Compositions and methods for cleaning post-cmp cobalt substrates

Abstract

The present application relates to compositions and methods for cleaning cobalt substrates after chemical mechanical polishing (POST-CMP). A cleaning composition for cleaning residues and / or contaminants from microelectronic devices having the 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

[0001] This application is a divisional application of the invention patent application filed on November 25, 2019, with application number "201980083648.0" and entitled "Composition and method for cleaning cobalt substrates after chemical mechanical polishing (POST-CMP)". Technical Field

[0002] The present invention generally relates to a cleaning composition for cleaning residues and / or contaminants from microelectronic devices having such residues and / or contaminants, wherein the composition has modified cobalt compatibility. Background Technology

[0003] Microelectronic device wafers are used to form integrated circuits and include, for example, a substrate of silicon, in which regions are patterned to deposit different materials having insulating, conductive, or semiconductive properties.

[0004] To achieve proper patterning, excess material used to form layers on the substrate must be removed. Furthermore, for the fabrication of functional and reliable circuits, it is important to prepare a flat or planar surface on the microelectronic wafer prior to subsequent processing. Therefore, certain surfaces of the microelectronic device wafer must be removed and / or ground.

[0005] Chemical mechanical polishing or planarization (“CMP”) is a method of removing material from the surface of a microelectronic device wafer and polishing (more specifically, planarizing) the surface by combining physical methods (e.g., abrasion) with chemical methods (e.g., oxidation or chelation). Essentially, CMP involves applying a slurry (e.g., a combination of abrasives containing active chemicals in an aqueous solution) to an abrasive pad that polishes the surface of the microelectronic device wafer to achieve a removal, planarization, and polishing process. The synergistic combination of physical and chemical operations enables rapid and uniform removal. In the fabrication of integrated circuits, CMP slurries should also be able to preferentially remove films containing complex layers of metals and other materials, thereby producing highly flat surfaces for subsequent photolithography, patterning, etching, and thin-film processing. A key to achieving good uniformity across the entire wafer surface after polishing is using a CMP slurry with appropriate removal selectivity for each of the present materials.

[0006] Most processing operations (including wafer substrate surface preparation, deposition, electroplating, etching, and chemical mechanical polishing) require cleaning operations to ensure that microelectronic device products are free of contaminants that could otherwise adversely affect the product's functionality or render it unusable for its intended purpose. Typically, these contaminant particles are smaller than 0.3 μm. If these residues are not removed, they can damage, for example, copper wires or severely roughen copper metallization, and cause poor adhesion of layers applied after CMP on the device substrate.

[0007] There is a continued need in the industry for compositions and methods that can effectively and selectively remove various residues (e.g., post-CMP residues, post-etching residues, and post-ashing residues) from substrates, particularly with the increasing demand for improved device performance and reduced device size and feature size. The compositions and methods should eliminate particles and other contaminants without corroding or otherwise damaging components such as cobalt. Summary of the Invention

[0008] This invention generally relates to compositions and methods for cleaning residues and / or contaminants from microelectronic devices having such residues and / or contaminants. The residues may include post-CMP, post-etching, and / or post-ashing residues. Advantageously, the compositions described herein exhibit improved cobalt compatibility compared to compositions previously described in the art.

[0009] 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 amine compound or a 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 sources, abrasive materials, and tetramethylammonium hydroxide.

[0010] In another aspect, a method for removing residues and contaminants from a microelectronic device having such residues and contaminants is described. This method includes contacting the microelectronic device with a cleaning composition for a time sufficient to at least partially remove the residues and contaminants from the microelectronic device. The cleaning composition comprises at least one complexing agent, at least one cleaning additive, water, at least one pH adjuster, and at least one amine compound or a 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 sources, abrasive materials, and tetramethylammonium hydroxide.

[0011] Other aspects, features, and advantages will become more fully apparent from the following disclosure and the appended claims. Such compositions have been found to achieve improved cobalt compatibility compared to compositions in the prior art. This compatibility offers considerable benefit, for example, in post-CMP cleaning in modern microelectronic device processes. Detailed Implementation

[0012] This invention generally relates to compositions suitable for removing such materials from microelectronic devices containing residues and contaminants. The compositions are particularly suitable for removing CMP, etching, or ashing residues from cobalt-containing substrates without damaging the bulk cobalt.

[0013] For ease of reference, "microelectronic device" refers to semiconductor substrates, flat panel displays, phase-change memory devices, solar panels, and other products including solar substrates, photovoltaics, and microelectromechanical systems (MEMS), manufactured for microelectronic applications, integrated circuit applications, or computer chip applications. Solar substrates include, but are not limited to, silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the term "microelectronic device" is not intended to limit or include in any way any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0014] The microelectronic device may contain cobalt-containing materials. As used herein, "cobalt-containing material" and "cobalt species" include any material containing more than 50 wt% elemental cobalt by total weight of the material. Examples of cobalt-containing materials include, but are not limited to, pure cobalt, cobalt nitride (including cobalt nitride containing additional elements such as Ta or Li), CoP, CoSi, CoW, cobalt oxide, and cobalt hydroxide. Those skilled in the art will understand that the chemical formulas used for various cobalt oxides and cobalt nitrides may vary based on the oxidation state of the cobalt ion, where common oxidation states of cobalt are -3, -1, +1, +2, +3, +4, or +5.

[0015] As used herein, “residue” refers 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.

[0016] As used herein, “contaminant” refers to chemicals present in CMP slurries, reaction byproducts of grinding slurries, chemicals present in wet etching compositions, reaction byproducts of wet etching compositions, and any other materials that are byproducts of CMP processes, wet etching, plasma etching, or plasma ashing processes. Common contaminants include benzotriazole, which is commonly present in CMP slurries.

[0017] As defined herein, “post-etching residue” refers to the material remaining after a vapor-phase plasma etching process (e.g., BEOL bimetallic damascene process or wet etching process). Post-etching residue 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.

[0018] As defined herein, “ash residue” as used herein refers to the material remaining after oxidative or reduction plasma ashing used to remove the hardened photoresist and / or undercoat (BARC) material. Ash residue can be organic, organometallic, organosilicon, or inorganic in nature.

[0019] As used herein, “CMP post-residue” refers to particles from the grinding slurry, such as silica-containing particles, chemicals present in the slurry, reaction byproducts of the grinding slurry, carbon-rich particles, grinding pad particles, brush-off particles, equipment materials used to build the particles, metals, metal oxides, organic residues, barrier layer residues, and any other materials that are byproducts of the CMP process. As defined herein, “metals” typically ground include copper, aluminum, and tungsten.

[0020] As defined herein, "reactants or degradation products" include, but are not limited to, one or more products or byproducts formed by catalysis, oxidation, reduction, reaction with constituent components, or other polymerization at a surface; one or more products or byproducts formed by one or more changes or transformations in which a substance or material (e.g., molecules, compounds, 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 one or more intermediates or byproducts of any of the aforementioned reactions, changes, and / or transformations, or any combination thereof. It should be understood that reactants or degradation products may have a larger or smaller molar mass than the original reactants.

[0021] As used herein, “low-k dielectric material” refers to any material used as a dielectric material in layered microelectronic devices, wherein said 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, organosilicon glasses (OSG), TEOS, fluorinated silicate glasses (FSG), silicon dioxide, and carbon-doped oxide (CDO) glasses. It should be understood that low-k dielectric materials can have different densities and different porosities.

[0022] As defined herein, the term "barrier material" refers to any material in the art used to seal metal wires (e.g., copper interconnects) to minimize the diffusion of the metal (e.g., copper) into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, tungsten, cobalt, and nitrides and silicides of any of the aforementioned metals.

[0023] 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 clamping agents. A complexing agent will chemically combine with or physically clamp said metal atoms and / or metal ions to be removed using the composition described herein.

[0024] As used herein, “fluorine-containing compound” refers to a salt or acid compound in which a fluoride ion (F-) is ionically bonded to another atom.

[0025] "Substantially free of" is defined herein as less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and most preferably less than 0.1 wt.%. In one embodiment, "substantially free of" corresponds to zero percent, indicating that the composition does not contain a specific component.

[0026] As used in this article, “about” is intended to correspond to ±5% of the stated value.

[0027] As used herein, the “suitability” for cleaning residues and contaminants from a microelectronic device with such residues and contaminants corresponds to at least partial removal of the residues / contaminants from the microelectronic device. Cleaning effectiveness is assessed by the reduction of objects on the microelectronic device. For example, atomic force microscopy can be used for pre-cleaning and post-cleaning analyses. Particles on the sample can be recorded as pixel ranges. Histograms (e.g., Sigma Scan Pro) can be applied to filter pixels at a certain intensity (e.g., 231-235) and count the number of particles. Particle reduction can be calculated using the following:

[0028]

[0029] It is worth noting that the methods for measuring cleaning effectiveness are provided as examples only and are not intended to limit us to these examples. Alternatively, cleaning effectiveness can be considered as the percentage of the total surface covered by particulate matter. For example, an AFM can be programmed to perform a z-plane scan to identify areas of surface morphology of interest above a certain height threshold, and then the total surface area covered by said areas of interest can be calculated. Those skilled in the art will readily understand that the smaller the area covered by said areas of interest after cleaning, the more effective the cleaning composition. Preferably, the composition described herein removes at least 75% of residues / contaminants from microelectronic devices, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99%.

[0030] As described more fully below, the compositions described herein can be embodied in a wide variety of specific formulations.

[0031] In all such compositions, where reference weight percentage ranges (including the lower limit of zero) are used to describe a particular component of the composition, it should be understood that the component may be present or absent in various specific embodiments of the composition, and in instances where such a component is present, it may be present at a concentration as low as 0.001 weight percentage based on the total weight of the composition employing such a component.

[0032] Throughout the specific embodiments and claims of this specification, the terms "comprise" and "contain," as well as variations thereof, such as "comprising / comprises," mean "including but not limited to" and do not exclude other components, integers, or steps. However, wherever the term "comprise" is used, it also expressly encompasses embodiments in which "comprise" is understood as "consisting of" or "substantially consisting of."

[0033] In this document, unless the context otherwise requires, the singular form encompasses the plural form. Specifically, when using the indefinite article, unless the context otherwise requires, this instruction should be understood to consider both the plural and singular forms.

[0034] Preferred features of various aspects of the invention may be described as in conjunction with any of the other aspects. Within the scope of this application, it is expressly contemplated that various aspects, embodiments, examples, and alternatives, and particularly their individual features, set forth in the foregoing paragraphs, claims, and / or in the following description and figures, may be employed independently or in any combination. That is, unless such features are incompatible, features of all embodiments and / or any embodiments may be combined in any manner and / or combination.

[0035] Prior to removing residual material from microelectronic devices, the cleaning compositions described herein may be substantially free of or contain no fluoride sources, abrasive materials, tetramethylammonium hydroxide (TMAH), or combinations thereof. Furthermore, the cleaning compositions should not cure to form polymeric solids, such as photoresists. As will be readily understood by those skilled in the art, although formulations are considered to include at least one surfactant, they are also considered to be substantially surfactant-free.

[0036] The cleaning composition comprises, consists of, or is substantially composed of the following components: at least one complexing agent, at least one cleaning additive, at least one pH adjuster, water, and at least one amine compound or a 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 in microelectronic devices while simultaneously reducing the corrosion rate of exposed cobalt.

[0037] In a preferred embodiment, the cleaning composition of this disclosure comprises, is composed of, or substantially comprises: at least one complexing agent, at least one cleaning additive, at least one pH adjuster, at least one oxyamine compound or a salt thereof, and water, wherein the cleaning composition is formulated in the following weight percentage ratios:

[0038]

[0039] Whenever the concentration of a component is specified herein, it should be understood that water can compensate for the remainder of the composition to 100%. The amount of water in the washing composition may be at least 80 wt%, preferably at least 85 wt%, and more preferably at least 90 wt%, based on the total weight of the composition.

[0040] The cleaning compositions disclosed herein comprise at least one complexing agent (metal chelator, metal complexing agent, or metal clamping agent). The complexing agent chemically combines with or physically clamps the metal atoms and / or metal ions to be removed using the compositions described herein. Suitably, the composition may comprise a complexing agent component consisting of a plurality of complexing agents. Illustrative complexing agents may include those having the general formula NR. 1 R 2 R 3 Species, of which R 1 R 2 and R 3 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), straight-chain or branched C1-C6 hydroxyalkyl groups (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl), and C1-C6 alkyl ethers of straight-chain or branched C1-C6 hydroxyalkyl groups, as defined above. Most preferably, R 1 R 2 and R 3 At least one of them is a straight chain or a branched chain C 1- C6 hydroxyalkyl. 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 includes an alkyl ether component, the amine may be considered an alkoxyamine, such as 1-methoxy-2-aminoethane.

[0041] Alternatively or excluding NR 1 R 2 R3 In addition to amines, the complexing agent may also 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), hypozinotriacetic 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.

[0042] Alternatively, in addition to the aforementioned complexing agents, additional complexing agents may 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'''-tetra(methylenephosphonic acid) (DOTP), nitrilotri(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DETAP), aminotris(methylenephosphonic acid), bis(hexyl)triaminepentylphosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid)). (NOTP), hydroxyethyl diphosphonates, tri(methylene)phosphonic acid, 2-phosphono-butane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid), phenylphosphonic acid, its salts and derivatives) and / or carboxylic acids (e.g., oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, trimethylolpropionic acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or sulfonic acids such as styraquinone (disodium salt of 4,5-dihydroxy-1,3-benzenedisulfonic acid). For example, at least one complexing agent may comprise a species selected from the group consisting of monoethanolamine, triethanolamine, sulfuric acid, citric acid and combinations thereof.

[0043] The amount of one or more complexing agents in the cleaning composition is in the range of about 0.01 wt% to about 20 wt% based on the total weight of the cleaning composition. Preferably, the complexing agent is present in an amount of about 0.01 wt% to about 10 wt% based on the total weight of the cleaning composition, and more preferably in an amount of about 0.01 wt% to about 5 wt%.

[0044] The cleaning compositions disclosed herein comprise at least one cleaning additive, which may include various solvents, water-soluble polymers, and surfactants. Suitably, the composition may comprise a cleaning additive component consisting of a variety of cleaning additives. Illustrative cleaning additives include, but are not limited to, 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl ethyl ketone, acetone, isopropanol, octanol, ethanol, butanol, methanol, isophorone, and 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 (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 (e.g., DOWANOL PnB), dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol phenyl ether, propylene glycol phenyl ether (PPh, e.g., DOWANOL PnB) PPh), 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-phenylethylone, acetophenone, benzophenone, 2-hexanone, 3-hexanone 2-Hepanotone, 3-Hepanotone, 4-Hepanotone, 2,6-Dimethyl-4-Hepanotone, 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, Ethyl carbonate, Propylene carbonate, Cyrene, Dimethyl ethyl urea, and combinations thereof.

[0045] Alternatively or additionally, the cleaning additive may include water-soluble polymers or surfactants, including, for example, homopolymers of methacrylic acid and copolymers with, for example, acrylamide methylpropane sulfonic acid and maleic acid; maleic acid / vinyl ether copolymers; poly(vinylpyrrolidone) / vinyl acetate; homopolymers, such as phosphonated polyethylene glycol oligomers, poly(acrylic acid) (PAA), poly(acrylamide), poly(vinyl acetate), poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(styrene sulfonic acid), poly(vinyl sulfonic acid), poly(vinyl phosphonic acid), poly(vinyl phosphate), poly(ethylene imine), poly(propylene imine), 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.

[0046] Alternatively or additionally, at least one cleaning additive may be a surfactant, including but not limited to anionic, nonionic, cationic, and / or amphoteric surfactants. Examples include alginate 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, 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, acrylamidopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyl dimethylammonium chloride (DADMAC). Diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethylallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(β-hydroxyethyl)ammonium chloride, diallyldi(β-ethoxyethyl)ammonium chloride, addition salts and quaternary salts of dimethylaminoethyl(meth)acrylate acid, addition salts and quaternary salts of diethylaminoethyl(meth)acrylate acid, addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl(meth)acrylate acid, addition salts and quaternary salts of N,N'-dimethylaminopropylacrylamide acid, homopolymers of allylamine, diallylamine, ethyleneamine, and vinylpyridine; and chlorinated Diallyl dimethylammonium (DADMAC), diallyl dimethylammonium bromide, diallyl dimethylammonium sulfate, diallyl dimethylammonium phosphate, dimethyl allyl dimethylammonium chloride, diethyl allyl dimethylammonium chloride, diallyl di(β-hydroxyethyl)ammonium chloride, diallyl di(β-ethoxyethyl)ammonium chloride, addition salts and quaternary salts of dimethylaminoethyl (meth)acrylate, addition salts and quaternary salts of diethylaminoethyl (meth)acrylate, addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl (meth)acrylate, addition salts and quaternary salts of N,N'-dimethylaminopropylacrylamide, allylamine, diallylamine, ethyl... Copolymers of enamine and vinylpyridine; cocodimethyl carboxymethyl betaine; lauryl dimethyl carboxymethyl betaine; lauryl dimethyl-α-carboxyethyl betaine; hexadecyl dimethyl carboxymethyl betaine; lauryl-bis-(2-hydroxyethyl)carboxymethyl betaine; stearyl-bis-(2-hydroxypropyl)carboxymethyl betaine; oleoyl dimethyl-γ-carboxypropyl betaine; lauryl-bis-(2-hydroxypropyl)α-carboxyethyl betaine; cocodimethyl sulfopropyl betaine; stearyl dimethyl sulfopropyl betaine; lauryl-bis-(2-hydroxyethyl)sulfopropyl betaine; sodium dodecyl sulfate (SDS); Surfynol 104. Sodium dioctyl sulfosuccinate; Sodium lauryl ether sulfate; Polyethylene glycol branched-nonylphenyl ether ammonium sulfate; Disodium 2-dodecyl-3-(2-sulfonylphenoxy); PEG25-PABA;Sodium sulfate of polyethylene glycol mono-C10-16-alkyl ether; (2-N-butoxyethoxy)acetic acid; hexadecylbenzenesulfonic acid; cetyltrimethylammonium hydroxide; dodecyltrimethylammonium hydroxide; dodecyltrimethylammonium chloride; cetyltrimethylammonium chloride; N-alkyl-N-benzyl-N,N-dimethylamine chloride; dodecylamine; polyoxyethylene lauryl ether; dodecenylsuccinic acid monodiethanolamide; ethylenediaminetetra(ethoxylate-block-propoxylate); and combinations thereof.

[0047] 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 synthesized using N-vinylpyrrolidone monomer, poly(vinyl alcohol), polyacrylates and polyacrylate analogs, polyamino acids (e.g., polyalanine, polyleucine, polyglycine, etc.), polyamide hydroxycarbamates, polylactones, polyacrylamide, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyethyleneimine, sugar alcohols such as sorbitol esters and xylitol, esters of dehydrated sorbitol, secondary alcohol ethoxylates such as TERGITOL, and combinations thereof.

[0048] The amount of cleaning additive in the cleaning composition is in the range of about 0.01 wt% to about 20 wt% based on the total weight of the cleaning composition. Preferably, the cleaning additive is present in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the cleaning composition, and more preferably in an amount of about 0.5 wt% to about 5 wt%.

[0049] The cleaning composition disclosed herein comprises at least one pH adjuster for raising or lowering the pH of the composition to a target value. While the pH adjuster may include acids and / or bases, it is preferably a base used to raise the pH of the cleaning composition. Illustrative bases include, but are not limited to, 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 compounds having the formula NR. 1 R 2 R 3 R 4 OH tetraalkylammonium hydroxide compounds, wherein R 1 R 2 R 3 and R 4They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C1-C6 hydroxyalkyl groups (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl), and substituted or unsubstituted C6-C 10 Aryl (e.g., benzyl). Commercially available tetraalkylammonium hydroxides include 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.

[0050] Alternatively or additionally, the pH adjuster may be a pH-adjusting agent having the formula (PR 1 R 2 R 3 R 4 )OH quaternary base, of which R 1 R 2 R 3 and R 4 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), branched C1-C6 alkyl, C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl), substituted C6-C 10 Aryl, unsubstituted C6-C 10 Aryl groups (e.g., benzyl) and any combination thereof, such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, and n-propyltriphenylphosphonium hydroxide.

[0051] The amount of one or more pH adjusters added depends on the desired pH, as disclosed herein and as understood by those skilled in the art. For example, the pH adjuster may be present in an amount from about 0.1 wt% to about 10 wt% of the total weight of the cleaning composition, and more preferably in an amount from about 1 wt% to about 5 wt%. 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 and at least one additional hydroxide listed herein. In another embodiment, the pH adjuster comprises KOH and at least one additional hydroxide listed herein. In yet another embodiment, the pH adjuster comprises KOH and at least one of choline hydroxide and ammonium hydroxide.

[0052] The pH of the cleaning compositions described herein may vary depending on the target application. In one embodiment, the pH of the composition is greater than 7, and thus it may be an alkaline aqueous cleaning composition. For 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. Those skilled in the art will understand that upon dilution, for example by forming the concentration described below and subsequently adding water, the pH of the cleaning composition will decrease to the range of about 10 to about 12.

[0053] The cleaning compositions described herein contain at least one oxyamine compound or a salt thereof. Specifically, the oxyamine compound may be a hydroxylamine or an aminooxy (nitryl) compound. For example, the composition may contain at least one hydroxylamine compound, at least one aminooxy compound, or a combination thereof. The oxyamine compound may, in principle, include an oxygen group (e.g., -O) bonded to a nitrogen (N) atom. . Any compound containing -OH. In some cases, the salt form of the oxyamine compound may be more stable or readily available, wherein the compound includes a hydroxylated (-OM) group bonded to a nitrogen atom. Examples include Na+, K+, Li+, or ammonium salts.

[0054] More specifically, oxyamine compounds can be hydroxylamine compounds having the general formula (I):

[0055]

[0056] It may be an aminooxyl compound having the general formula (II):

[0057]

[0058] R 1 and R 2They may be the same as or different from each other and are selected from the group consisting of: hydrogen and straight-chain, branched or cycloalkyl, including C1-C8 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl). Therefore, oxamine compounds may be alkyloxamines (e.g., alkyl hydroxylamines, especially dialkyl hydroxylamines). Suitably, oxamine compounds may be symmetrical, wherein R in formulas (I) and (II) 1 and R 2 Same. Illustrative examples of hydroxylamine compounds include, but are not limited to, hydroxylamine (NH2OH), dimethylhydroxylamine, methylethylhydroxylamine, methylpropylhydroxylamine, methylbutylhydroxylamine, diethylhydroxylamine (DEHA), ethylpropylhydroxylamine, ethylbutylhydroxylamine, dipropylhydroxylamine, propylbutylhydroxylamine, dibutylhydroxylamine, di(tert-butyl)hydroxylamine, morpholine-N-hydroxide, N-hydroxysuccinylamine, N-hydroxycis-butenedimide, or salts thereof. Examples of salts include, but are not limited to, hydroxylamine hydrochloride, hydroxylamine sulfate, or hydroxylamine acetate. Illustrative examples of aminooxyl compounds include, but are not limited to, 2,2,6,6-tetramethylpiperidin-1-yl)oxy (sometimes also called (2,2,6,6-tetramethylpiperidin-1-yl)oxoalkyl or TEMPO), 4-amino-TEMPO, 4-carboxyl-TEMPO, 4-phosphinooxy-TEMPO, 4-hydroxy-TEMPO, and polymers having covalently bonded TEMPO side groups or end groups. Other suitable examples include 2,2,5,5-tetramethylpyrrolidine-1-yl)oxoalkyl (sometimes also called 2,2,5,5-tetramethylpyrrolidine-N-oxynitrooxide or PROXYL), 3-amino-PROXYL, 3-carboxy-PROXYL, 3-phosphono-PROXYL, 3-hydroxy-PROXYL, and polymers having covalently bonded PROXYL side groups or end groups.

[0059] In some embodiments, the hydroxylamine may be further functionalized, wherein, for example, R 1 and R 2 The following groups can be freely selected: straight-chain or branched C1-C8 alcohols (e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol), and those having the formula R 4 -OR 5 Straight-chain or branched ethers, wherein R 4 and R 5 They may be the same or different from each other and are selected from the group consisting of C1-C8 alkyl groups, wherein R 4 or R 5 Bonded to N. As a specific instance, R 1 and / or R 2 It may contain C1-C4 alkyl groups.

[0060] In various embodiments, the composition comprises, by weight of the total composition, an oxamine compound or oxamine compound component as described anywhere herein in the range of 0.1 to 20% w / w. Suitably, the amount of oxamine compound or oxamine compound component may be in the range of 0.01 to 10% w / w, for example, in the range of 0.1 to 7% w / w.

[0061] The amount of the amine compound or its salt in the cleaning composition is in the range of about 0.01 wt% to about 25 wt% based on the total weight of the cleaning composition. Preferably, the amine compound is present in an amount of about 0.1 wt% to about 10 wt% based on the total weight of the cleaning composition, and more preferably in an amount of about 0.5 wt% to about 5 wt%.

[0062] The cleaning compositions disclosed herein may optionally further comprise one or more additional components, which may provide additional benefits, particularly for cleaning microelectronic devices containing cobalt-containing materials. In some embodiments, the cleaning composition may comprise at least one etchant, at least one corrosion inhibitor, and / or at least one reducing agent.

[0063] For example, the cleaning composition may optionally contain at least one etchant. Suitably, the composition may contain an etchant component consisting of a variety of additional etchants. Examples of etchants include (but are not limited to) morpholine, diethylene glycolamine, 3-butoxypropylamine, propylene glycol monobutyl ether (e.g., DOWANOL PnB), hydroxyethylmorpholine, hydroxypropylmorpholine, aminoethylmorpholine, aminopropylmorpholine, pentamethyldiethylenetriamine (PMDETA), piperazine, N,N-dimethylpropanolamine, ethanolamine, diethanolamine, diethylamine, diethylamine, ethylenediamine, diethylenetriamine, tetraethylenepentamine, triethylenetetramine, trimethylaminoethylethanolamine, trimethylaminopropylethanolamine, and combinations thereof. In various embodiments, the amount of etchant (if present) in the cleaning is in the range of 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 wt% to about 20 wt% by weight of the total composition, and more preferably in an amount of about 1 wt% to about 10 wt%. In various embodiments, the cleaning composition does not contain an etchant.

[0064] The cleaning composition may optionally contain at least one corrosion inhibitor. Illustrative corrosion inhibitors include, but are not limited to, acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, glutamate, 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, etc. Mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, catechol, benzopyrenic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, benzopyrenic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, pyridinecarboxylic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid Pyruvic acid, pyruvic acid, propanethiol, benzohydroxyxamic acid, 2,5-dicarboxypyridine, 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), hypozoxytriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperidine, N-(2-aminoethyl)piperidine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyxamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropynyl alcohol, lauroyl sarcosine, stearoyl sarcosine, saccharin, and combinations thereof. In various embodiments, the amount of corrosion inhibitor (if present) in the cleaning is in the range of about 0.01 wt% to about 10 wt% based on the total weight of the cleaning composition. Preferably, the corrosion inhibitor is present in an amount of about 0.01 wt% to about 5 wt% based on the total weight of the composition, and more preferably in an amount of about 0.05 wt% to about 5 wt%. In various embodiments, the cleaning composition does not contain corrosion inhibitor.

[0065] The cleaning composition may optionally contain at least one reducing agent. Illustrative 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, hypophosphite, hypophosphite, 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, at least one reducing agent may contain at least one sulfite ion and at least one other enumerated reducing agent, such as sulfurous acid, potassium sulfite, ammonium sulfite, hypophosphite, and any combination thereof. It should be understood that when ammonium sulfite is present, ammonium sulfite can be generated on-site, wherein a combination of specific components results in the formation of ammonium sulfite to aid in the removal of residues, such as cerium dioxide particles and other post-CMP residues. In various embodiments, the amount of reducing agent (if present) in the cleaning process is in the range of about 0.0001 wt% to about 1 wt% based on the total weight of the cleaning composition. Preferably, the reducing agent is present in an amount of about 0.0001 wt% to about 0.2 wt% based on the total weight of the composition, and more preferably in an amount of about 0.01 wt% to about 0.2 wt%. In various embodiments, the cleaning composition does not contain a reducing agent.

[0066] The range of weight percentage ratios of the components will cover all possible concentrated or diluted embodiments of the composition. For this purpose, in one embodiment, a concentrated removal composition is provided that can be diluted for use as a cleaning solution. The concentrated composition, or “concentrate,” advantageously allows users (e.g., CMP process engineers) to dilute the concentrate to the desired strength and pH during use. The dilution ratio of the concentrated aqueous removal composition can 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, wherein the aqueous removal composition is diluted with a solvent (e.g., deionized water) at or just before the tool. Those skilled in the art will understand that the range of weight percentages of the components disclosed herein should remain unchanged after dilution.

[0067] The compositions described herein are effective in applications including, but not limited to, removal of residues after etching, surface preparation for removal of residues after ashing, cleaning after electroplating, and removal of residues after CMP. In addition to cleaning cobalt-containing components, the aqueous cleaning compositions described herein are also suitable for cleaning and protecting other metal (e.g., copper- and tungsten-containing) products, including but not limited to decorative metals, wire bonding, printed circuit boards, and other electronic packages using metals or metal alloys.

[0068] Aqueous cleaning compositions are readily formulated by simply adding the individual components and mixing until homogeneous. Furthermore, the compositions can be readily formulated as single-component formulations or as multi-component formulations to be mixed at or before use; for example, individual portions of a multi-component formulation may be mixed at the tool or in a reservoir upstream of the tool. The concentration of individual components can vary widely across specific multiples of the composition, i.e., becoming more dilute or more concentrated, and it should be understood that the compositions described herein may differently and alternatively comprise, consist of, or substantially consist of any combination of components consistent with the disclosure herein.

[0069] Therefore, another aspect relates to a kit comprising, in one or more containers, one or more components adapted to form the cleaning composition 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 oxyamine compound, water, optionally at least one etchant, optionally at least one corrosion inhibitor, and optionally at least one reducing agent, for use in combination with an additional solvent (e.g., water) during manufacturing or in use. Alternatively, the kit may comprise, in one or more containers, at least one complexing agent, at least one cleaning additive, at least one oxyamine compound, water, optionally at least one etchant, optionally at least one corrosion inhibitor, and optionally at least one reducing agent, for use in combination with at least one pH adjuster and an additional solvent (e.g., water) during manufacturing or in use. The container of the kit must be suitable for storing and transporting the composition and may be, for example, a NOWPak® container (Entegris, Inc., Billerica, Mass., USA).

[0070] One or more containers containing components of an aqueous cleaning composition preferably include means for fluid communication of the components in the one or more containers for blending and dispensing. For example, referring to the NOWPak® container, gas pressure can be applied to the outside of the liner in the one or more containers to expel at least a portion of the contents of the liner and thus enable fluid communication for blending and dispensing. Alternatively, gas pressure can be applied to the top space of a conventional pressurized container or pump that can be used to enable fluid communication. Additionally, the system preferably includes a dispensing port for dispensing the blended removal composition to a treatment tool.

[0071] When applied to microelectronics manufacturing operations, the cleaning compositions described herein are effectively used to remove residues and contaminants, including particles, post-CMP residues, post-ashing residues, and post-etching residues, from the surfaces of microelectronic devices. Advantageously, the cleaning compositions of the present invention described herein exhibit improved cobalt compatibility compared to previously described alternative cleaning compositions in the art. Therefore, this disclosure further relates to a method for removing residues and contaminants from microelectronic devices having residues and contaminants using the cleaning compositions described herein.

[0072] The method includes contacting the microelectronic device with a cleaning composition for a time sufficient to at least partially remove the residues and contaminants from the microelectronic device. In use, the cleaning composition is typically contacted with the device for about 5 seconds to about 10 minutes, preferably about 1 second to 20 minutes, and preferably about 15 seconds to about 5 minutes, at a temperature ranging from about 20°C to about 90°C, preferably about 20°C to about 50°C. Such contact times and temperatures are illustrative, and any other suitable time and temperature conditions that effectively at least partially remove residues and contaminants from the device can be used within the broad practice of the method. Both "at least partially cleaned" and "substantially removed" correspond to removing at least 85%, more preferably at least 90%, even more preferably at least 95%, or most preferably at least 99% of the cerium oxide particles present on the device prior to particle removal.

[0073] After contacting the device and removing the desired residues and / or contaminants, the cleaning composition can be readily removed from the device to which it was previously applied, as is desirable and effective in the intended end-use application of the composition described herein. For example, a rinsing solution comprising deionized water is preferably used. Subsequently, the device can be dried using nitrogen or a rotary drying cycle, as known in the art.

[0074] Another aspect of this disclosure relates to modified microelectronic devices prepared according to the methods described herein and to products containing such microelectronic devices. Another aspect relates to a recyclable cleaning composition, wherein, as readily determined by those skilled in the art, the composition can be recycled until the particle and / or contaminant load reaches a maximum amount that an aqueous removal composition can accommodate. Therefore, the cleaning compositions disclosed herein may include residues and / or contaminants. Residues and contaminants may be soluble in the composition. Alternatively, residues and contaminants may be suspended in the composition. Preferably, residues include post-CMP residues, post-etching residues, post-ashing residues, contaminants, or combinations thereof. Another aspect relates to a method of manufacturing an article containing a microelectronic device, the method comprising contacting the microelectronic device with the cleaning composition of the present invention for a time sufficient to remove residues and / or contaminants from the microelectronic device, and incorporating the cleaned microelectronic device into the article. Another aspect relates to articles produced by this method.

[0075] Example

[0076] Unless otherwise expressly stated, the features and advantages of the cleaning compositions disclosed herein are more fully illustrated by the following non-limiting examples, wherein all parts and percentages are by weight. The disclosed cleaning compositions are particularly suitable for cleaning residues and contaminants (e.g., post-CMP residues, post-etching residues, post-ashing residues and contaminants) from microelectronic device structures while remaining compatible with cobalt-containing materials present on the surface.

[0077] Example 1

[0078] The following examples demonstrate the effectiveness of adding at least one hydroxylamine to a cleaning composition.

[0079] Two compositions were prepared and are shown in Table 1 below. All values ​​in the table refer to wt% of the total composition, and any values ​​not reaching 100% are simply due to rounding.

[0080] Table 1

[0081]

[0082] As shown, the only difference between the compositions of Comparative Example 1 and Example 1 is the use of DEHA instead of a certain amount of water. Comparative Example 1 is a comparative example not based on this disclosure.

[0083] Each composition was diluted with deionized water at a ratio of 60:1 (water to composition), and cobalt samples were subsequently exposed to the diluted compositions at 30°C for 15 minutes. The degree of etching of the cobalt samples was determined and is shown in Table 1. As can be seen, the cleaning composition of Comparative Example 1 showed an etching rate of 0.6 A / min with a standard deviation of 0.02. By comparison, the composition of Example 1 showed an etching rate of 0.4 A / min with a standard deviation of 0.05. These results demonstrate that hydroxylamine, including, for example, DEHA, effectively reduces cobalt etching.

[0084] Example 2-3

[0085] The following examples illustrate the cleaning compositions of this disclosure, which contain at least one hydroxylamine and have high cobalt compatibility.

[0086] The present disclosure describes the preparation of compositions comprising at least one complexing agent, at least one cleaning additive, at least one pH adjuster, and at least one hydroxylamine. The compositions are as follows:

[0087] Example 2 The composition consists of 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 is 13.5.

[0088] 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.

[0089] All figures refer to wt% of the total composition, and any figure not reaching 100% is simply due to rounding.

[0090] Each composition was diluted with deionized water at a ratio of 60:1 (water to composition). Cobalt samples were then exposed to each diluted composition for 15 minutes at 30°C, and the degree of etching of the cobalt samples was measured. The compositions of Examples 2 and 3, containing DEHA as a hydroxylamine, were found to have improved cobalt compatibility based on their reduced cobalt etching rate.

[0091] Example 4-13

[0092] The following examples demonstrate the effectiveness of various cleaning compositions of this disclosure, which contain at least one hydroxylamine for removing silica slurry from a cobalt substrate.

[0093] Compositions of this disclosure comprising at least one complexing agent, at least one cleaning additive, at least one pH adjuster, and at least one hydroxylamine are prepared and are shown in Table 2 below. All values ​​in the table refer to wt% of the total composition, and any values ​​not reaching 100% of the total are due to rounding.

[0094] The composition shown was prepared and diluted with water at a ratio of 100:1. The cobalt sample was immersed in a silica-containing slurry for 5 minutes, rinsed in deionized water for 30 seconds, and then immersed in the cleaning composition for 60 seconds, followed by a second rinse with deionized water for 30 seconds. The temperature during immersion was room temperature. The degree of cleaning was determined using scanning electron microscopy (SEM), and the results are shown in Table 3 below.

[0095] Table 2

[0096]

[0097] Table 3

[0098]

[0099] As shown, each of the cleaning compositions containing diethylhydroxylamine can effectively remove silica slurry particles from cobalt-containing substrates. Therefore, the hydroxylamine-containing compositions can remove residual particles from cobalt substrates while maintaining effective cobalt compatibility (as demonstrated by the reduced etching rate in Examples 1-3).

[0100] Although the invention has been disclosed herein with reference to illustrative embodiments and features, it should be understood that the embodiments and features described above are not intended to limit the invention, and other variations, modifications, and other embodiments will be apparent to those skilled in the art based on the disclosure herein. Therefore, the invention will be generally explained as all such variations, modifications, and alternative embodiments are covered within the spirit and scope of the claims set forth below.

Claims

1. A cleaning composition for cleaning residues and contaminants from a microelectronic device having such residues and contaminants thereon, the cleaning composition comprising... The composition is an aqueous cleaning composition having a pH of 10 to 14 and containing at least 50% water by weight. The cleaning additives described herein comprise species selected from the group consisting of: 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, tetramethylene sulfone (sulfolane), dimethyl sulfone, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl ethyl ketone, isopropanol, octanol, ethanol, butanol, methanol, isophorone, 4-methyl-2-pentanone, 2,4-dimethyl-3-pentanone, 5-methyl 3-Hepanotone, 3-Pentanone, 5-Hydroxy-2-Pentanone, 2,5-Hexanedione, 4-Hydroxy-4-Methyl-2-Pentanone, 2-Methyl-2-Butanone, 3,3-Dimethyl-2-Butanone, 4-Hydroxy-2-Butanone, Cyclopentanone, 2-Pentanone, 3-Pentanone, 1-Phenylacetone, Acetophenone, Benzophenone, 2-Hexanone, 3-Hexanone, 2-Hepanotone, 3-Hepanotone, 4-Hepanotone, 2,6-Dimethyl-4-Hepanotone, 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), Ammonium dodecyl sulfate, Potassium dodecyl sulfate, Ammonium carboxymethyl cellulose, Potassium carboxymethyl cellulose, Polyvinylpyrrolidone (PVP), Polyamino acids, Polyamide hydroxycarbamates, Polylactones, Polyacrylamide, Xanthan gum, Chitosan, Polyvinyl alcohol, Polyvinyl acetate, Polyacrylic acid, Polyethyleneimine, Sorbitol esters, Xylitol, Esters of dehydrated sorbitol, Secondary alcohol ethoxylates, Potassium alginate, Ammonium alginate, Calcium alginate, Poly(ethylene glycol methacrylate) and combinations thereof.

2. The cleaning composition according to claim 1, wherein the complexing agent comprises a species selected from the group consisting of: 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, 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), hypozinotriacetic 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, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tri (Methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N,N'',N'''-tetra(methylenephosphonic acid) (DOTP), nitrotri(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), bis(hexyl)triaminepentylphosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tri(methylenephosphonic acid) (NOTP), hydroxyethyl diphosphonate, hypozonyltris(methylene)phosphonic acid, 2-phosphono-butane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid), phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarboxylic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, disodium salt of 4,5-dihydroxy-1,3-benzenedisulfonic acid and combinations thereof.

3. The cleaning composition according to claim 1, wherein the pH adjuster comprises 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, tri(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.

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

5. The cleaning composition according to claim 1, wherein the cleaning composition further comprises at least one corrosion inhibitor, wherein the corrosion inhibitor comprises a species selected from the group consisting of: acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, m-phenylene oxide. Dicarboxylic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, catechol, benzoyltriol, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, benzoyltriol, tyrosine, valine, xylitol, oxalic acid, tannic acid, pyridinecarboxylic acid, 1,3-cyclopentanedione, catechol, pyrogallol, meta- Hydroquinone, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxyxamic acid, 2,5-dicarboxypyridine, 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), hypozinotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperidine, N-(2-aminoethyl)piperidine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyxamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropynyl alcohol, lauroyl sarcosine, stearoyl sarcosine, saccharin and combinations thereof.

6. The cleaning composition according to claim 1, wherein the cleaning composition further comprises at least one reducing agent, wherein the reducing agent comprises 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, hypophosphite, 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.

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