Compositions and methods for post-CMP cleaning of cobalt substrates

Abstract

A cleaning composition for removing residues and / or contaminants from microelectronic devices having such residues and / or contaminants thereon is disclosed. The composition comprises at least one complexing agent, at least one cleaning additive, at least one pH adjuster, water, and at least one oxylamine compound. Advantageously, the composition exhibits effective cleaning of cobalt-containing substrates and improved cobalt compatibility.

Description

[Technical Field]

[0001] The present invention generally relates to compositions for removing residues and / or contaminants from microelectronic devices having such residues and / or contaminants thereon, the compositions having improved cobalt compatibility. [Background technology]

[0002] Microelectronic device wafers are used to form integrated circuits and include a substrate, such as silicon, that is patterned with areas for the deposition of different insulating, conductive, or semiconductive materials.

[0003] To obtain accurate patterning, excess material used in forming layers on the substrate must be removed. Furthermore, to fabricate functional and reliable circuits, it is important to prepare a flat or planar microelectronic wafer surface prior to subsequent processing. Therefore, certain surfaces of microelectronic device wafers must be removed and / or polished.

[0004] Chemical-mechanical polishing or planarization ("CMP") is a process that removes material from the surface of a microelectronic device wafer and polishes (more specifically, planarizes) the surface by combining a physical process, such as abrasion, with a chemical process, such as oxidation or chelation. Essentially, CMP involves applying a slurry, such as a combination of abrasives in an aqueous solution containing active chemicals, to a polishing pad that buffs the surface of the microelectronic device wafer to achieve the removal, planarization, and polishing process. The synergistic combination of physical and chemical actions achieves rapid and uniform removal. In integrated circuit manufacturing, CMP slurries must also be able to preferentially remove films, including composite layers of metals and other materials, thereby producing highly planar surfaces for subsequent photolithography, or patterning, etching, and thin-film processing. One key to achieving good uniformity across the entire wafer surface after polishing is to use a CMP slurry with precise removal selectivity for each of the materials present.

[0005] The majority of processing operations, including wafer substrate surface preparation, deposition, plating, etching, and chemical-mechanical polishing, require cleaning operations to ensure that the product is free of contaminants that would otherwise adversely affect the functionality of microelectronic device products or even render the product unusable for its intended function. In many cases, these contaminant particles are smaller than 0.3 μm. If not removed, these residues can, for example, damage copper lines or significantly roughen copper metallization, as well as cause poor adhesion of post-CMP applied layers on the device substrate.

[0006] In particular, as the demand for improved device performance and reduced device and feature sizes increases, there is a continuing need in the industry to provide compositions and methods that effectively and selectively remove various residues from substrates, such as post-CMP residues, post-etch residues, and post-ash residues, that must exclude particles and other contaminants and must not corrode or damage components such as cobalt. Summary of the Invention

[0007] The present invention generally relates to compositions and processes for removing residues and / or contaminants from microelectronic devices having such residues and contaminants on their surfaces. The residues may include post-CMP residues, post-etch residues, and / or post-ash residues. Advantageously, the compositions described herein exhibit improved cobalt compatibility compared to compositions previously described in the art.

[0008] In one aspect, a cleaning composition is described, the composition comprising at least one complexing agent, at least one cleaning additive, at least one pH adjuster, water, and at least one oxylamine compound or salt thereof. In some embodiments, the composition further comprises at least one etchant, at least one corrosion inhibitor, and / or at least one reducing agent. Preferably, the cleaning composition is substantially free of fluoride-containing sources, abrasives, and tetramethylammonium hydroxide.

[0009] In another aspect, a method for removing residue and contaminants from a microelectronic device having the residue and contaminants thereon is described, the method comprising contacting the microelectronic device with a cleaning composition for a time sufficient to at least partially remove the residue and contaminants from the microelectronic device, the cleaning composition comprising at least one complexing agent, at least one cleaning additive, water, at least one pH adjuster, and at least one oxylamine compound or salt thereof. In some embodiments, the composition further comprises at least one etchant, at least one corrosion inhibitor, and / or at least one reducing agent. Preferably, the cleaning composition is substantially free of fluoride-containing sources, abrasives, and tetramethylammonium hydroxide.

[0010] Other aspects, features, and advantages will become more fully apparent from the following disclosure and appended claims. It has been discovered that such compositions can achieve improved cobalt compatibility compared to prior art compositions. Such compatibility is highly beneficial, for example, in post-CMP cleaning in modern microelectronic device manufacturing processes. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention relates generally to compositions useful for removing residues and contaminants from microelectronic devices having such materials thereon, and is particularly useful for removing post-CMP, post-etch, or post-ash residues from cobalt-containing substrates without damaging the bulk cobalt.

[0012] For ease of reference, "microelectronic device" corresponds to semiconductor substrates, flat panel displays, phase change memory devices, solar cell panels and substrates, other products including photovoltaic cells, and microelectronic integrated circuit or microelectromechanical systems (MEMS) fabricated for use in computer chip applications. Solar cell substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar cell substrates may be doped or undoped. The term "microelectronic device" is not meant to be limiting in any way and should be understood to include any substrate that ultimately becomes a microelectronic device or microelectronic assembly.

[0013] The microelectronic device may include a cobalt-containing material. As used herein, "cobalt-containing material" and "cobalt species" include any material containing greater than 50% by weight of elemental cobalt, based on the total weight of the material. Examples of cobalt-containing materials include, but are not limited to, pure cobalt, cobalt nitride (including cobalt nitrides containing additional elements such as Ta or Li), CoP, CoSi, CoW, cobalt oxide, and cobalt hydroxide. Those skilled in the art should understand that the chemical formulas of various cobalt oxides and cobalt nitrides can vary based on the oxidation state of the cobalt ion, with common oxidation states of cobalt being -3, -1, +1, +2, +3, +4, or +5.

[0014] As used herein, "residue" corresponds to particles generated during the manufacture of microelectronic devices, including, but not limited to, plasma etching, ashing, chemical mechanical polishing, wet etching, and combinations thereof.

[0015] As used herein, "contaminants" refers to chemicals present in CMP slurries, reaction by-products of polishing slurries, chemicals present in wet etching compositions, reaction by-products of wet etching compositions, and any other materials that are by-products of CMP processes, wet etching, plasma etching, or plasma ashing processes. Common contaminants include benzotriazole, which is often present in CMP slurries.

[0016] As defined herein, "post-etch residue" corresponds to materials remaining after a gas-phase plasma etching process, such as a BEOL dual damascene process, or after a wet etching process. Post-etch residues can be organic, organometallic, organosilicon, or inorganic in nature, such as silicon-containing materials, carbon-based organic materials, and etching gas residues such as oxygen and fluorine.

[0017] As defined herein, "post-ash residue" as used herein corresponds to materials remaining after oxidizing or reducing plasma ashing to remove hardened photoresist and / or bottom anti-reflective coating (BARC) materials. Post-ash residue may be organic, organometallic, organosilicone, or inorganic in nature.

[0018] As used herein, "post-CMP residue" refers to particles from the polishing slurry, such as silica-containing particles, chemicals present in the slurry, reaction by-products of the polishing slurry, carbon-rich particles, polishing pad particles, brush-shed particles, device component particles, metals, metal oxides, organic residues, barrier layer residues, and any other materials that are by-products of the CMP process. As defined herein, "metals" that are typically polished include copper, aluminum, and tungsten.

[0019] As defined herein, "reaction or decomposition products" include, but are not limited to, products or by-products formed as a result of catalytic reactions at a surface, oxidation, reduction, reaction with a composition component, or otherwise polymerization, and products or by-products formed as a result of a change or transformation in which a substance or material (e.g., a molecule, compound, etc.) combines with other substances or materials, exchanges components with other substances or materials, decomposes, rearranges, or is otherwise chemically and / or physically altered, including intermediate products or by-products of any of the above or any combination of the above reactions, changes, and / or transformations. It is understood that reaction or decomposition products may have a molar mass that is greater or less than that of the original reactants.

[0020] As used herein, "low-k dielectric material" refers to any material used as a dielectric material in integrated microelectronic devices, which material has a dielectric constant of less than about 3.5. Preferably, low-k dielectric materials include low-polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorosilicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is understood that low-k dielectric materials can have varying densities and varying porosities.

[0021] As defined herein, the term "barrier material" corresponds to any material used in the art to encapsulate metal lines, e.g., copper interconnects, to minimize the diffusion of the metal, e.g., copper, into dielectric materials. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, tungsten, cobalt, and nitrides and silicides of any of the foregoing metals.

[0022] As used herein, "complexing agent" includes those compounds that are understood by those skilled in the art to be complexing agents, chelating agents, and / or sequestering agents that chemically bind to or physically retain metal atoms and / or metal ions to be removed using the compositions described herein.

[0023] As used herein, a "fluoride-containing compound" corresponds to a salt or acid compound that contains a fluoride ion (F-) ionically bonded to another atom.

[0024] "Substantially free" is defined herein as less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, and most preferably less than 0.1% by weight. In one embodiment, "substantially free" corresponds to 0%, indicating that the composition does not contain the particular component.

[0025] As used herein, "about" is intended to correspond to ±5% of the stated value.

[0026] As used herein, "suitability" for removing residues and contaminants from a microelectronic device having the residues and contaminants on its surface corresponds to at least partial removal of the residues / contaminants from the microelectronic device. Cleaning effectiveness is evaluated by the reduction of objects on the microelectronic device. For example, pre- and post-cleaning analysis can be performed using an atomic force microscope. Particles on the sample can be recorded as a range of pixels. A histogram (e.g., Sigma Scan Pro) can be applied to filter pixels of a particular intensity, e.g., 231-235, and the number of particles counted. Particle reduction can be calculated using the following: Cleaning effectiveness = (number of objects before cleaning - number of objects after cleaning) / number of objects before cleaning x 100 In particular, the method for determining cleaning effectiveness is provided for illustrative purposes only and is not intended to be limiting. Alternatively, cleaning effectiveness may be considered as the percentage of the total surface covered by particulate matter. For example, an AFM may be programmed to perform a z-plane scan to identify topographical regions of interest above a certain height threshold, and then the total area covered by the target regions may be calculated. Those skilled in the art will readily understand that the smaller the area covered by the target regions after cleaning, the more effective the cleaning composition. Preferably, using the compositions described herein, at least 75% of the residue / contaminants are removed from the microelectronic device, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99% of the residue / contaminants are removed.

[0027] The compositions described herein can be embodied in a wide variety of specific formulations, as described in more detail below.

[0028] In all such compositions where particular components of the composition are discussed in terms of a weight percent range including a zero lower limit, it will be understood that such components may or may not be present in various particular embodiments of the composition, and that when such components are present, they may be present in concentrations as low as 0.001 weight percent, based on the total weight of the composition in which such component is used.

[0029] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations thereof, such as "comprising" and "comprises," mean "including but not limited to" and do not exclude other elements, integers, or steps. However, whenever the word "comprising" is used, embodiments in which "comprising" is interpreted as "consisting of" or "consisting essentially of" are also expressly encompassed.

[0030] As used herein, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating the singular as well as the plural, unless the context otherwise requires.

[0031] Preferred features of each aspect of the invention may be as described in relation to any of the other aspects. Within the scope of this application, it is expressly intended that the various aspects, embodiments, examples and alternatives described in the preceding paragraphs, claims and / or the following description and drawings, particularly individual features thereof, may be employed independently or in any combination. That is, all embodiments and / or features of any embodiment may be combined in any way and / or combination, unless such features are incompatible.

[0032] The cleaning compositions described herein can be substantially free of or free of fluoride-containing sources, abrasives, tetramethylammonium hydroxide (TMAH), and combinations thereof prior to removing residue materials from microelectronic devices. Additionally, the cleaning compositions should not solidify to form polymeric solids, such as photoresists. While it is contemplated that the formulations may include at least one surfactant, it is also contemplated that the formulations may be substantially free of surfactants, as would be readily understood by one skilled in the art.

[0033] The cleaning composition comprises, consists of, or consists essentially of at least one complexing agent, at least one cleaning additive, at least one pH adjuster, water, and at least one oxylamine compound or salt thereof. Preferably, the cleaning composition is an aqueous cleaning composition containing at least 50% water. Advantageously, the cleaning composition increases the removal of contaminants and residues (e.g., benzotriazole, slurry particles, and other post-CMP residues) remaining on exposed cobalt of microelectronic devices while simultaneously reducing the corrosion rate of the exposed cobalt.

[0034] In one preferred embodiment, the cleaning composition of the present disclosure comprises, consists of, or consists essentially of at least one complexing agent, at least one cleaning additive, at least one pH adjuster, at least one oxylamine compound or salt thereof, and water, wherein the cleaning composition is formulated in the following weight percentage ratios: Ingredient Weight Percent Preferred Weight Percent complexing agent Approx. 0.01% to approx. 20% by weight Approx. 0.1% to approx. 10% by weight cleaning additives Approx. 0.01% to approx. 20% by weight Approx. 0.1% to approx. 10% by weight pH adjuster Approximately 0.1% to approximately 10% by weight Approximately 1% to approximately 5% by weight Oxylamine: about 0.01% by weight to about 25% by weight, about 0.1% by weight to about 10% by weight Compound or salt Whenever a component concentration is specified herein, it is understood that water may bring the balance of the composition to 100%. The amount of water in the cleaning composition may be at least 80% by weight, preferably at least 85% by weight, and more preferably at least 90% by weight, based on the total weight of the composition.

[0035] The cleaning compositions of the present disclosure include at least one complexing agent (metal chelating agent, metal complexing agent, or sequestering agent). The complexing agent chemically bonds with or physically retains the metal atoms and / or metal ions to be removed using the compositions described herein. Suitably, the compositions may include a complexing agent component consisting of multiple complexing agents. Exemplary complexing agents are of the general formula NR 1 R 2 R 3 wherein R 1 , R 2 and R 3 may be the same or different and are selected from the group consisting of hydrogen, linear or branched C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, linear or branched C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, and C1-C6 alkyl ethers of linear or branched C1-C6 hydroxyalkyl groups as defined above. Most preferably, R 1 , R 2 and R 3 At least one of the C1-C6 hydroxyalkyl groups is a linear or branched C1-C6 hydroxyalkyl group. Examples include, but are not limited to, alkanolamines such as aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine (MEA), triethanolamine (TEA), isopropanolamine, diisopropanolamine, aminopropyldiethanolamine, N,N-dimethylpropanolamine, N-methylpropanolamine, 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine, triethylenediamine, other C1-C8 alkanolamines, and combinations thereof. When the amine contains an alkyl ether moiety, the amine may be considered an alkoxylamine, such as 1-methoxy-2-aminoethane.

[0036] NR 1 R 2 R 3 Alternatively, or in addition to, an amine, the complexing agent may be a polyfunctional amine, including, but not limited to, 4-(2-hydroxyethyl)morpholine (HEM), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), ethylenediaminetetraacetic acid (EDTA), m-xylenediamine (MXDA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, and combinations thereof.

[0037] Alternatively or in addition to the above-mentioned complexing agents, further complexing agents include phosphonates (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid) (NOTP), hydroxyethyldiphosphonic acid, ... The complexing agent may include a carboxylic acid (e.g., oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or a sulfonic acid (e.g., tiron (4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt)). For example, the at least one complexing agent may include a species selected from the group consisting of monoethanolamine, triethanolamine, sulfuric acid, citric acid, and combinations thereof.

[0038] The amount of complexing agent in the cleaning composition ranges from about 0.01% to about 20% by weight, based on the total weight of the cleaning composition. Preferably, the complexing agent is present in an amount of from about 0.01% to about 10% by weight, more preferably from about 0.01% to about 5% by weight, based on the total weight of the cleaning composition.

[0039] The cleaning compositions of the present disclosure include at least one cleaning additive, which may include various solvents, water-soluble polymers, and surfactants. Preferably, the composition may include a cleaning additive component consisting of multiple cleaning additives. Exemplary cleaning additives include 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraglyme, diglyme, methyl isobutyl ketone, methyl ethyl ketone, acetone, isopropanol, octanol, ethanol, butanol, methanol, isophorone, glycol ethers (e.g., diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether), and the like. ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monohexyl ether (EGHE), diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether, diethylene glycol phenyl ether, hexaethylene glycol monophenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether (DOWANOL PnB, etc.), dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol phenyl ether, propylene glycol phenyl ether (PPh, DOWANOL PPh, etc.), 4-methyl-2-pentanone, 2,4-Dimethyl-3-pentanone, cyclohexanone, 5-methyl-3-heptanone, 3-pentanone, 5-hydroxy-2-pentanone, 2,5-hexanedione, 4-hydroxy-4-methyl-2-pentanone, acetone, butanone, 2-methyl-2-butanone, 3,3-dimethyl-2-butanone, 4-hydroxy-2-butanone, cyclopentanone, 2-pentanone, 3-pentanone, 1-phenylethanone, acetophenone, benzophenone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone , 4-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, dicyclohexyl ketone, 2,6-dimethylcyclohexanone, 2-acetylcyclohexanone, 2,4-pentanedione, menthone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, N-ethylpyrrolidone, ethylene carbonate, propylene carbonate, silane, dimethylethyleneurea, and combinations thereof, but are not limited thereto.

[0040] Alternatively or additionally, the cleaning additive may be, for example, a homopolymer of methacrylic acid and a copolymer thereof, for example, with acrylamidomethylpropanesulfonic acid and maleic acid; a maleic acid / vinyl ether copolymer; a poly(vinylpyrrolidone) / vinyl acetate; a homopolymer such as, for example, a phosphonated polyethylene glycol oligomer, poly(acrylic acid) (PAA), poly(acrylamide), poly(vinyl acetate), poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(styrenesulfonic acid), poly(vinyl sulfonate), poly(vinyl ether ... The surfactants may include water-soluble polymers or surfactants, including poly(vinyl phosphate), poly(vinyl phosphonic acid), poly(vinyl phosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), poly(vinyl alcohol), hydrophilic water-soluble or dispersible polyurethanes, poly(ethylene glycol acrylate), poly(ethylene glycol methacrylate), PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, and combinations thereof.

[0041] Alternatively or in addition, the at least one cleaning additive may be a surfactant, including, but not limited to, anionic, nonionic, cationic, and / or zwitterionic surfactants. Examples include alginic acid and its salts; hydroxyl or carboxyalkyl cellulose; dextran sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; copolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyldimethylammonium chloride (DADMAC), dimethicone, ... Allyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(β-hydroxyethyl)ammonium chloride, diallyldi(β-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamido acid addition salts and quaternary salts, homopolymers of allylamine, diallylamine, vinylamine, vinylpyridine;and diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(β-hydroxyethyl)ammonium chloride, diallyldi(β-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamide acid addition salts and quaternary salts, allylamine, diallylamine , Vinylamine, Vinylpyridine Copolymer;Cocodimethylcarboxymethylbetaine;Lauryldimethylcarboxymethylbetaine;Lauryldimethyl-α-carboxyethylbetaine;Cetyldimethylcarboxymethylbetaine;Lauryl-bis-(2-hydroxyethyl)carboxymethylbetaine;Stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine;Oleyldimethyl-γ-carboxypropylbetaine;Lauryl-bis-(2-hydroxypropyl)α-carboxyethylbetaine;Cocodimethylsulfopropylbetaine;Stearyldimethylsulfopropylbetaine;Lauryl-bis-(2-hydroxyethyl)sulfopropylbetaine;Sodium dodecyl sulfate (SDS);Surfynol 104, Dioctyl sulfosuccinate sodium salt; Sodium lauryl ether sulfate; Polyethylene glycol branched-nonylphenyl ether sulfate ammonium salt; 2-Dodecyl-3-(2-sulfonatophenoxy) disodium salt; PEG25-PABA; Polyethylene glycol mono-C10-16-alkyl ether sulfate sodium salt; (2-N-Butoxyethoxy)acetic acid; Hexadecylbenzenesulfonic acid; Cetyltrimethylammonium hydroxide; Dodecyltrimethylammonium hydroxide; Dodecyltrimethylammonium chloride; Cetyltrimethylammonium chloride; N-Alkyl-N-benzyl-N,N-dimethylammonium chloride; Dodecylamine; Polyoxyethylene lauryl ether;Dodecenyl succinic acid monodiethanolamide; ethylenediamine tetrakis(propoxylate-block-propoxylate); and combinations thereof.

[0042] Specific cleaning additives include, but are not limited to, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose (NaCMC), sodium dodecyl sulfate (SDS); ammonium dodecyl sulfate, potassium dodecyl sulfate, ammonium carboxymethyl cellulose, potassium carboxymethyl cellulose, ammonium alginate, potassium alginate, calcium alginate, Surfynol 104, polyvinylpyrrolidone (PVP), any polymer prepared using N-vinylpyrrolidone monomer, poly(vinyl alcohol), polyacrylates and analogs of polyacrylates, polyamino acids (e.g., polyalanine, polyleucine, polyglycine, etc.), polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyethyleneimine, sugar alcohols such as sorbitol and xylitol, esters of sorbitol anhydrides, secondary alcohol ethoxylates such as TERGITOL, and combinations thereof.

[0043] The amount of cleaning additive in the cleaning composition ranges from about 0.01% to about 20% by weight, based on the total weight of the cleaning composition. Preferably, the cleaning additive is present in an amount of from about 0.1% to about 10% by weight, more preferably from about 0.5% to about 5% by weight, based on the total weight of the cleaning composition.

[0044] The cleaning compositions of the present disclosure include at least one pH adjuster, which is used to raise or lower the pH of the composition to a target value. The pH adjuster may include an acid and / or a base, but preferably the pH adjuster is a base, which is used to raise the pH of the cleaning composition. Exemplary bases include alkali metal hydroxides (e.g., LiOH, KOH, RbOH, CsOH), alkaline earth metal hydroxides (e.g., Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2), ammonium hydroxide (i.e., ammonia), and bases of the formula NR 1 R 2 R 3 R 4 OH (in the formula, R 1 , R 2 , R 3 and R 4 may be the same or different and include hydrogen, linear or branched C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, and substituted or unsubstituted C6-C 10 Examples of suitable tetraalkylammonium hydroxides include, but are not limited to, tetraalkylammonium hydroxide compounds having an aryl group (e.g., benzyl group) selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, and combinations thereof.

[0045] Alternatively or additionally, the pH adjuster may be a compound represented by the formula (PR 1 R 2 R 3 R4 )OH(wherein, R 1 , R 2 , R 3 , and R 4 may be the same or different and include hydrogen, a linear C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) group, a branched C1-C6 alkyl group, a C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) group, a substituted C6-C 10 Aryl groups, unsubstituted C6-C 10 and any combination thereof), such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide.

[0046] The amount of pH adjuster added depends on the desired pH, as disclosed herein and understood by those skilled in the art. For example, the pH adjuster may be present in an amount of about 0.1% to about 10% by weight, more preferably about 1% to about 5% by weight, based on the total weight of the cleaning composition. In one embodiment, the pH adjuster comprises KOH. In another embodiment, the pH adjuster comprises choline hydroxide. In yet another embodiment, the pH adjuster comprises ammonium hydroxide. In another embodiment, the pH adjuster comprises at least one alkali metal hydroxide enumerated herein and at least one additional hydroxide. In another embodiment, the pH adjuster comprises KOH and at least one additional hydroxide enumerated herein. In yet another embodiment, the pH adjuster comprises KOH and at least one additional hydroxide enumerated herein.

[0047] The pH of the cleaning compositions described herein can vary depending on the target application. In one embodiment, the pH of the composition is greater than 7, and thus may be a basic aqueous cleaning composition. In this embodiment, the pH is preferably in the range of about 10 to greater than 14, more preferably in the range of about 12 to about 14, and most preferably in the range of about 13 to 14. It will be understood by those skilled in the art that upon dilution, for example, by forming the concentrations described below and then adding water, the pH of the cleaning composition will be reduced to a range of about 10 to about 12.

[0048] The cleaning compositions described herein contain at least one oxylamine compound or a salt thereof. In particular, the oxylamine compound may be a hydroxylamine or an aminoxyl (nitroxyl) compound. For example, the compositions may contain at least one hydroxylamine compound, at least one aminoxyl compound, or a combination thereof. The oxylamine compound can, in principle, be any compound containing an oxygen group (such as -O or -OH) attached to a nitrogen (N) atom. In some cases, salt forms of the oxylamine compound may be more stable or readily available, and the compound contains a hydroxylate (-OM) group attached to the nitrogen atom. Examples include Na+, K+, Li+, or ammonium salts.

[0049] More specifically, the oxylamine compound is represented by the general formula (I): TIFF0007759807000001.tif28170, or general formula (II) It may also be an aminoxyl compound having the formula TIFF0007759807000002.tif28170. R 1 and R 2may be the same or different and are selected from the group consisting of hydrogen and linear, branched or cyclic alkyl groups including C1-C8 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl). Thus, the oxylamine compound may be an alkyloxylamine (e.g., an alkylhydroxylamine, especially a dialkylhydroxylamine). Suitably, the oxylamine compound may be symmetrical, and R in formula (I) and (II) may be substituted or unsubstituted. 1 and R 2are the same. Examples of hydroxylamine compounds include, but are not limited to, hydroxylamine (NHOH), dimethylhydroxylamine, methylethylhydroxylamine, methylpropylhydroxylamine, methylbutylhydroxylamine, diethylhydroxylamine (DEHA), ethylpropylhydroxylamine, ethylbutylhydroxylamine, dipropylhydroxylamine, propylbutylhydroxylamine, dibutylhydroxylamine, di(t-butyl)hydroxylamine, morpholine-N-hydroxide, N-hydroxysuccinamine, N-hydroxymaleimide, or salts thereof. Examples of salts include, but are not limited to, hydroxylamine hydrochloride, hydroxylamine sulfate, or hydroxylamine acetate. Illustrative examples of aminoxyl compounds include, but are not limited to, 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (sometimes referred to as (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl, or TEMPO), 4-amino-TEMPO, 4-carboxy-TEMPO, 4-phosphonoxy-TEMPO, 4-hydroxy-TEMPO, and polymers with covalently attached TEMPO side or end groups. Other suitable examples include 2,2,5,5-tetramethylpyrrolidin-1-yl)oxidanyl (sometimes referred to as 2,2,5,5-tetramethylpyrrolidine-N-oxyl nitroxide, or PROXYL), 3-amino-PROXYL, 3-carboxy-PROXYL, 3-phosphonoxy-PROXYL, 3-hydroxy-PROXYL, and polymers with covalently attached PROXYL side or end groups.

[0050] In some embodiments, the hydroxylamine may be further functionalized, e.g., R 1 and R 2 is a linear or branched C1-C8 alcohol (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol), and a carboxylic acid of the formula R 4 -OR 5and R 4 and R 5 may be the same or different, and R 4 or R 5 is selected from the group consisting of C1-C8 alkyl attached to N. 1 and / or R 2 may contain a C1-C4 alkyl group.

[0051] In various embodiments, the composition comprises an oxylamine compound or oxylamine compound component described anywhere herein in the range of 0.1-20% w / w, based on the total weight of the composition. Suitably, the amount of oxylamine compound or oxylamine compound component may be in the range of 0.01-10% w / w, for example, in the range of 0.1-7% w / w.

[0052] The amount of the oxylamine compound or salt thereof in the cleaning composition ranges from about 0.01% to about 25% by weight, based on the total weight of the cleaning composition. Preferably, the oxylamine compound is present in an amount of from about 0.1% to about 10% by weight, more preferably from about 0.5% to about 5% by weight, based on the total weight of the cleaning composition.

[0053] The cleaning compositions of the present disclosure may optionally further comprise one or more additional components that may provide additional benefits, particularly for cleaning microelectronic devices that include cobalt-containing materials. In some embodiments, the cleaning compositions may include at least one etchant, at least one corrosion inhibitor, and / or at least one reducing agent.

[0054] For example, the cleaning composition may optionally include at least one etchant. Preferably, the composition may include an etchant component consisting of multiple additional etchants. Examples of etchants include, but are not limited to, morpholine, diglycolamine, 3-butoxypropylamine, propylene glycol monobutyl ether (e.g., DOWANOL PnB), hydroxyethyl morpholine, hydroxypropyl morpholine, aminoethyl morpholine, aminopropyl morpholine, pentamethyldiethylenetriamine (PMDETA), piperazine, N,N-dimethylpropanolamine, ethanolamine, diethanolamine, diethylamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, triethylenetetramine, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, and combinations thereof. In various embodiments, the amount of etchant in the cleaning composition, if present, ranges from about 0.1 wt. % to about 20 wt. % based on the total weight of the cleaning composition. Preferably, the etchant is present in an amount of about 1% to about 20% by weight, more preferably about 1% to about 10% by weight, based on the total weight of the composition. In various embodiments, the cleaning composition does not contain an etchant.

[0055] The cleaning composition may optionally include at least one corrosion inhibitor. Exemplary corrosion inhibitors include acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanediol, methylparaben ... ion, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzoic acid Zohydroxamic acid, 2,5-dicarboxypeptide, 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEdTA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethyl Examples of corrosion inhibitors include, but are not limited to, urea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropargyl alcohol, lauroyl sarcosine, steroyl sarcosine, saccharin, and combinations thereof. In various embodiments, the amount of corrosion inhibitor in the cleaning composition, if present, ranges from about 0.01% to about 10% by weight, based on the total weight of the cleaning composition.Preferably, the corrosion inhibitor is present in an amount of about 0.01% to about 5% by weight, more preferably about 0.05% to about 5% by weight, based on the total weight of the composition. In various embodiments, the cleaning composition does not contain a corrosion inhibitor.

[0056] The cleaning composition may optionally include at least one reducing agent. Exemplary reducing agents include, but are not limited to, ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, sulfurous acid, ammonium sulfite, potassium sulfite, sodium sulfite, dopamine HCl, phosphorous acid, phosphinic acid, hypophosphorous acid, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, potassium pyruvate, sodium pyruvate, ammonium pyruvate, formic acid, sodium formate, potassium formate, ammonium formate, dopamine, sulfur dioxide solution, and any combination thereof. For example, the at least one reducing agent may include at least one sulfite ion and at least one other listed reducing agent, such as sulfurous acid, potassium sulfite, ammonium sulfite, phosphinic acid, and any combination thereof. It should be understood that when ammonium sulfite is present, ammonium sulfite can be generated in situ, and certain combinations of components result in the generation of ammonium sulfite, which aids in the removal of residues, such as ceria particles and other post-CMP residues. In various embodiments, the amount of reducing agent in the cleaning composition, if present, ranges from about 0.0001% to about 1% by weight, based on the total weight of the cleaning composition. Preferably, the reducing agent is present in an amount of from about 0.0001% to about 0.2% by weight, more preferably from about 0.01% to about 0.2% by weight, based on the total weight of the composition. In various embodiments, the cleaning composition does not contain a reducing agent.

[0057] The weight percent ratio ranges of the components encompass all possible concentrated or diluted embodiments of the composition. To that end, in one embodiment, a concentrated removal composition is provided that can be diluted for use as a cleaning solution. Concentrated compositions or "concentrates" advantageously allow the user (e.g., a CMP process engineer) to dilute the concentrate to the desired strength and pH at the point of use. The dilution of the concentrated aqueous removal composition may range from about 1:1 to about 2500:1, preferably from about 5:1 to about 200:1, and most preferably from about 20:1 to about 120:1, and the aqueous removal composition is diluted with a solvent, such as deionized water, at or immediately before the tool. Those skilled in the art will understand that after dilution, the weight percent ratio ranges of the components disclosed herein must remain unchanged.

[0058] The compositions described herein may have utility in applications including, but not limited to, post-etch residue removal, post-ash residue removal surface preparation, post-plating cleaning, and post-CMP residue removal. In addition to cleaning cobalt-containing components, it is contemplated that the aqueous cleaning compositions described herein may also be useful for cleaning and protecting other metal (e.g., copper- and tungsten-containing) articles, including, but not limited to, decorative metals, metal wire bonding, printed circuit boards, and other electronic packages that use metal or metal alloys.

[0059] The aqueous cleaning compositions are easily formulated by simply adding and mixing the individual components to a homogeneous state. Furthermore, the compositions can be easily formulated as single-package or multi-part formulations that are mixed at or before the point of use; for example, the individual parts of a multi-part formulation can be mixed at the tool or in a storage tank upstream of the tool. It should be understood that the concentration of each component can vary widely within a specific number of compositions, i.e., can be more dilute or more concentrated, and that the compositions described herein can variously and alternatively comprise, consist of, or consist essentially of any combination of components consistent with the disclosure herein.

[0060] Accordingly, another aspect relates to a kit comprising, in one or more containers, one or more components adapted to produce the cleaning compositions described herein. The kit may comprise, in one or more containers, at least one complexing agent, at least one cleaning additive, at least one pH adjuster, at least one oxylamine compound, water, optionally at least one etchant, optionally at least one corrosion inhibitor, and optionally at least one reducing agent, for combination with an additional solvent (e.g., water) at a manufacturing plant or at the point of use. Alternatively, the kit may comprise, in one or more containers, at least one complexing agent, at least one cleaning additive, at least one oxylamine compound, water, optionally at least one etchant, optionally at least one corrosion inhibitor, and optionally at least one reducing agent, for combination with the at least one pH adjuster and additional solvent (e.g., water) at a manufacturing plant or at the point of use. The containers of the kit should be suitable for storing and shipping the compositions and may be, for example, NOWPak® containers (Entegris, Inc., Billerica, Massachusetts, USA).

[0061] The one or more containers containing the components of the aqueous cleaning composition preferably include a means for fluidly connecting the components in the one or more containers for blending and dispensing. For example, with reference to a NOWPak® container, gas pressure can be applied to the outside of a liner in the one or more containers to evacuate at least a portion of the contents of the liner, thus enabling fluid communication for blending and dispensing. Alternatively, gas pressure can be applied to the headspace of a conventional pressurizable container, or a pump can be used to enable fluid communication. Additionally, the system preferably includes a dispense port for dispensing the blended removal composition to a process tool.

[0062] When applied to microelectronic manufacturing operations, the cleaning compositions described herein are useful for removing residues and contaminants, including particles, post-CMP residues, post-ash residues, and post-etch residues, from surfaces of microelectronic devices. Advantageously, the disclosed cleaning compositions described herein exhibit improved cobalt compatibility compared to alternative cleaning compositions previously described in the art. Accordingly, the present disclosure further relates to methods of using the cleaning compositions described herein to remove residues and contaminants from microelectronic devices having such residues and contaminants on their surfaces.

[0063] The method comprises contacting a microelectronic device with the disclosed cleaning composition for a time sufficient to at least partially remove residue and contaminants from the microelectronic device; in use, the cleaning composition is typically contacted with the device at a temperature ranging from about 20° C. to about 90° C., preferably from about 20° C. to about 50° C., for a time period ranging from about 5 seconds to about 10 minutes, preferably from about 1 second to about 20 minutes, and preferably from about 15 seconds to about 5 minutes. Such contact times and temperatures are exemplary, and any other suitable time and temperature conditions effective to at least partially remove residue and contaminants from the device may be used within the broad practice of the method. "At least partially remove" and "substantially remove" both correspond to removal of at least 85%, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99% of the ceria particles present on the device prior to particle removal.

[0064] After contacting the device and removing the desired target residue and / or contaminants, the cleaning composition can be easily removed from the device to which the aqueous removal composition was previously applied, as may be desired and effective for a given end-use application of the compositions described herein. For example, a rinse solution may preferably be used, including deionized water. The device can then be dried using nitrogen or a spin cycle, as known in the art.

[0065] Yet another aspect of the present disclosure relates to improved microelectronic devices manufactured according to the methods described herein, and to products comprising such microelectronic devices. Another aspect relates to recycled cleaning compositions, which can be recycled until the particle and / or contaminant load reaches the maximum that the aqueous removal composition can accommodate, as readily determined by one of ordinary skill in the art. As such, the cleaning compositions disclosed herein can contain residue and / or contaminants. The residue and contaminants may be dissolved in the composition. Alternatively, the residue and contaminants may be suspended in the composition. Preferably, the residue comprises post-CMP residue, post-etch residue, post-ash residue, contaminants, or a combination thereof. Yet another aspect relates to a method for manufacturing an article comprising a microelectronic device, the method comprising contacting the microelectronic device with a cleaning composition of the present invention for a time sufficient to remove residue and / or contaminants from the microelectronic device and incorporating the cleaned microelectronic device into the article. Another aspect relates to an article manufactured by this method. [Example]

[0066] The features and advantages of the cleaning compositions of the present disclosure are further illustrated by the following non-limiting examples, in which all parts and percentages are by weight unless otherwise specified. Cleaning compositions are disclosed that are particularly useful for removing residues and contaminants, such as post-CMP residues, post-etch residues, post-ash residues, and contaminants from microelectronic device structures, while remaining compatible with cobalt-containing materials present on the surface.

[0067] Example 1 The following examples demonstrate the effectiveness of adding at least one hydroxylamine to a cleaning composition.

[0068] Two compositions were prepared and are shown below in Table 1. All numbers in the table refer to weight percent based on the total composition, and any deficiencies in the total to 100% are due to rounding only. TIFF0007759807000003.tif31170

[0069] As shown, the only difference between the compositions of Comparative Example 1 and Example 1 is the replacement of an amount of water with DEHA. Comparative Example 1 is a comparative example not according to the present disclosure.

[0070] Each composition was diluted with deionized water at a water to composition ratio of 60:1, and then cobalt coupons were exposed to each diluted composition for 15 minutes at a temperature of 30°C. The extent of etching of the cobalt coupons was determined and is shown in Table 1. As can be seen, the cleaning composition of Comparative Example 1 exhibited an etch rate of 0.6 A / min with a standard deviation of 0.02. In comparison, the composition of Example 1 exhibited an etch rate of 0.4 A / min with a standard deviation of 0.05. These results demonstrate that the inclusion of a hydroxylamine, such as DEHA, is effective in reducing cobalt etching.

[0071] Examples 2 and 3 The following examples demonstrate cleaning compositions of the present disclosure that include at least one hydroxylamine and have high cobalt compatibility.

[0072] A composition of the present disclosure was prepared containing at least one complexing agent, at least one cleaning additive, at least one pH adjuster, and at least one hydroxylamine. The composition was as follows: Example 2: 18.2% choline hydroxide (added as a 46.7% aqueous solution), 1.13% MEA, 0.05% cysteine, 4.9% DEHA, and 75.625% deionized water. The pH of the composition was 13.5. Example 3: 2.09% KOH (added as a 45% aqueous solution), 1.25% MEA, 0.1% cysteine, 0.8% HEDP (added as a 60% aqueous solution), 5.3% morpholine, 1% 1-butoxy-2-propanol, 3% DMSO, 0.9% DEHA, and 85.56% deionized water. All figures refer to weight percent based on total composition and any deficiencies in the total to 100% are due to rounding only.

[0073] Each composition was diluted with deionized water at a ratio of 60:1 water to composition. Cobalt coupons were then exposed to each diluted composition for 15 minutes at a temperature of 30°C, and the extent of etching of the cobalt coupons was determined. Both the compositions of Example 2 and Example 3, which contained DEHA as the hydroxylamine, were found to have improved cobalt compatibility based on their reduced cobalt etching rates.

[0074] Examples 4 to 13 The following examples demonstrate the efficacy of various cleaning compositions of the present disclosure containing at least one hydroxylamine for removing silica slurry from cobalt substrates.

[0075] Compositions of the present disclosure comprising at least one complexing agent, at least one cleaning additive, at least one pH adjuster, and at least one hydroxylamine were prepared and are shown below in Table 2. All numbers in the table refer to weight percent based on the total composition, and any deficiencies in the total to 100% are due only to rounding.

[0076] The indicated compositions were prepared and diluted 100:1 with water. Cobalt coupons were immersed in the silica-containing slurry for 5 minutes, rinsed with deionized water for 30 seconds, then immersed in the cleaning composition for 60 seconds, followed by a second deionized water rinse for 30 seconds. The temperature during immersion was room temperature. The extent of cleaning was determined using scanning electron microscopy (SEM), and the results are shown in Table 3 below. TIFF0007759807000004.tif52170TIFF0007759807000005.tif56170

[0077] As shown, each of the cleaning compositions containing diethylhydroxylamine was able to effectively remove silica slurry particles from the cobalt-containing substrate. Thus, the hydroxylamine-containing compositions are capable of removing residual particles from the cobalt substrate while maintaining effective cobalt compatibility (as demonstrated by the reduced etch rates in Examples 1-3).

[0078] While the invention has been variously disclosed herein with reference to exemplary embodiments and features, it should be understood that the above-described embodiments and features are not intended to limit the invention, and that other variations, modifications, and alternative embodiments may occur to those skilled in the art based on the disclosure herein. Accordingly, the invention should be broadly construed as encompassing all such variations, modifications, and alternative embodiments that fall within the spirit and scope of the claims set forth below.

Claims

1. 1. A cleaning composition for removing residues and contaminants from microelectronic devices having residues and contaminants thereon, the cleaning composition comprising: 0.01% to 20% by weight of at least one complexing agent; 0.01% to 20% by weight of at least one cleaning additive; 0.1% to 10% by weight of at least one pH adjuster; water; and 0.01% to 25% by weight of at least one oxylamine compound or salt thereof; the cleaning composition is an aqueous cleaning composition having a pH in the range of 10 to 14 and comprising at least 50% water; the complexing agent consists of monoethanolamine (MEA), cysteine, and 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP); Detergent additives include 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraglyme, diglyme, methyl isobutyl ketone, methyl ethyl ketone, acetone, isopropanol, octanol, ethanol, butanol, methanol, isophorone, glycol ethers, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, cyclohexanone, 5-methyl-3-heptanone, 3-pentanone, 5-hydroxy-2-pentanone, 2,5-hexanedione, 4-hydroxy-4-methyl-2-pentanone, acetone, butanone, 2-methyl-2-butanone, 3,3-dimethyl-2-butanone, butanone, 4-hydroxy-2-butanone, cyclopentanone, 2-pentanone, 3-pentanone, 1-phenylethanone, acetophenone, benzophenone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, dicyclohexyl ketone, 2,6-dimethylcyclohexanone, 2-acetylcyclohexanone, 2,4-pentanedione, menthone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, N-ethylpyrrolidone, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose (NaCMC), sodium dodecyl sulfate (SDS); Surfynol 104, comprising a species selected from the group consisting of polyvinylpyrrolidone (PVP), polyamino acids, polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyethyleneimine, sorbitol esters, xylitol, esters of sorbitol anhydride, secondary alcohol ethoxylates, potassium alginate, ammonium alginate, poly(ethylene glycol methacrylate), and combinations thereof; the pH adjuster comprises a species selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and combinations thereof; The oxylamine compound has the formula: [In the formula, R １ and R ２ may be the same or different and are selected from the group consisting of hydrogen and linear alkyl, cyclic alkyl, or branched alkyl. or a salt thereof, Cleaning composition.

2. The cleaning additives include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monohexyl ether (EGHE), diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether, diethylene glycol phenyl ether, hexaethylene glycol monophenyl ether, and propylene glycol methyl ether.

10. The cleaning composition of claim 1, comprising a species selected from the group consisting of propylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol phenyl ether, propylene glycol phenyl ether (PPh), and combinations thereof.

3. 10. The cleaning composition of claim 1, wherein the cleaning composition further comprises at least one etchant, the etchant comprising a species selected from the group consisting of morpholine, diglycolamine, 3-butoxypropylamine, hydroxyethylmorpholine, hydroxypropylmorpholine, aminoethylmorpholine, aminopropylmorpholine, pentamethyldiethylenetriamine (PMDETA), piperazine, N,N-dimethylpropanolamine, ethanolamine, diethanolamine, diethylamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, triethylenetetramine, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, and combinations thereof.

4. The cleaning composition may further comprise at least one corrosion inhibitor, and the corrosion inhibitor may be selected from the group consisting of acetic acid, acetone oxime, acrylic acid, adipic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutaric acid, glyceric acid, glycerin, glycolic acid, glyoxylic acid, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, maleic anhydride, mandelic acid, 2,4-pentanedione, phenylacetic acid, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, sorbitol, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, xylitol, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamic acid, 2,5-dicarboxylate, 2,5-dimethylbenzyl benzoate ...

10. The cleaning composition of claim 1, comprising a species selected from the group consisting of puridine, N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEdTA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, salicylic acid, p-toluenesulfonic acid, salicylhydroxamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropargyl alcohol, lauroyl sarcosine, steroyl sarcosine, saccharin, and combinations thereof.

5. 10. The cleaning composition of claim 1, wherein the cleaning composition further comprises at least one reducing agent, the reducing agent comprising a species selected from the group consisting of ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, sulfurous acid, ammonium sulfite, potassium sulfite, sodium sulfite, dopamine HCl, phosphorous acid, phosphinic acid, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, hydroxylamine, potassium pyruvate, sodium pyruvate, ammonium pyruvate, formic acid, sodium formate, potassium formate, ammonium formate, dopamine, sulfur dioxide solution, and combinations thereof.

6. 1. A method of removing residue and contaminants from a microelectronic device having residue and contaminants thereon, comprising contacting the microelectronic device with a cleaning composition for a time sufficient to at least partially remove the residue and contaminants from the microelectronic device, the cleaning composition comprising: 0.01% to 20% by weight of at least one complexing agent; 0.01% to 20% by weight of at least one cleaning additive; 0.1% to 10% by weight of at least one pH adjuster; water; and 0.01% to 25% by weight of at least one oxylamine compound or salt thereof; the cleaning composition is an aqueous cleaning composition having a pH in the range of 10 to 14 and comprising at least 50% water; the complexing agent consists of monoethanolamine (MEA), cysteine, and 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP); Detergent additives include 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraglyme, diglyme, methyl isobutyl ketone, methyl ethyl ketone, acetone, isopropanol, octanol, ethanol, butanol, methanol, isophorone, glycol ethers, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, cyclohexanone, 5-methyl-3-heptanone, 3-pentanone, 5-hydroxy-2-pentanone, 2,5-hexanedione, 4-hydroxy-4-methyl-2-pentanone, acetone, butanone, 2-methyl-2-butanone, 3,3-dimethyl-2-butanone, butanone, 4-hydroxy-2-butanone, cyclopentanone, 2-pentanone, 3-pentanone, 1-phenylethanone, acetophenone, benzophenone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 4-octanone, dicyclohexyl ketone, 2,6-dimethylcyclohexanone, 2-acetylcyclohexanone, 2,4-pentanedione, menthone, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methylpyrrolidone, N-ethylpyrrolidone, hydroxypropyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose (NaCMC), sodium dodecyl sulfate (SDS); Surfynol 104, comprising a species selected from the group consisting of polyvinylpyrrolidone (PVP), polyamino acids, polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyethyleneimine, sorbitol esters, xylitol, esters of sorbitol anhydride, secondary alcohol ethoxylates, potassium alginate, ammonium alginate, poly(ethylene glycol methacrylate), and combinations thereof; the pH adjuster comprises a species selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and combinations thereof; The oxylamine compound has the formula: [In the formula, R １ and R ２ may be the same or different and are selected from the group consisting of hydrogen and linear alkyl, cyclic alkyl, or branched alkyl. or a salt thereof, method.

7. The cleaning additives include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monohexyl ether (EGHE), diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether, diethylene glycol phenyl ether, hexaethylene glycol monophenyl ether, propylene glycol methyl ether 7. The method of claim 6, wherein the propylene glycol comprises a species selected from the group consisting of propylene glycol n-propyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol phenyl ether, propylene glycol phenyl ether (PPh), and combinations thereof.

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