selected from the group consisting of sulfonic acid (salt) groups and carboxylic acid (salt) groups, the cleaning agent further containing a phosphonic acid (salt) group-containing (co)polymer, a phosphonic acid compound or a surfactant as needed; and a method for cleaning semiconductor parts with the above cleaning agent. See U.S. Patent No. 6,440,856. [00453] Example 42:
  • the present invention also includes a non-corrosive cleaning composition for removing residues from a substrate.
  • the composition comprises: (a) water; (b) at least one hydroxylammonium compound; (c) at least one basic compound, preferably selected from the group consisting of amines and quaternary ammonium hydroxides; (d) one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, (e) optionally at least one organic carboxylic acid; and (f) optionally, a polyhydric compound.
  • the pH of the composition is preferably between about 2 to about 6. See U.S. Patent No. 6,413,923.
  • Example 43 Another embodiment of the present invention is a composition comprising a slurry having an acidic pH and a corrosion inhibitor with one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally a carboxylic acid corrosion inhibitor, wherein said carboxylic acid is selected from the group consisting of: glycine, oxalic acid, malonic acid, succinic acid and nitrilotriacetic acid. U.S. Patent No. 6,409,781. [00457] Example 44:
  • An alternative embodiment of the present invention is a chemical formulation consisting of a chelating agent, wherein said chelating agent is one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally one or more additional chelating agents selected from the group consisting of iminodiacetic, malonic, oxalic, succinic, boric and malic acids and 2,4 pentanedione; a fluoride; and a glycol solvent, wherein said chelating agents consist of approximately 0.1-10% by weight of the formulation; and wherein said fluoride consists of a compound selected from the group consisting of ammonium fluoride, an organic derivative of ammonium fluoride, and a organic derivative of a polyammonium fluoride; and wherein said fluoride consists of approximately 1.65-7% by weight of the formulation; and wherein said glycol solvent consists of approximately 73-98.25% by weight of said formulation, further comprising
  • the chelating agents generally contain one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally contain two carboxylic acid groups or two hydroxyl groups or two carbonyl groups such that the two groups in the chelating agent are in close proximity to each other.
  • Other chelating agents which are also weakly to moderately acidic and are structurally similar to those claimed are also expected to be suitable. See U.S. Patent No. 6,383,410. [00459] Example 45:
  • Another embodiment of the present invention is a cleaning composition
  • a cleaning composition comprising a partially fluorinated solvent, a co-solvent, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and ozone
  • said fluorinated solvent comprises hydrofluoroethers
  • said co-solvent is selected from the group consisting of ethers, esters, tertiary alcohols, carboxylic acids, ketones and aliphatic hydrocarbons. See U.S. Patent No. 6,372,700.
  • Example 46 Example 46:
  • Yet another embodiment of the present invention is a combination of one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound and optionally a carboxylic acid corrosion inhibitor.
  • the combination of corrosion inhibitors can effectively inhibit metal corrosion of aluminum, copper, and their alloys.
  • Suitable carboxylic acids include monocarboxylic and polycarboxylic acids.
  • the carboxylic acid may be, but is not limited to, formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, filmaric acid, phthalic acid, 1,2,3- benzenetricarboxylic acid, glycolic acid, lactic acid, citric acid, salicylic acid, tartaric acid, gluconic acid, and mixtures thereof.
  • the preferred carboxylic acid is citric acid.
  • composition for selective etching of oxides over a metal comprising: (a) water; (b) hydroxylammonium salt in an amount about 0.1 wt. % to about 0.5 wt.
  • Example 48 one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound; (d) optionally a carboxylic acid selected from the group consisting of: formic acid, acetic acid, propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fimaric acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, citric acid, salicylic acid, tartaric acid, gluconic acid, and mixtures thereof; (e) a fluorine-containing compound; and (e) optionally, base. See U.S. Patent No. 6,361,712. [00465] Example 48:
  • the invention relates to a semiconductor wafer cleaning formulation for use in post plasma ashing semiconductor fabrication, comprising the following components in the percentage by weight (based on the total weight of the formulation) ranges shown:
  • Another example of the present invention includes an essentially anhydrous cleaning composition
  • a fluorinated solvent comprising 88 weight percent or more of a fluorinated solvent, from 0.005 to 2 weight percent of hydrogen fluoride or complex thereof, and from 0.01 to 5 weight percent of a co-solvent, wherein said co-solvent is selected from one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, ethers, polyethers, carboxylic acids, primary and secondary alcohols, phenolic alcohols, ketones, aliphatic hydrocarbons and aromatic hydrocarbons. See U.S. Patent No. 6,310,018. [00469]
  • Example 50 Example 50:
  • Another embodiment of the present invention includes a chelating agent, a fluoride salt, and a glycol solvent, wherein said chelating agent is weakly to moderately acidic, and consists of approximately 0.1-10% by weight of the formulation; and wherein said fluoride salt consists of a compound selected from the group consisting of ammonium fluoride, an organic derivative of ammonium fluoride, and a organic derivative of a polyammonium fluoride; and wherein said fluoride salt consists of approximately 1.65-7% by weight of the formulation; and wherein said glycol solvent consists of 73-98.25% by weight of said formulation; and further including an amine, wherein said amine consists of approximately 0.1-10% by weight of said formulation; and wherein said chelating agent is an amidoxime or hydroxamic acid. See U.S. Patent No. 6,280,651.
  • Another example of the present invention is a cleaning agent for use in producing semiconductor devices, which consists essentially of an aqueous solution containing (A) 0.1 to 15% by weight based on the total amount of the cleaning agent of at least one fluorine-containing compound selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium hydrogenfluoride, acidic ammonium fluoride, methylamine salt of hydrogen fluoride, ethylamine salt of hydrogen fluoride, propylamine salt of hydrogen fluoride and tetramethylammonium fluoride, (B) 0.1 to 15% by weight based on the total amount of the cleaning agent of a salt of boric acid and (C) 0.5 to 50% by weight of one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound; and (d) 5 to 80% by weight based on the total amount of the cleaning agent of a water-soluble organic solvent, and optionally further containing at least
  • Another embodiment of the present invention includes a cleaning liquid in the form of an aqueous solution for cleaning a semiconductor device during production of a semiconductor device, which comprises (A) a fluorine-containing compound; (B) a water-soluble or water-miscible organic solvent; (C) one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound; (D) optionally, an organic acid; and (E) a quaternary ammonium salt.
  • the cleaning solution also contains a surfactant.
  • the organic acid is typically selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, heptanoic acid, lauric acid, palmitic acid, stearic acid, acrylic acid, crotonic acid, methacrylic acid, oxalic acid, malonic acid, maleic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, benzoic acid, toluic acid, phthalic acid, trimellitic acid, pyromellitic acid, benzenesulfonic acid, toluenesulfonic acid, salicylic acid and phthalic anhydride. See U.S. Patent No.
  • Another embodiment is a method for semiconductor processing comprising etching of oxide layers, especially etching thick SiO2 layers and/or last step in the cleaning process wherein the oxide layers are etched in the gas phase with a mixture of hydrogen fluoride, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally one or more carboxylic acids, eventually in admixture with water.
  • etching of oxide layers especially etching thick SiO2 layers and/or last step in the cleaning process wherein the oxide layers are etched in the gas phase with a mixture of hydrogen fluoride, one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally one or more carboxylic acids, eventually in admixture with water.
  • the complexing agents of the present invention may also be added to the rinse containing a peroxide of U.S. Patent No. 5,911,836.
  • the amidoxime compound is 1, 2, 3, 4, 5, 6-hexakis-0-[3-(hydroxyamino)-3-iminopropyl
  • Hexitol is mixed with hydroxylamine (50%) increases the etch rates exponentially from about 8 A/min to 62 A/min. This indicates the combination of amidoxime compound with hydroxylamine to improve copper and copper oxide debries removal from the CMP processes in the manufacturing of semiconductor devices.
  • Example 61 [00495] Particle performance comparison
  • the wafer After polishing, the wafer is transferred to a brush unit capable of dispensing cleaning chemistries and DI water, and then the wafer is moved to a pencil unit for DI rinse with high pressure jet spray water to the wafer surface.
  • Step 1 Bulk Copper Removal - Standard post CMP clean using process of record
  • Wafer samples from Example 65 are immersed in the cleaning solutions at 6O 0 C for 1 and 4 hours. The samples are then inspected using a Hitachi S- 5200 Scanning Electron Microscope. The results from the SEM pictures show that approximately 25 nm of copper has been eroded using the amidoxime solution of the invention, compared to 130 nm lost in PCMP EKC551O from EKC Technology, Inc.
  • Benzotriazole is commonly used as corrosion inhibitor in CMP slurry mixtures to protect the surface from erosion and dishing. It is highly desirable to remove this BTA/copper complex layer during the post CMP cleaning step.
  • Experiments are carried out to compare the efficacy of amidoxime containing solution to commercial available PCMP5510 solution from EKC Technology. A blanket copper wafer is immersed in 0.2% BTA solution for 30 sec. The BTA treated wafer is then processed through AmiSorbTM DS6 (AmiSorbTM DS6 is 60% l,2,3,4,5,6-hexakis-O-[3-
  • amidoxime solution reduces the surface contact angle much better than PCMP5510, a product from EKC Technology. This indicates a clean copper surface with low contact angle measurement.
  • Amidoxime is capable to remove the BTA/omplex by displacing the BTA and form a water soluble complex.
  • Example 70 [00518] Amidoxime inhibits copper corrosion
  • Adding a composition comprising 5% of amidoxime into a PCMP cleaning formulation decreases the copper etch rate from about 32 A/Min to 0.2 A/Min. This suggests the amidoxime solution of the invention inhibits copper corrosion in an existing PCMP cleaning formulation.
  • Another example of the present invention is a method and apparatus for increasing the deposition of ions onto a surface, such as the adsorption of uranium ions on the detecting surface of a radionuclide detector.
  • the method includes the step of exposing the surface to one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound, and optionally, a phosphate ion solution, which has an affinity for the dissolved species to be deposited on the surface.
  • This provides, for example, enhanced sensitivity of the radionuclide detector. See U.S. Patent No. 5,652,013.
  • Another embodiment of the present invention is a stripping and cleaning agent for removing dry-etching photoresist residues, and a method for forming aluminum based line pattern using the stripping and cleaning agent.
  • the stripping and cleaning agent contains (a) from 5 to 50% by weight of one or more compounds with one or more chelating groups/agents, at least one being an amidoxime functional group/compound; (b) from 0.5 to 15% by weight of a fluorine compound; and (c) a solvent, including water.
  • the inventive method is advantageously applied to treating a dry-etched semiconductor substrate with the stripping and cleaning agent.
  • the semiconductor substrate comprises a semiconductor wafer having thereon a conductive layer containing aluminum.
  • the conductive layer is dry-etched through a patterned photoresist mask to form a wiring body having etched side walls.
  • the dry etching forms a side wall protection film on the side walls.
  • the side wall protection film and other resist residues are completely released without corroding the wiring body. See, U.S. Patent No. 5,630,904.
  • United States Patent No. 6,927,176 describes the effectiveness of chelating compound due to their binding sites and is illustrated in Figures 2a and 2b in US 6,927,176. It highlights there are 6 binding sites
  • the claimed amidoxime chelating agent can substitute in application to replace polyacrylates, carbonates, phosphonates, and gluconates, ethylenediaminetetraacetic acid (EDTA), N,N'-bis(2- hydroxyphenyl)ethylenediiminodiacetic acid (HPED), ,triethylenetetranitrilohexaacetic acid (TTHA) , desferriferrioxamin B ,N,N',N"-tris[2-(N-hydroxycarbonyl)ethyl]-l,3,5- benzenetricarboxamide (BAMTPH) , and ethylenediaminediorthohydroxyphenylacetic acid (EDDHA).
  • EDTA ethylenediaminetetraacetic acid
  • HPED N,N'-bis(2- hydroxyphenyl)ethylenediiminodiacetic acid
  • TTHA triethylenetetranitrilohexaacetic acid
  • BAMTPH benzenetricarboxamide
  • Cleaning solutions of the present application include compositions comprising
  • R a and R b are independently hydrogen, alkyl, hetero-alkyl, alkyl-aryl, or alkyl-heteroaryl groups.
  • R is independently selected from alkyl, alkyl-aryl, or alkyl- heteroaryl groups.
  • chelation of the amidoxime to metal centres may be favoured because, in reaction with a metal centre, a proton can be lost from NR a R b so as to form a nominally covalent bond with the metal centre.
  • NR a R b is further substituted with R c so the amidoxime has the following chemical formula:
  • a counter-ion balances the positive charge on the nitrogen atom.
  • Any counter- ion may be used, for example chloride, bromide, iodide, a SO 4 ion, a PF 6 ion or a ClO 4 ion.
  • R c may be hydrogen, alkyl, alkyl-aryl, or alkyl-heteroaryl group.
  • R a , R b and / or R c can join onto one another and / or join onto R so as to form one or more cycles.
  • amidoxime can exist as their tautomers:
  • amidoxime functional group includes the following functionalities and their tautomers:
  • R may be connected to one or more of R a , R b and R c .
  • amidoxime functional group includes within its scope:
  • AIk is an alkyl group as defined below.
  • the three alkyl groups may be independently selected or may be the same.
  • the alkyl group is methyl or ethyl.
  • R may be an alkyl group (in other words, a group containing carbon and hydrogen).
  • the alkyl group may be completely saturated or may contain unsaturated groups (i.e. may contain alkene and alkyne functional groups, so the term “alkyl” encompasses the terms “alkylene” and “alkylyne” within its scope).
  • the alkyl group may be straight-chained or branched.
  • the alkyl group may contain any number of carbon and hydrogen atoms. While alkyl groups having a lesser number of carbon atoms tend to be more soluble in polar solvents such as DMSO and water, alkyl groups having a greater number of carbons can have other advantageous properties, for example surfactant properties. Therefore, in one embodiment, the alkyl group contains 1 to 10 carbon atoms, for example the alkyl group is a lower alkyl group containing 1 to 6 carbon atoms. In another embodiment, the alkyl group contains 10 or more carbon atoms, for example 10 to 24 carbon atoms.
  • the alkyl group may be unsubstituted (i.e. the alkyl group contains only carbon and hydrogen).
  • the unsubstituted alkyl group may be unsaturated or saturated.
  • saturated unsubstituted alkyl groups include methyl, ethyl, n-propyl, sec-propyl, cyclopropyl, n-butyl, .sec-butyl, tert-buty ⁇ , cyclobutyl, pentyl (branched or unbranched), hexyl (branched or unbranched), heptyl (branched or unbranched), octyl (branched or unbranched), nonyl (branched or unbranched), and decyl (branched or unbranched).
  • Saturated unsubstituted alkyl groups having a greater number of carbons may also be used.
  • Cyclic alkyl groups may also be used, so the alkyl group may comprise, for example, a cyclopropyl group, a cylcobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cylcononyl group and / or a cyclodecyl group.
  • These cyclic alkyl groups may directly append the amidoxime group or may be joined to the amidoxime through one or more carbon atoms.
  • Examples of amidoxime compounds containing unsubstituted saturated alkyl groups include:
  • Examples further include:
  • AIk is methyl or ethyl and R is an alkyl group, typically but not necessarily straight chained.
  • R may be for example an alkyl group containing 8 to 25 carbon atoms.
  • the alkyl group may for example be substituted at the opposite end of the alkyl group to the amidoxime group.
  • it may be substituted antipodally to the amidoxime group by one or more halogens, for example fluorine.
  • Examples further include alkyl groups appending two or more amidoxime functnional groups.
  • amidoxime may be:
  • R is an alkyl group.
  • R is independently selected from alkylene, heteroalkylene, arylene, heteroarylene, alkylene-heteroaryl, or alkylene-aryl group.
  • suitable groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl.
  • alkyl group is unsaturated, it may be any of the groups just listed except for having one or more unsaturated carbon-carbon bonds (so it may contain one or more alkene and / or alkyne groups). These unsaturated group(s) may optionally be in conjugation with the amidoxime group.
  • unsaturated group(s) may optionally be in conjugation with the amidoxime group.
  • a specific example of an unsubstituted unsaturated alkyl amidoxime molecules is:
  • the alkyl group may also be substituted with one or more hetero-atoms or group of hetero-atoms. If more than one hetero-substituent is present, the substituents are independently selected from one another unless they form a part of a particular functional group (e.g. an amide group).. (Groups containing hetero-atoms joined to carbon atoms are contained within the scope of the term "heteroalklyl" as discussed below).
  • the alkyl group may comprise the following functionality: -(CZi)-CH- (CZ 2 )-, wherein Zi and Z 2 are independently selected from O, NH and NOH.
  • the CH in this group is further substituted with hydrogen or an alkyl group or joined to the amidoxime functional group.
  • an alkyl group appending an amidoxime group may simply be substituted with, for example one or more independently-selected halogens, for example fluorine, chlorine, bromine or iodine.
  • the halogens are substituted at the antipodal (i.e. opposite) end of the alkyl group to the amidoxime group. This can for example provide surfactant activity, in particular for example if the halogen is fluorine.
  • a specific example of an amidoxime group substituted with a substituted alkyl group is:
  • R 1 and R 2 are independently-selected alkyl groups or hydrogen atoms.
  • R 1 and R 2 are independently-selected alkyl groups or hydrogen atoms.
  • the different isomers can be differentiated by carbon- 13 NMR. Characterization of this isomer is provided in the example.
  • R may be a heteroalkyl group.
  • heteroalkyl refers to optionally a first alkyl group connected to one or more independently-selected hetero-atoms or groups of hetero-atoms, which itself is substituted with one or more independently-selected groups containing one or more carbon atoms.
  • the presence of the first alkyl group is optional because the amidoxime group may be attached directly to the one or more heteroatoms.
  • an alkyl group substituted with an ether group is a heteroalkyl group because the alkyl group is substituted with oxygen, which itself is substituted with a second alkyl group.
  • an -0-CH 3 group is an example of a heteroalkyl group.
  • the amidoxime may have the following chemical structure:
  • Ri is independently-selected alkylene groups; R y is independently selected from alkyl, or hetero-alkyl groups, or adjoins Ri so to form a heterocycle with the directly appending X n . Ri may also be a direct bond, so that the amidoxime group is connected directly to the one or more heteroatoms.
  • X n is a heteroatom or a group of heteroatoms selected from boron, nitrogen, oxygen, silicon, phosphorus and sulphur. Each heteroatom or group of heteroatoms and each alkyl group is independently selected from one another.
  • the above formula includes an amidoxime group directly bearing an alkyl group.
  • the alkyl group is substituted with N independently-selected heteroatoms or groups of heteroatoms.
  • Each heteroatom or group of heteroatoms is itself substituted with one or more independently-selected alkyl groups or hetero-alkyl groups.
  • X is one or more hetero-atoms.
  • X may be or may comprise boron, nitrogen, oxygen, silicon, phosphorus or sulphur.
  • X is oxygen.
  • X may be part of an ether group (-O-), an ester (-O-CO-), -O-CO- O-, -O-CO-NH-, -0-CO-NR 2 -, -O-CNH-, -O-CNH-O-, -O-CNH-NH-, -0-CNH-NR 2 -, -O- CNOH-, -O-CNOH-O-, -O-CNOH-NH- or -0-CNOH-NR 2 -, wherein R 2 is independently selected alkyl group, hetero-alkyl group, or hetero-aryl group.
  • X is a nitrogen atom.
  • X may be part of one of the following groups: -NR 2 H, - NR 2 -, -NR 2 R 3 - (with an appropriate counter-ion), -NHNH-, -NH-CO-, -NR2-C0-, -NH- CO-O-, -NH-CO-NH-, -NH-CO-NR 2 -, -NR 2 -CO-NH-, -NR 2 -CO-NR 3 -, -NH-CNH-, - NR2-CNH-, -NH-CNH-O-, -NH-CNH-NH-, -NH-CNH-NR 2 -, -NR 2 -CNH-NH-, -NR 2 - CNH-NR 3 -, -NH-CNOH-, -NR2-CN0H-, -NH-CNOH-O-, -NH-CNOH-NH-, -NH-CNOH-NR 2 -, -NH
  • R 2 to R 3 are independently selected alkyl groups, hetero-alkyl groups, or hetero-aryl groups, wherein the heteroalkyl group and hetero-aryl group may be unsubstituted or substituted with one or more heteroatoms or group of heteroatoms or itself be substituted with another heteroalkyl group. If more than one hetero-substituent is present, the substituents are independently selected from one another unless they form a part of a particular functional group (e.g., an amide group).
  • X comprises boron. In this case, X may also comprise oxygen. In another embodiment, X comprises phosphorus.
  • X may also comprise oxygen, for example in an -OPO(OH)(OR 2 ) group or an -OPO(OHR 2 )(OR 3 ) group.
  • X comprises sulphur, for example as a thiol ether or as a sulphone.
  • heteroalkyl also includes within its scope cyclic alkyl groups containing a heteroatom. If X is N or O, examples of such groups include a lactone, lactam or lactim. Further examples of heteroalkyl groups include azetidines, oxetane, thietane, dithietane, dihydrofuran, tetrahydrofuran, dihydrothiophene, tetrahydrothiophene, piperidine, pyroline, pyrolidine, tetrahydropyran, dihydropyran, thiane, piperazine, oxazine, dithiane, dioxane and morpholine.
  • cyclic groups may be directly joined to the amidoxime group or may be joined to the amidoxime group through an alkyl group.
  • the heteroalkyl group may be unsubstituted or substituted with one or more hetero-atoms or group of hetero-atoms or itself be substituted with another heteroalkyl group. If more than one hetero-substituent is present, the substituents are independently selected from one another unless they form a part of a particular functional group (e.g. an amide group).
  • the heteroalkyl group may also be itself substituted with one or more amidoxime functional groups.
  • the heteroalkyl group may comprise an aldehyde, a ketone, a carboxylic acid or an amide.
  • the heteroalkyl group may comprise the following functionality: -(CZO-CH-(CZ 2 )-, wherein Zi and Z 2 are independently selected from O, NH and NOH.
  • the CH in this group is further substituted with hydrogen or an alkyl group or heteroalkyl group or joined to the amidoxime functional group.
  • Amines are particularly versatile functional groups for use in the present invention, in part because of their ease of preparation. For example, by using acrylonitrile as described later, a variety of functionalized amines can be synthesized. [00562] Examples include:
  • R may itself be an alkylene group or a heteroatom or group of heteroatoms.
  • the heteroatoms may be unsubstituted or substituted with one or more alkyl groups.
  • R may itself be a hetero-atom or group of heteroatoms.
  • the heteroatoms may be unsubstituted or substituted with one or more alkyl groups.
  • R may be H, NH 2 , NHR], ORi or NR]R 2 , wherein Ri and R 2 are independently-selected alkyl groups.
  • R may be an aryl group.
  • aryl refers to a group comprising an aromatic cycle.
  • a particular example of an aryl substituent is a phenyl group.
  • the aryl group may be unsubstituted.
  • a specific example of an amidoxime bearing an unsubstituted aryl is:
  • the aryl group may also be substituted with one or more alkyl groups, heteroalkyl groups or heteroatom substituents. If more than one substituent is present, the substituents are independently selected from one another. [00565] Specific examples of amidoximes comprising a heteroalkyl group include:
  • aryl refers to a group comprising an aromatic cycle.
  • the cycle is made from carbon atoms.
  • the cycle itself may contain any number of atoms, for example 3 to 10 atoms. For the sake of convenient synthesis, cycles comprising 5 or 6 atoms have been found to be particularly useful.
  • An example of an aryl substituent is a phenyl group.
  • the aryl group may be unsubstituted.
  • a specific example of an amidoxime bearing an unsubstituted aryl is:
  • the aryl group may also be substituted with one or more alkyl groups, heteroalkyl groups or hetero-atom substituents. If more than one substituent is present, the substituents are independently selected from one another.
  • the one or more alkyl groups are the alkyl groups defined previously and the one or more heteroalkyl groups are the heteroalkyl groups defined previously.
  • substituted aryl amidoxime molecules are:
  • R may also be hetero-aryl.
  • hetero-aryl refers to an aryl group containing one or more hetero-atoms in its aromatic cycle.
  • the one or more hetero-atoms are independently-selected from, for example, boron, nitrogen, oxygen, silicon, phosphorus and sulfur.
  • hetero-aryl groups include pyrrole, furan, thiophene, pyridine, melamine, pyran, thiine, diazine and thiazine.
  • the hetero-aryl group may be unsubstituted.
  • a specific example of an unsubstituted heteroaryl amidoxime molecule is:
  • heteroaryl group may be attached to the amidoxime group through its heteroatom, for example (the following molecule being accompanied by a counter anion):
  • the hetero-aryl group may be substituted with one or more alkyl groups, heteroalkyl groups or hetero-atom substituents. If more than one substituent is present, the substituents are independently selected from one another.
  • the one or more alkyl groups are the alkyl groups defined previously and the one or more heteroalkyl groups are the heteroalkyl groups defined previously.
  • alkyl-aryl refers to an amidoxime group bearing (i.e. directly joined to) an alkyl group. The alkyl group is then itself substituted with an aryl group.
  • heteroaryl are alkyl-heteroaryl groups.
  • the alkyl group may be any alkyl group previously defined.
  • the aryl / heteroaryl group may also be any aryl group previously defined.
  • Both the alkyl group and the aryl / heteroalkyl group may be unsubstituted.
  • unsubstituted alkyl-aryl amidoxime molecules are:
  • one or both of the alkyl group and the aryl / heteroalkyl group may be substituted. If the alkyl group is substituted, it may be substituted with one or more hetero-atoms or groups containing hetero-atoms. If the aryl / heteroalkyl group is substituted, it may be substituted with one or more alkyl groups, heteroalkyl groups or hetero-atom substituents. If more than one substituent is present, the substituents are independently selected from one another.
  • the alkyl group may also be itself substituted with one or more amidoxime functional groups.
  • the alkyl group may comprise an aldehyde, a ketone, a carboxylic acid or an amide.
  • the alkyl group may comprise the following functionality: -(CZi)-CH- (CZ 2 )-, wherein Zi and Z 2 are independently selected from O, NH and NOH.
  • the CH in this- group is further substituted with hydrogen or an alkyl group or heteroalkyl group or joined to the amidoxime functional group.
  • heteroalkyl-aryl refers to an amidoxime group bearing (i.e. directly joined to) an heteroalkyl group. The heteroalkyl group is then itself substituted with an aryl group.
  • heteroaryl are also heteroalkyl-aryl groups.
  • the heteroalkyl group may be any alkyl group previously defined.
  • heteroaryl group may also be any aryl group previously defined. [00584] ' Both the heteroalkyl group and the aryl / heteroaryl group may be unsubstituted. Alternatively, one or both of the heteroalkyl group and the aryl / heteroaryl group may be substituted. If the heteroalkyl group is substituted, it may be substituted with one or more hetero-atoms or groups containing hetero-atoms. If the aryl / heteroaryl group is substituted, it may be substituted with one or more alkyl groups, heteroalkyl groups or hetero-atom substituents. If more than one substituent is present, the substituents are independently selected from one another.
  • the alkyl group may also be itself substituted with one or more amidoxime functional groups.
  • the heteroalkyl group may comprise an aldehyde, a ketone, a carboxylic acid or an amide.
  • the heteroalkyl group may comprise the following functionality: -(CZi)-CH-(CZ 2 )-, wherein Z 1 and Z 2 are independently selected from O, NH and NOH.
  • the CH in this group is further substituted with hydrogen or an alkyl group or heteroalkyl group or joined to the amidoxime functional group.
  • a preferred substituent to any type of R group is a tetra-valent nitrogen.
  • any of the above groups may be substituted with -NR 2 RbRcRd where R a to Ra are independently-selected R groups as defined herein.
  • R 3 to Rj are unsubstituted saturated alkyl groups having 1 to 6 carbon atoms.
  • R a to R d are methyl and / or ethyl.
  • the tetra-valent nitrogen is preferably substituted in an antipodal position to the amidoxime group.
  • the present invention provides an amidoxime molecule that contains only one amidoxime functional group.
  • the present invention provides an amidoxime molecule containing two or more amidoxime functional groups. In fact, a large number of functional groups can be contained in a single molecule, for example if a polymer has repeating units having appending amidoxime functional groups. Examples of amidoxime compounds that contain more than one amidoxime functional groups have been described previously throughout the specification. [00589] Amidoximes may be conveniently prepared from nitrile-containing molecules as follows:
  • hydroxylamine is used. If one or both of R a and R b in the desired amidoxime is not hydrogen, the amidoxime can be prepared either using the corresponding hydroxylamine or by further reacting the amidoxime once it has been formed. This may, for example, occur by intramolecular reaction of the amidoxime.
  • amidoxime molecules containing more than one amidoxime functional groups can be conveniently prepared from precursors having more than one nitrile group.
  • Specific amidoxime molecules having two amidoxime functional groups which have been synthesised in this way include:
  • nucleophiles are well known to the person skilled in the art, see for example the Guidebook to Mechanism in Organic Chemistry by Peter Sykes.
  • suitable nucleophiles are molecules having an OH, SH, NH- or a suitable CH- group, for example one having a low pK a (for example below about 15).
  • OH, SH and NH- the hydrogen is optionally removed before acting as a nucleophile in order to augment its nucleophilicity.
  • CH- they hydrogen is usually removed with a suitable base so that it can act as a nucleophile.
  • Leaving groups are well known to the person skilled in the art, see for example the Guidebook to Mechanism in Organic Chemistry by Peter Sykes. Examples of suitable leaving groups include Cl, Br, I, O-tosyl, O-mesolate and other leaving group well known to the person skilled in the art. The ability to act as a leaving group may be enhanced by adding an acid, either protic or Lewis.
  • a nitrile can be formed accordingly:
  • R 3 is independently selected from alkylene, heteroalkylene, arylene, heteroarylene, alkylene-heteroaryl, or alkylene-aryl group.
  • R n is independently selected from hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, alkyl-heteroaryl, or alkyl-aryl group.
  • X may be any a nucleophile selected from O, S, N, and suitable C. N varies from 1 to 3.
  • Y is a leaving group.
  • the NH may be part of a primary or secondary amine (i.e.
  • XH CH-, wherein a stabilized anion may be formed.
  • XH may be selected from but not limited to -CHCO-R 5 , -CHCOOH, -CHCN, -CHCO-OR 5 , -CHCO- NR 5 R 6 , -CHCNH-R 5 , -CHCNH-OR 5 , -CHCNH-NR 5 R 6 , -CHCNOH-R 5 , -CHCNOH-OR 5 and -CHCNOH-NR 5 R 6 .
  • a preferred example is:
  • R 5 and R 6 are independently-selected alkyl, heteroalkyl, aryl, heteroaryl or alkyl- aryl or a heteroatom optionally substituted with any of these groups.
  • either one or both of R 5 and R 6 are oxygen or nitrogen atoms optionally independently substituted with alkyl, heteroalkyl, aryl, heteroaryl or alkyl-aryl groups, for example:
  • the compounds may also be formed by any type of nucleophilic reaction using any of the above nucleophiles.
  • Rb [00600]
  • X bears N independently-selected substituents.
  • Each R n is independently chosen from hydrogen, alkyl, heteroalkyl, aryl, heteroaryl and alkylaryl as previously defined.
  • X is a nucleophile as previously defined.
  • the acrylonitrile may be substituted as desired. [00601]
  • the acrylonitrile may have the following formula:
  • R 4 , R 5 and R 6 are independently selected from hydrogen, heteteroatoms, heterogroups, alkyl, heteroalkyl, aryl and heteroaryl.
  • the present invention also relates to amidoxime compounds for use in semiconductor processing prepared by the addition of a nucleophile to an unsubstituted or substituted acrylonitrile.
  • the intermediate can be functionalized using standard chemistry known to the person skilled in the art:
  • This reaction is particularly versatile, especially when applied to the synthesis of multidentate amidoxime compounds (i.e. molecules containing two or more amidoxime functional groups). For example, it can be used to functionalize compounds having two or more NH groups. In one example, the reaction can be used to functionalize a molecule containing two or more primary amines. [00605] For example: H 2 N ⁇ ⁇ NH 2 ⁇ ⁇ N ⁇ >* N ⁇ ⁇
  • n 1 or more, for example 1 to 24.
  • a tetradentate amidoxime for example the functional equivalent of EDTA, may be conveniently formed:
  • R 10 is alkyl, heteroalkyl, aryl or heteroaryl.
  • R 1O is nothing: the starting material is hydrazine.
  • An example of this reaction where R 10 is CH 2 CH 2 is provided in the examples.
  • a molecule having two or more secondary amines can be functionaized: ⁇
  • Rio is defined as above and Rn and Ri 2 are independently selected alkyl, heteroalkyl, aryl or heteroaryl. Again, an embodiment where Rio is nothing is contemplated.
  • the secondary amines can be part of a cyclic system:
  • an oxygen nucleophile may be used to provide nitrile precursors to amidoxime molecules.
  • the nucleophile is an alcohol:
  • R 3 is alkyl, heteroalkyl, aryl or heteroaryl.
  • polyalcohol compounds may be functionalized.
  • Poly- alcohols are molecules that contain more than one alcohol functional group.
  • the following is a polyalcohol:
  • n is 0 or more, for example 0 to 24.
  • n is 0 (glycol).
  • n is 6 (sorbitol).
  • the polyalcohol forms part of a polymer.
  • reaction may be carried out with a polymer comprising polyethylene oxide.
  • the polymer may contain just ethylene oxide units, or may comprise polyethylene oxide units as a copolymer (i.e. with one or more other monomer units).
  • the polymer may be a block copolymer comprising polyethylene oxide.
  • the polymer may comprise a monomer unit not containing alcohol units.
  • the polymer may comprise blocks of polyethylene glycol • (PEG).
  • Copolymer (e.g. block copolymers) of polyethylene oxide and polyethylene glycol may be advantageous because the surfactant properties of the blocks of polyethylene glycol can be used and controlled.
  • Carbon nucleophiles can also be used. Many carbon nucleophiles are known in the art. For example, an enol group can act as a nucleophile. Harder carbon- based nucleophiles can be generated by deprotonation of a carbon. While many carbons bearing a proton can be deprotonated if a strong enough base is provided, it is often more convenient to be able to use a weak base to generate a carbon nucleophile, for example NaOEt or LDA. As a result, in one embodiment, a CH group having a pK a of 20 or less, for example 15 or less, is deprotonated to form the carbon-based nucleophile.
  • Ri and R 2 are independently selected alkyl groups, heteroalkyl groups, aryl groups, heteroaryl groups and heteroatoms.
  • Nitrile groups themselves act to lower the pK a of hydrogens in the alpha position. This in fact means that sometimes control of reaction conditions is preferably used to prevent a cyano compound, once formed by reaction of a nucleophile with acrylonitrile, from deprotonating at its alpha position and reacting with a second acrylonitrile group. For example, selection of base and reaction conditions (e.g. temperature) can be used to prevent this secondary reaction.
  • base and reaction conditions e.g. temperature
  • this observation can be taken advantage of to functionalize molecules that already contain one or more nitrile functionalities. For example, the following reaction occurs in basic conditions:
  • the cyanoethylation process usually requires a strong base as a catalyst.
  • alkali metal hydroxides such as, e.g., sodium oxide, lithium hydroxide, sodium hydroxide and potassium hydroxide.
  • These metals can exist as impurities in the amidoxime compound solution.
  • the existence of such metals in the amidoxime compound solution is not acceptable for use in electronic, and more specifically, semiconductor manufacturing processes and as stabilizer for hydroxylamine freebase and other radical sensitive reaction chemicals.
  • Preferred alkali bases are metal ion free organic ammonium hydroxide compound, such as tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide and the like.
  • water may be introduced into the composition essentially only in chemically and/or physically bound form or as a constituent of the raw materials or compounds.
  • the compositon further comprises chemicals from one or more groups selecting from the following:
  • Solvent - From about 1% to 99% by weight.
  • compositions of the present invention also include 0% to about 99% by weight and more typically about 1% to about 80% by weight of a water miscible organic solvent.where the solvent(s) is/are preferably chosen from the group of water miscible organic solvents.
  • water miscible organic solvents include, but are not limited to, dimethylacetamide (DMAC), N-methyl pyrrolidinone (NMP), N-Ethyl pyrrolidone (NEP),
  • HEP N-Hydroxyethyl Pyrrolidone
  • CHP N-Cyclohexyl Pyrrolidone
  • DMSO dimethylformamide
  • NMF N-methylformamide
  • formamide N-methylformamide
  • N-morpholine-N-Oxide tetrahydrofurfuryl alcohol, cyclohexanol, cyclohexanone, polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and/or isopropanol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy,
  • the preferred solvents when employed, are dimethyl acetamide and dimethyl-2-piperidone, dimethylsufoxide and N-methylpyrrolidinone, diglycolamine, and monoethanolamine.
  • Acids From about 0.001% to 15% by weight
  • Possible acids are either inorganic acids or organic acids provided these are compatible with the other ingredients.
  • Inorganic acids include hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, nitric acid, and the like.
  • Organic acids include monomelic and/or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, of branched saturated or unsaturated monocarboxylic acids, of saturated and unsaturated dicarboxylic acids, of aromatic mono-, di- and tricarboxylic acids, of sugar acids, of hydroxy acids, of oxo acids, of amino acids and/or of polymeric carboxylic acids are preferred.
  • hydroxy acids hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), 2,3- dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-l,2,3-propanetricarboxylic acid
  • Bases from about 1% to 45% by weight
  • Possible bases are either inorganic bases or organic bases provided these are compatible with the other ingredients.
  • Inorganic bases include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
  • Organic bases including organic amines, and quaternary alkylammonium hydroxide which may include, but are not limited to, tetramethylammonium hydroxide (TMAH), TMAH pentahydrate, benzyltetramethylammonium hydroxide (BTMAH), TBAH, choline, and Tris(2-hydroxyethyl)methylammonium hydroxide (TEMAH).
  • TMAH tetramethylammonium hydroxide
  • BTMAH benzyltetramethylammonium hydroxide
  • TBAH benzyltetramethylammonium hydroxide
  • TEMAH Tris(2-hydroxyethyl)methylammonium hydroxide
  • the cleaning compositions comprise one or more substances from the group of activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N- acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n- methylmorpholiniumacetonitrile, methylsulfate (MMA), and "nitrile quaternary" compound in amounts of from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight and in particular from 1 to 10% by weight, in each case based on the total composition to enhance the oxidation/reduction performance of the cleaning solutions.
  • the "nitrile quats", cationic nitrites has the formula,
  • hydroxylamine and its salts such as hydroxylamine chloride, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine phosphate or its derivatives, such as N,N-diethylhydroxylamine, N-Phenylhydroxylamine.
  • Hydrazine and its derivatives; hydrogen peroxide; persulfate salts of ammonium, potassium and sodium, permanganate salt of potassium, sodium; and other sources of peroxide are selected from the group consisting of: perborate monohydrate, perborate tetrahydrate, percarbonate, salts thereof, and combinations thereof.
  • hydroxylamine phosphate is not preferred.
  • diacyl peroxides such as, for example, dibenzoyl peroxide.
  • peroxy acids such as the alkyl peroxy acids and the aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, c-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,2-diperoxycarboxylic acid, 1,9- diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-l,
  • the cleaning composition comprises
  • a further possible group of ingredients are the chelate complexing agents.
  • Chelate complexing agents are substances which form cyclic compounds with metal ions, where a single ligand occupies more than one coordination site on a central atom, i.e. is at least "bidentate". In this case, stretched compounds are thus normally closed by complex formation via an ion to give rings. The number of bonded ligands depends on the coordination number of the central ion.
  • Complexing groups (ligands) of customary complex forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals, some-of which have very specific activities toward ions of different metals.
  • chelating/complexing agents include the following, individually or in a mixture with one another: [00651] 1) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
  • nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxy-ethyliminodiacetic acid, nitridodiacetic acid- 3-propionic acid, isoserinediacetic acid, N,N-di( ⁇ -hydroxyethyl)glycine, N-(1, 2- dicarboxy-2-hydroxyethyl)glycine, N-(l,2-dicarboxy-2-hydroxyethyl)-aspartic acid or nitrilotriacetic acid (NTA),
  • geminal diphosphonic acids such as l-hydroxyethane-l,l-diphosphonic acid (HEDP), higher homologs thereof having up to 8 carbon atoms, and hydroxy or amino group-containing derivatives thereof and 1-aminoethane- 1,1 -diphosphonic acid, higher homologs thereof having up to 8 carbon atoms, and hydroxy or amino group- containing derivatives thereof,
  • HEDP l-hydroxyethane-l,l-diphosphonic acid
  • 1-aminoethane- 1,1 -diphosphonic acid higher homologs thereof having up to 8 carbon atoms, and hydroxy or amino group- containing derivatives thereof
  • aminophosphonic acids such as ethylenediamine- tetra(methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri(methylenephosphonic acid),
  • phosphonopolycarboxylic acids such as 2-phosphonobutane- 1,2,4- tricarboxylic acid
  • compositions according to the invention may thus also comprise anionic, cationic, and/or amphoteric surfactants as surfactant component.
  • Source of fluoride ions - From an amount about 0.001% to 10% .
  • Sources of fluoride ions include, but are not limited to, ammonium bifluoride, ammonium fluoride, hydrofluoric acid, sodium hexafluorosilicate, fluorosilicic acid and tetrafluoroboric acid.
  • compositions can be metered and mixed in situ just prior dispensing to the substrate surface for treatment.
  • analytical devices can be installed to monitor the composition and chemical ingredients can be re-constituted to mixture to the specification to deliver the cleaning performance.
  • Critical paramenters that can be monitored includes physical and chemical properties of the composition, such as pH, water concentration, oxidation/reduction potential and solvent components.
  • composition claims a range at point of use and also as mixtures which can be diluted to meet the specific cleaning requirements.
  • N3 represents 3-hydroxypropionitrile and AO3 is N',3- dihydroxypropanimidamide from reacting 3-hydroxypropionitrile with hydroxylamine to form its corresponding amidoxime
  • CE36 represents cyanoethylated product of ethylene glycol and AO36 is from reacting3-(2-ethoxyethoxy) propanenitrile with hydroxylamine to form its corresponding amidoxime.

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Abstract

L'invention concerne un procédé destiné à enlever des résidus et des contaminants de surfaces métalliques ou diélectriques, ainsi qu'un procédé de polissage mécano-chimique d'une surface de cuivre ou d'aluminium. Les procédés de l'invention consistent à utiliser une solution aqueuse renfermant un complexe d'amidoxime. Le pH de la solution peut éventuellement être ajusté avec un acide ou une base. Le procédé consiste à appliquer la composition susmentionnée sur la surface de cuivre ou d'aluminium et à polir la surface en présence de cette composition.
PCT/US2008/012238 2007-10-29 2008-10-29 Procédés de nettoyage de plaquettes après polissage mécano-chimique au moyen de compositions à base d'amidoxime Ceased WO2009058275A1 (fr)

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