Post cmp cleaning compositions

Abstract

This invention generally provides high-pH cleaning compositions for dielectric surfaces such as PETEOS, SiO2, thermal oxides, silicon nitride, silicon, etc. The compositions of this invention provide superior surface wetting, dispersion of particles and organic residues, and prevention of redeposition and re-agglomeration of dispersed residues during cleaning, thereby providing superior cleaning and a low defect rate.

Description

Technical Field

[0001] This invention relates generally to compositions for removing CMP residues from the surface of microelectronic devices. Prior Technology

[0002] Microelectronic device wafers are used to form integrated circuits. A microelectronic device wafer includes a substrate (such as silicon), and regions in the substrate are patterned to deposit different materials with insulating, conductive, or semiconductive properties.

[0003] 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 microelectronic wafer surface before subsequent processing. Therefore, removing and / or grinding certain surfaces of microelectronic device wafers is necessary.

[0004] Chemical mechanical polishing or planarization ("CMP") is a process in which materials are removed from the surface of a microelectronic device wafer, and that surface is polished (e.g., planarized) by a combination of physical processes (such as polishing) and chemical processes (such as oxidation or chelation). In its most basic form, CMP involves applying an abrasive slurry containing active chemicals to a polishing pad that polishes the surface of the microelectronic device wafer during the removal, planarization, and polishing processes. Removal or polishing processes using purely physical or purely chemical actions are not as effective as a synergistic combination of both for achieving rapid and uniform removal. Furthermore, in the fabrication of integrated circuits, CMP slurries should also be able to preferentially remove films containing complex layers of metals and other materials to produce highly planar surfaces for subsequent photolithography or patterning, etching, and thin-film processing.

[0005] In the front-end process (FEOL) method for forming isolation regions in a silicon substrate using the shallow trench isolation (STI) method, pad oxide films and pad nitride films are deposited and patterned on a semiconductor substrate to expose portions of the substrate corresponding to the isolation regions. The exposed areas of the substrate are then etched to form trenches. The substrate is then subjected to a sacrificial oxidation process to remove damage caused by the substrate etching, followed by the formation of a wall oxide film on the trench surface. Next, a trench-buried oxide film (e.g., an oxide film formed by high-density plasma chemical vapor deposition, referred to as an HDP-oxide film) is deposited on the substrate surface in a manner that embeds it within the trenches. The surface of the HDP-oxide film is then subjected to chemical mechanical polishing until the pad nitride film is exposed. The resulting substrate is then cleaned and the pad nitride film, which served as an etching barrier during trench etching, is removed, thus completing the formation of the isolation regions.

[0006] CMP slurries using cerium dioxide particles generally achieve faster polishing speeds for insulators compared to silicon dioxide-containing slurries. Furthermore, cerium dioxide-based slurries are most commonly used due to their ability to achieve STI pattern planarization with minimal oxide etching. Disadvantageously, cerium dioxide-based slurries are difficult to remove from STI structures because of the zeta potential of cerium dioxide particles relative to the surfaces of silicon oxide and silicon nitride. If devices are fabricated with these residues remaining on the wafer, these residues will cause short circuits and increased resistance. Cerium dioxide particles also pose a problem when using FinFET structures after CMP processing with cerium dioxide slurries.

[0007] Post-CMP cleaning of dielectric substrates (PETEOS, SiO2, thermal oxides, silicon nitride, silicon, etc.) polished with slurries containing silicon dioxide and other surface-hydroxylated metal oxides as abrasive particles is difficult and results in high residue and defect rates. This is due to the strong interactions between abrasive particles and the dielectric surface via hydrogen bonding and van der Waals forces at low and medium pH levels, and particle aggregation and redeposition at high pH levels. Theoretically, at pH levels above the pH IEP (isoelectric point), both the abrasive residue particles and the dielectric surface should be highly negatively charged, and therefore, electrostatic repulsion between the particle and substrate should lead to a lower defect rate. In reality, most CMP slurry organic additives prevent and neutralize these strong repulsive forces, and sometimes promote better particle adhesion to the wafer surface—an undesirable effect that leads to high defect rates. Therefore, there is a need for improved post-CMP cleaning compositions that effectively remove both residual particles and other residues adhering to the dielectric wafer surface. Summary of the Invention

[0008] This invention generally provides high-pH cleaning compositions for dielectric surfaces (such as PETEOS, SiO2, thermal oxides, silicon nitride, silicon, etc.). The compositions of this invention provide superior surface wetting, dispersion of particles and organic residues, and prevention of redeposition and re-agglomeration of dispersed residues during cleaning to provide superior cleaning and a low defect rate. In one embodiment, this invention provides a composition comprising: a.Water; b. Alkanolamines having 2 to 7 carbon atoms; c. Diol ethers; d. pH adjusters; and e. Surface-active hydrophobic acids. Simple Explanation of the Diagram

[0009] Figure 1 shows the particle area results of each formulation obtained by the particle counting program, which is followed by immersion test and SEM measurement, comparing sample 1 (comparative example) with samples 2, 3 and 4.

[0010] Figure 2 shows the surface tension and water contact angle (WCA) of Sample 1 (Comparative Example) and the modified composition of the present invention.

[0011] Figure 3 illustrates the particle area results for various compositions. [] Implementation

[0012] This invention generally relates to compositions that can be used to remove such materials from microelectronic devices having residues and contaminants thereon. These compositions are particularly useful for removing CMP, etching, or ashing residues from dielectric surfaces (such as PETEOS, SiO2, thermal oxides, silicon nitride, silicon, etc.).

[0013] As used in this specification and the accompanying claims, unless otherwise expressly specified, the singular forms "a / an" and "the" include the plural references. As used in this specification and the accompanying claims, unless otherwise expressly specified, the term "or" generally includes "and / or" in its meaning.

[0014] The term "approximately" generally refers to a range of numbers that are considered equivalent to the detailed value (e.g., having the same function or result). In many instances, the term "approximately" may include numbers rounded to the nearest significant figure.

[0015] The range of numbers represented by endpoints includes all numbers that fall within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0016] In the first state sample, the present invention provides a composition comprising the following: a.Water; b. Alkanolamines having 2 to 7 carbon atoms; c. Diol ethers; d. pH adjusters; and e. Surface-active hydrophobic acids.

[0017] In one embodiment, the alkanolamine is selected from aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, aminoethoxyethoxyethanol, methoxypropylamine, butoxyisopropylamine, 2-ethylhexylisopropylamine, ethanolpropylamine, ethylethanolamine, N-hydroxyethylmorpholine, aminopropyldiethanolamine, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, diisopropylamine, aminomethylpropanediol, N,N- Dimethylaminomethylpropylene glycol, aminoethylpropylene glycol, N,N-dimethylaminoethylpropylene glycol, isopropylamine, 2-amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino-4-hydroxyoctane, 2-aminobutanol, trimethylaminomethane (TRIS), N,N-dimethyltrimethylaminomethane, hydroxypropylamine, benzylamine, hydroxyethylamine, trimethylaminomethane, diethylene glycolamine, and combinations thereof.

[0018] In one embodiment, the glycol ether has a methylene linking group of the formula -(CH2)x-, where x is an integer from 2 to 6, and, where appropriate, an aromatic group, such as a phenyl group. In another embodiment, the glycol ether is selected from 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 (BDG, 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 (such as DOWANOL™ PnB glycol ether, Dow), Inc.), dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol phenyl ether, propylene glycol phenyl ether (such as DOWANOL™ PPh dipropylene glycol phenyl ether).

[0019] In one embodiment, the pH adjuster is a type of alkali that effectively increases the pH of the composition to the desired pH during use. In some embodiments, the pH will be greater than 7, or between about 8 and 14, or between about 9 and 14.

[0020] The base can be any base that can be used to control the pH of the composition. As specified, many different basic compounds are known for use as cleaning solutions adapted for cleaning the surface of microelectronic device substrates (e.g., as a post-CMP cleaning solution). Bases include (but are not limited to) potassium hydroxide, ammonium hydroxide (i.e., ammonia), and tetraalkylammonium hydroxide having the formula NR1R2R3R4OH, wherein R1, R2, R3, and R4 may be the same or different from each other and selected from hydrogen, straight-chain or branched C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl), and substituted or unsubstituted C6-C10 aryl (e.g., benzyl). Non-limiting examples of basic compounds include: choline hydroxide, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), trimethylethylammonium hydroxide, diethyldimethylammonium hydroxide, tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), tetramethylammonium hydrochloride (TMAH), tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, guanidine acetate, ammonium hydroxide, 1,1,3,3-tetramethylguanidine, guanidine carbonate, arginine, potassium hydroxide, cesium hydroxide, and combinations thereof.

[0021] Alternatively or additionally, the pH adjuster may be a compound having the formula (PR5R6R7R8)OH, wherein R5, R6, R7 and R8 may be the same or different from each other and are selected from hydrogen, straight-chain C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl and hexyl), branched-chain C1-C6 alkyl, C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl and hydroxyhexyl), substituted C6-C10 aryl, unsubstituted C6-C10 aryl (e.g., benzyl) and any combination thereof, such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide.

[0022] In another embodiment, the pH adjuster (i.e., the base) is selected from choline hydroxide and tetraethylammonium hydroxide (TEAH).

[0023] These basic compounds may be contained separately (e.g., alone) as the only basic compound in the composition; combined with each other in the composition, i.e., as only two basic compounds in the composition; or combined with one or more other (e.g., a second) bases in the composition.

[0024] As used herein, the term "surfactant hydrophobic acid" refers to an acid species having hydrophobic groups, as will be readily understood by those skilled in the art, but does not include polymeric surfactants. Exemplary surfactant hydrophobic acids or salts used in the compositions described herein include sodium dodecyl sulfate (SDS), decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, bis(2-ethylhexyl)phosphate, octadecylphosphonic acid, perfluoroheptanoic acid, perfluorodecanoic acid, trifluoromethanesulfonic acid, phosphonoacetic acid, dodecylbenzenesulfonic acid, other benzenesulfonic acids or their salts substituted with the group R' (wherein R' is a straight-chain or branched C8-C18 alkyl), myristylsulfonic acid, tridecylsulfonic acid, laurylsulfonic acid, decylsulfonic acid, undecylsulfonic acid, dodecenylsuccinic acid, di-(octadecyl)hydrogen phosphate, octadecyl dihydrogen phosphate, dodecenylsuccinic acid, lauric acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, palmitic acid, oleic acid, juniperic acid, 12-hydroxystearic acid, sodium lauryl sarcosinate, C1-C 6-alkylaryl phosphates, octadecylphosphonic acid, dodecyl phosphates, sodium lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate, bis(2-ethylhexyl)sulfosuccinate, sodium lauryl sarcosinate, alkylaryl phosphates, stearyl sarcosinate, stearic acid, arachidic acid (C 20H 40O 2), carboxylic acid (C 22H 44O 2), decanoic acid (C 10H 20O 2), 2-ethylhexanoic acid (C 8H 16O 2), heptadecanoic acid (C 17H 34O 2), heptanoic acid (C 7H 14O 2), heptadecanoic acid (C 37H 74O 2), hexanoic acid (C 6H 12O 2), hexadecanoic acid (C 36H 72O 2), lauric acid (C 12H 24O 2), triacontacosic acid (C 30H 60O 2) 2) 13-Methyltetradecanoic acid (C 15H 30O 2), octacosic acid (C 28H 56O 2), myristic acid (C 14H 28O 2), neodecanoic acid (C 10H 20O 2), nonacosanoic acid (C 29H 58O 2), nonacosanoic acid (CH 3(CH 2) 17COOH), nonanoic acid (C 9H 18O 2), palmitic acid (C 16H 32O 2), pentacosanoic acid (C 25H 50O 2), pentadecanoic acid (C 15H 30O 2), phytic acid (C 20H 40O 2), teicosanoic acid (C 33H 66O 2), stearic acid (C 18H 36O 2), tetradecanoic acid (C 34H 68O 2), trichosanoic acid (C 23H 46O 2) 2) Tridecanoic acid (C 13H 26O 2), tuberculin stearic acid (C 19H 38O 2), undecanoic acid (C 11H 22O 2), caprylic acid, sebacic acid and octanoic acid.

[0025] In one embodiment, the surface-active hydrophobic acid is selected from octanoic acid, dodecylbenzenesulfonic acid, and nonanoic acid.

[0026] In one embodiment, the composition further comprises a corrosion inhibitor. Illustrative corrosion inhibitors include (but are not limited to) phosphorous acid, hypophosphite, sulfurous acid, diethylhydroxylamine, hydroxylamine sulfate, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, quaternary surfactants selected from N-alkyl-N-benzyl-N,N-dimethylammonium chloride and 4-(3-phenylpropyl)pyridine, acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, aspartic acid, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, glutamate, glutamate, glutamate, glyceric acid, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, and maleic acid. Acid anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, catechol, pyromellitic acid, quinic acid, serine, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, styramine, 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, 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, salicylhydroxyoxime, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropargyl alcohol, saccharin and combinations thereof.

[0027] In another embodiment, the corrosion inhibitor is a compound used as a reducing agent. Exemplary compounds 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, phosphoric 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, the corrosion inhibitor / reducing agent may contain at least one sulfite ion and at least one other listed reducing agent, such as sulfurous acid, potassium sulfite, ammonium sulfite, hypophosphite, diethylhydroxylamine sulfate, diethylhydroxylamine phosphate, and any combination thereof. It should be understood that when ammonium sulfite is present, it can be generated in situ, wherein a combination of specific components results in the formation of ammonium sulfite to help remove residues.

[0028] In another embodiment, the corrosion inhibitor is selected from ascorbic acid, phosphorous acid, hypophosphite, sulfurous acid, diethylhydroxylamine, hydroxylamine sulfate, sodium / ammonium / potassium metabisulfite and sodium / ammonium / potassium sulfite, and quaternary surfactants, including N-alkyl-N-benzyl-N,N-dimethylammonium chloride (benzalkonium chloride) and 4-(3-phenylpropyl)pyridine.

[0029] In various embodiments, when present, the amount of corrosion inhibitor in the composition ranges from about 0.0001 wt% to about 1 wt% based on the total weight of the composition. In another embodiment, the reducing agent is present in an amount from about 0.0001 wt% to about 0.2 wt% based on the total weight of the composition, and in another embodiment, it is present in an amount from about 0.01 wt% to about 0.2 wt%. In some embodiments, the cleaning composition does not contain a corrosion inhibitor / reducing agent.

[0030] In other embodiments, the composition includes compounds that function as hydrogen-bonding additives, which are used to reduce the adhesion of silicon dioxide particles to brushes used in the cleaning of microelectronic devices after CMP. See, for example, U.S. Patent Publication No. 2019 / 0168265, which is incorporated herein by reference. Exemplary compounds include nonionic, anionic, cationic, and zwitterionic small molecules and polymers that can behave as polyelectrolytes at neutral pH. Anionic polymers or anionic polyelectrolytes can be natural polymers, modified natural polymers, or synthetic polymers. Exemplary natural and modified natural anionic polymers that may be included in the composition include (but are not limited to) alginic acid (or its salts), carboxymethyl cellulose, dextran sulfate, poly(galacturonic acid), and their salts. Exemplary synthetic anionic polyelectrolytes include (but are not limited to): homopolymers or copolymers of (meth)acrylic acid (or its salts), poly(acrylic acid), maleic acid (or its anhydride), styrene sulfonic acid (or its salts), vinyl sulfonic acid (or its salts), allyl sulfonic acid (or its salts), acrylamide propyl sulfonic acid (or its salts), and the like, wherein the salts of carboxylic acids and sulfonic acids are preferably neutralized by ammonium or alkylammonium cations. In one embodiment, the cation of the polyelectrolyte anionic polymer is an ammonium cation (NH₄⁺), cholinemonium +N(CH₃)₃(CH₂CH₂OH), and +N(CH₃)₄. Therefore, examples of combined synthetic and natural polyelectrolyte anionic polymers are homopolymers or copolymers of (meth)acrylic acid, maleic acid (or its anhydride), styrene sulfonic acid, vinyl sulfonic acid, allyl sulfonic acid, vinylphosphonic acid, acrylamide propyl sulfonic acid, alginic acid, carboxymethyl cellulose, dextran sulfate, poly(galacturonic acid), and their salts.

[0031] Cationic polymers and cationic polyelectrolytes can be natural polymers, modified natural polymers, or synthetic polymers. Exemplary natural and modified natural cationic polymers include (but are not limited to): chitosan, cationic starch, polylysine, and their salts. Exemplary cationic synthetic polyelectrolytes include (but are not limited to): diallyl dimethyl ammonium chloride (DADMAC), diallyl dimethyl ammonium bromide, diallyl dimethyl ammonium sulfate, diallyl dimethyl phosphonate ammonium, dimethyl allyl dimethyl ammonium chloride, diethyl allyl dimethyl ammonium chloride, diallyl di(β-hydroxyethyl) ammonium chloride, diallyl di(β-ethoxyethyl) ammonium chloride, addition salts and quaternary salts of (meth)acrylate dimethylaminoethyl ester, (methyl... Addition salts and quaternary salts of diethylaminoethyl acrylate, addition salts and quaternary salts of (meth)acrylate 7-amino-3,7-dimethyloctyl acrylate, addition salts and quaternary salts of N,N'-dimethylaminopropylacrylic acid (wherein such quaternary salts include alkyl and benzyl quaternary amination salts), allylamine, diallylamine, ethyleneamine (obtained by hydrolysis of vinylalkyl acetylamine polymers), vinylpyridine, chitosan, cationic starch, polyisocyanates and their salts, homopolymers or copolymers.

[0032] Other examples include 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfonium (cyclobutane), dimethyl sulfonium, ethylene glycol, propylene glycol, dipropylene glycol, tetraethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.

[0033] Alternatively, or furthermore, these hydrogen-bonding additives include hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone (PVP), any polymer synthesized using N-vinylpyrrolidone monomer, polyacrylates and similar polyacrylates, polyamino acids (e.g., polyacrylic acid, polyleucine, polyglycine), polyaminohydroxycarbamate, polylactone, polyacrylamide, xanthan gum, chitosan, polyethylene oxide, and polyvinyl alcohol (PVA). Polyvinyl acetate, polyacrylic acid, polyethyleneimine, sugar alcohols (such as sorbitol, sucrose, fructose, lactose, galactose, maltose, erythritol, maltitol, threitol, arabinitol, ribitol, mannitol, galactitol, inositol, and xylitol), esters of dehydrated sorbitol, secondary alcohol ethoxylates (such as TERGITOL™ surfactants), polyfunctional alcohols (including neopentyl tertetrol, dinepentyl tertetrol, trimethylolpropane, dimethylpropionic acid, and xylic acid), nucleobases (such as uracil, cytosine, guanine, and thymine), and combinations thereof.

[0034] Other examples of hydrogen-bonding additives include lactic acid, maleic acid, urea, glycolic acid, sorbitol, borax (i.e., sodium borate), proline, betaine, glycine, histidine, TRIS (tris(hydroxymethyl)aminomethane), dimethyl sulfoxide, cyclobutane, glycerol, SDS (sodium dodecyl sulfate), dodecylphosphonic acid, or combinations thereof. Among these, certain particle removal agents are preferably used in the post-CMP cleaning steps of microelectronic device substrates, such as maleic acid, borax (i.e., sodium borate), dimethyl sulfoxide, glycerol, or combinations thereof. When present, these additives will be present in amounts of about 0.0001 to 15% by weight, or about 0.001 to about 10% by weight, or about 1 to about 9% by weight.

[0035] In one embodiment, the composition further comprises a chelating agent. Generally, chelating agents used in post-CMP cleaning compositions are chemical compounds that typically form chelate molecules with metal ions (typically iron ions) to deactivate iron in the cleaning solution and prevent chemical reactions or activity of iron. Various chelating agents used in post-CMP cleaning compositions are known and can be used in the cleaning compositions and methods described herein. Certain specific examples include acidic organic molecules, particularly carboxylic acid organic molecules, such as straight-chain or branched C1-C6 carboxylic acid compounds, including phthalic acid, succinic acid, citric acid, tartaric acid, malic acid, gluconic acid, aspartic acid, or combinations thereof, as well as glycine, amino acids, and the like. Citric acid may be a preferred chelating agent for chelating iron ions (e.g., Fe²⁺, Fe³⁺). In some embodiments, sugar alcohols, such as arabinol, erythritol, glycerol, hydrogenated starch hydrolysate (HSH), isomaltitol, lactitol, maltitol, mannitol, sorbitol, and xylitol, are used as metal ion misalignment agents.

[0036] Other metal-linking reagents envisioned in this paper include (but are not limited to) acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, aspartic acid, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, 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, and mandelic acid. Acids, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, catechol, pyromellitic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, syrophthalic acid, tyrosine, valine, xylitol, ethylenediamine, oxalic acid, tannic acid, pyridinecarboxylic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid Pyruvic acid, propanethiol, benzohydroxyxamic acid, tetraethylpentamine (TEPA), 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) ), α-triacetic acid, aminosine (methylenephosphonic acid), hydroxyethyl bisphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), ethylenediaminepenta(methylenephosphonic 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, pyridinedicarboxylic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid and combinations thereof.

[0037] Other examples of suitable ligating agents include oligomers and polymers containing carboxylic acid groups derived from monomers, such monomers including acrylic acid, methacrylic acid, maleic acid, succinic acid, aspartic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide, phosphonomethacrylamidopropyltrimethylammonium chloride, allyl halides, or combinations thereof. Polyacrylic acid may be a preferred ligating agent for ligating silicon nitride (SiN). Other examples include propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid, trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid, phenylhexacarboxylic acid, and combinations thereof.

[0038] Generally, a misalignment agent can be included in a cleaning solution in a certain amount that can be used effectively as described herein. The specific type and amount of misalignment agent included in a given cleaning solution can be selected based on factors including: the type of substrate being cleaned, the type of residue present on the substrate surface, other components in the cleaning solution, and the conditions of the post-CMP cleaning process. When present, such misalignment agents are used at about 0.5 to about 20% by weight, about 0.5 to about 10% by weight, or about 0.8 to about 6% by weight.

[0039] The cleaning composition of the present invention may further include other ingredients or adjuvants (including polymers and surfactants) to improve the cleaning effect or efficiency of post-CMP cleaning steps using the cleaning solution. These ingredients include surfactants and biocides.

[0040] Exemplary surfactants and polymers include anionic, nonionic, cationic, and / or amphoteric surfactants. When present, these surfactants and polymers will be present in amounts from about 0.0001 to about 10% by weight. Examples include alginate and its salts; hydroxyl or carboxyalkyl cellulose; sulfated dextran 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, acrylaminopropyl 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, acrylaminopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyl dimethyl... Ammonium chloride (DADMAC), diallyl dimethyl ammonium bromide, diallyl dimethyl ammonium sulfate, diallyl dimethyl phosphonate ammonium, dimethyl allyl dimethyl ammonium chloride, diethyl allyl dimethyl ammonium chloride, diallyl di(β-hydroxyethyl) ammonium chloride, diallyl di(β-ethoxyethyl) ammonium chloride, addition salts and quaternary salts of dimethylaminoethyl methacrylate, addition salts and quaternary salts of diethylaminoethyl methacrylate, addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl methacrylate, N,N'-dimethylaminopropyl acrylamide Homopolymers of acid addition salts and quaternary salts, allylamine, diallylamine, ethyleneamine, and vinylpyridine; and diallyl dimethylammonium chloride (DADMAC), diallyl dimethylammonium bromide, diallyl dimethylammonium sulfate, diallyl dimethylphosphonate, dimethylallyl dimethylammonium chloride, diethylallyl dimethylammonium chloride, diallyl di(β-hydroxyethyl)ammonium chloride, diallyl di(β-ethoxyethyl)ammonium chloride, (meth)acrylate dimethylaminoethyl acetate addition salts and quaternary salts, (meth)acrylate diethylaminoethyl acetate addition salts and quaternary salts, (meth)acrylate... Addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl acrylate, addition salts and quaternary salts of N,N'-dimethylaminopropylacrylic acid, copolymers of allylamine, diallylamine, ethyleneamine, and vinylpyridine; cocoyl dimethyl carboxymethyl betaine; lauryl dimethyl carboxymethyl betaine; lauryl dimethyl-α-carboxyethyl betaine; cetyl dimethyl carboxymethyl betaine; lauryl-bis(2-hydroxyethyl)carboxymethyl betaine; stearyl-bis(2-hydroxypropyl)carboxymethyl betaine; oleyl dimethyl-γ-carboxypropyl betaine; lauryl-bis(2-hydroxypropyl) α-Carboxyethyl betaine; cocoyl dimethyl sulfopropyl betaine; stearyl dimethyl sulfopropyl betaine; lauryl-bis(2-hydroxyethyl)sulfopropyl betaine; Surfynol 104 (and its ethoxylated derivatives); sodium dioctyl sulfosuccinate; sodium lauryl ether sulfate; branched-chain polyethylene glycol-nonylphenyl ether ammonium sulfate; 2-dodecyl-3-(2-sulfonylphenoxy) disodium salt;PEG25-PABA; sodium sulfate of polyethylene glycol mono-C 10-16 alkyl ether; (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; dodecenylsuccinic acid monodiethanolamine; ethylenediamine tetra(ethoxylate-block-propoxylate); and combinations thereof.

[0041] In another embodiment, the composition further comprises a water-soluble or water-dispersible polymer. When present, such polymers include (but are not limited to) homopolymers of methacrylic acid and copolymers with acrylamide methylpropanesulfonic acid and maleic acid; maleic acid / vinyl ether copolymers; poly(vinylpyrrolidone) / vinyl acetate; phosphonated polyethylene glycol oligomers, poly(acrylic acid), poly(acrylamide), poly(vinyl acetate), poly(ethylene glycol), polypropylene glycol, poly(styrene sulfonic acid), poly(vinyl sulfonic acid), poly(vinylphosphonic acid), poly(vinyl phosphate), poly(ethylene imine), poly(propylene imine), polyallylamine, polyethylene oxide, polyvinylpyrrolidone, PPG-PEG-PPG block copolymers, and PEG-PPG. -PEG block copolymers, poly(vinyl alcohol), poly(hydroxyethyl) acrylate, poly(hydroxyethyl) methacrylate, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxypropyl cellulose, xanthan gum, potassium alginate, pectin, carboxymethyl cellulose, glucosamine, poly(diallyl dimethylammonium) chloride, poly(2-acrylamide-2-methyl-1-propanesulfonic acid), poly(styrene sulfonic acid), polyvinylpyrrolidone, PVA-poly(2-acrylamide-2-methyl-1-propanesulfonic acid) copolymer, polyethylene glycol-modified methacrylate / acrylate copolymer, poly(2-methacryloxyethyltrimethylammonium chloride) CAS No. 26161-33-1 and its copolymers, dimethylamino methacrylate polymers and their copolymers, trimethylammonium methyl methacrylate polymers and their copolymers, dimethylamino methacrylate polymers and their copolymers, trimethylammonium methyl methacrylate polymers and their copolymers, and combinations thereof. The above copolymers may be random or block copolymers. When present, the amount of polymer in the composition is in the range of about 0.0001% by weight to about 5% by weight based on the total weight of the composition.

[0042] Exemplary biocides contemplated herein include (but are not limited to) isothiazolinone biocides, such as 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, benzisothiazolinone, 1,2-benzisothiazolinone-3[2H]-one, methylisothiazolinone, methylchloroisothiazolinone, and combinations thereof. One example of a biocide is Proxel® GXL (BIT) 1,2-benzisothiazolinone-3(2H)-one.

[0043] In some embodiments, the components of the composition are present in the following proportions: a. 60 to 80% by weight water, for example, deionized water; b. 0.1 to 20% by weight of an alkanolamine having 2 to 7 carbon atoms; or 0.1 to 10% by weight, or 1 to 6% by weight; c. 0.01 to 30% by weight of glycol ethers; or 1 to 15% by weight, or 1 to 10% by weight; d. 0.001 to 10% by weight of pH adjuster; e. 0.00001 to 10% by weight, or 0.0001 to 8% by weight, or 0.005 to 5% by weight of a surface-active hydrophobic acid, wherein a., b., c., d. and e. total 100%.

[0044] The amount of pH adjuster depends on the final pH sought when preparing the removal composition for use, based on the pH values ​​disclosed herein and the knowledge of those skilled in the art. In some embodiments, the pH will be greater than 7, or between about 8 and 14, or between about 9 and 14.

[0045] The range of weight % ratios of the components will cover all possible concentrated or diluted embodiments of the composition. Therefore, in one embodiment, a concentrated composition is provided, which can be diluted for use as a cleaning solution. The concentrated composition, or "concentrate," advantageously allows a user (e.g., a CMP process engineer) to dilute the concentrate to the desired strength and pH at the point of use. The concentrated aqueous removal composition can be diluted in the range of about 1:1 to about 2500:1, about 5:1 to about 200:1, or about 20:1 to about 120:1, wherein the aqueous removal composition is diluted with a solvent (e.g., deionized water) when using the tool or immediately before using the tool. Those skilled in the art will understand that the range of weight % ratios of the components disclosed herein should remain unchanged after dilution.

[0046] According to some examples, the cleaning solution is in concentrated form before being diluted to the point of use composition. In some embodiments, the composition may be a concentrate ranging from up to 20%, or 0.5% to 10%, or 0.8% to 6%.

[0047] The compositions described herein are effective in applications including (but not limited to) removal of residues after etching, surface preparation with residues after ashing, cleaning after electroplating, and removal of residues after CMP. Furthermore, it is contemplated that the cleaning compositions described herein can be used to clean and protect other metal products (e.g., copper-containing, tungsten-containing, ruthenium-containing, cobalt-containing), including (but not limited to) decorative metals, wire bonding, printed circuit boards, and products using metals or metal alloys, along with other electronic packaging containing dielectric materials such as plasma-reinforced tetraethyl orthosilicate (PETEOS), silicon nitride, silicon oxynitride, silicon carbide, CVD carbon, porous organosilicon glass, CSOD, diamond-like carbon, silsesquioxane dielectrics (such as hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ)), silicon, BPSG, and HDP).

[0048] The removal compositions are readily formulated by simply adding the individual components and mixing to homogeneous conditions. Furthermore, these compositions can be readily formulated as single-package formulations or as multi-component formulations mixed at or before the point of use; for example, individual portions of a multi-component formulation may be mixed while using the tool or upstream of the tool's storage tank. The concentrations of the individual components can vary widely in compositions of specific multiples (i.e., further dilution or concentration), and it should be understood that the compositions described herein may comprise, consist of, or substantially consist of any combination of components consistent with those disclosed herein.

[0049] Therefore, another aspect relates to a kit comprising one or more containers having a component suitable for removal. A kit comprising one or more containers having a component suitable for removing cerium dioxide particles and chemimechanically ground contaminants from a microelectronic device thereon, wherein one or more containers of the kit contain a composition comprising: a.Water; b. Alkanolamines having 2 to 7 carbon atoms; c. Diol ethers; d. pH adjusters; and e. Surface-active hydrophobic acids.

[0050] The container for the kit must be suitable for storing and shipping the composition and may be, for example, a NOWPak® container (Entegris, Inc., Billerica, Mass., USA).

[0051] In one embodiment, one or more containers containing the components of the composition include means for bringing the components in the one or more containers into fluid communication for blending and dispensing. For example, referring to NOWPak® containers, air pressure can be applied to the outside of the liner of the one or more containers to cause at least a portion of the contents of the liner to be expelled and thus enable fluid communication for blending and dispensing. Alternatively, air pressure can be applied to the head space of a conventional pressurized container or a pump can be used to enable fluid communication. Furthermore, in some embodiments, the system includes a dispensing port for dispensing the blended removal composition to a processing tool.

[0052] When applied to microelectronics manufacturing operations, the removal compositions described herein can be used to clean residues and / or CMP contaminants (e.g., post-CMP residues and contaminants) from the surface of microelectronic devices. These removal compositions do not damage low-k dielectric materials (e.g., silicon oxide), silicon nitride layers, or tungsten-containing layers on the device surface. In one embodiment, the aqueous removal composition removes at least 85%, at least 90%, at least 95%, or at least 99% of the abrasive particles present on the device prior to particle removal.

[0053] Therefore, in another embodiment, the present invention provides a method for removing residues and / or contaminants from a microelectronic device having residues and / or contaminants thereon, the method comprising: (i) contacting the microelectronic device with a composition of the present invention; and (ii) at least partially removing the particles and contaminants from the microelectronic device, wherein the microelectronic device comprises a substrate selected from copper-containing, tungsten-containing, ruthenium-containing, and cobalt-containing products, such products including (but not limited to) decorative metals, wire bonding, printed circuit boards, and metals or metal alloys, together with dielectric materials such as plasma-reinforced tetraethyl orthosilicate (PETEOS), silicon nitride, silicon oxynitride, silicon carbide, CVD carbon, porous organosilicon glass, CSOD, diamond-like carbon, silsesquioxane dielectrics (such as hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ)), silicon, BPSG, and HDP) and other electronic packaging.

[0054] In post-CMP particle and contaminant removal applications, the aqueous removal compositions described herein can be used with a variety of conventional cleaning tools, such as ultrasonic cleaning and brush scrubbing, including (but not limited to) the Verteq single-wafer ultrasonic Goldfinger, the OnTrak system DDS (double-sided scrubber), SEZ or other single-wafer spray rinsing, Applied Materials Mirra-Mesa™ / Reflexion™ / Reflexion LK™, ultrasonic batch wet stage systems, EBARA Technologies, Inc. 300 mm models (FREX300S2 and FREX300X3SC) and 200 mm CMP systems (FREX200M).

[0055] In the use of the compositions described herein to remove residues and / or contaminants from microelectronic devices having such residues and / or contaminants thereon, the aqueous removal composition is typically contacted with the device for a period of about 5 seconds to about 10 minutes, or about 1 second to 20 minutes, or about 15 seconds to about 5 minutes at a temperature ranging from about 20°C to about 90°C, or about 20°C to about 50°C. These contact times and temperatures are illustrative, and any other suitable time and temperature conditions effective for at least partial removal of residues and / or contaminants from the device may be employed in a wide range of practices of the method. In some embodiments, "at least partially cleaned" and "substantially removed" both correspond to the removal of at least 85%, at least 90%, at least 95%, or at least 99% of the residues and / or contaminants present on the device prior to particle removal.

[0056] After achieving the desired particle removal effect, the aqueous removal composition can be easily removed from the device to which it was previously applied, as desired and effective in the given end-use application of the composition described herein. In one embodiment, the rinsing solution comprises deionized water. The device can then be dried using nitrogen or a rotary dryer cycle.

[0057] Another aspect relates to improved microelectronic devices prepared according to the methods described herein and products containing such microelectronic devices.

[0058] Another aspect relates to a recycleable aqueous removal composition, wherein the removal composition can be recycled until the residue and / or contaminant load reaches the maximum amount that the aqueous removal composition can accommodate, as can be easily determined by someone skilled in the art.

[0059] Another aspect relates to a method of manufacturing an article comprising a microelectronic device using the composition described herein, the method comprising contacting the microelectronic device with the composition of the present invention for a sufficient time to remove such residues and / or contaminants from the microelectronic device having residues and / or contaminants thereon, and incorporating the microelectronic device into the article.

[0060] The present invention can be further illustrated by the following examples of its preferred embodiments; however, it should be understood that, unless otherwise expressly specified, such examples are included for illustrative purposes only and are not intended to limit the scope of the invention.

[0061] [Example] [] Referring to Figure 1, samples 1, 2, 3, and 4 were prepared and subjected to beaker immersion tests on PETEOS. Generally, the procedure involves exposing the test wafer to a contaminated slurry at 100 rpm for approximately 5 minutes at room temperature using a magnetic stir bar. Next, the wafer is immersed in the composition of this invention at 550 rpm for approximately 30 seconds at room temperature using a magnetic stir bar. The wafer is then rinsed with deionized water in a third beaker for approximately 20 seconds, followed by drying with dry nitrogen. After the immersion test, the wafer samples are screened using SEM measurements and particle counting programs for comparison of cleaning performance via digital graph conversion.

[0062] As shown in Figure 1, where sample 1 is used as a comparative example, the composition of the present invention shows significant residue removal results. Sample 1 Blending order raw material CAS number Solvent (if applicable, as a solution) Original verification weight % Increase weight % Comparison by weight % 1 Deionized water 7732-18-5 - 77.24 81.77 2 monoethanolamine 141-43-5 100 4.50 4.5 3 PAA (MW approximately 2,000) 9003-01-04 H 2O 50.0 1.00 0.50 4 D-sorbitol 50-70-4 100.0 6.00 6.00 5 ascorbic acid 50-81-7 100.0 3.67 3.67 6 Proxel GXL (BIT) 1,2-Benzisothiazol-3(2H)-one 2634-33-5 100 0.008 0.008 7 Choline hydroxide (XHE-112) 123-41-1 H 2O 46.8 7.59 3.55 Total: 100 Sample 2: Mixing sequence raw material CAS number 1 Deionized water 7732-18-5 1 (G2) 1-Amino-2-propanol 78-96-6 3(E4) Ethylene glycol monohexyl ether 112-25-4 4 (M3) 4-Dodecylbenzenesulfonic acid 121-65-3 5 (A) Choline hydroxide (XHE-112) 123-41-1 6 ascorbic acid 50-81-7 7 D-sorbitol 50-70-4 8 Proxel® GXL (BIT) 1,2-Benzisothiazol-3(2H)-one 2634-33-5

[0063] Sample 3 is the same as Example 2, except that 4-dodecylbenzenesulfonic acid is omitted.

[0064] Sample 4 is the same as Example 2, except that ethylene glycol monohexyl ether is omitted. serial number sample TEOS area Standard deviation 1 Sample 1 (Comparative Example) 0.35 0.06 2 Sample 2 (modified) 0.08 0.05 3 Sample 3 (Modified DDBSA) 1.13 0.25 4 Sample 4 (Modified EGMHE) 0.63 0.08 serial number sample Surface tension (mN / m) WCA(°) average value deviation 1 Sample 1 (Comparative Example) 62.16 0.31 6.3 2 Sample 2 (modified) 23.93 0.15 7.1

[0065] Figure 2 shows the surface tension and water contact angle (WCA) of Sample 1 (Comparative Example) and the modified formulation. The newly introduced surface-active hydrophobic acid in Sample 2 illustrates that the reduction in surface tension contributes to the wafer cleaning effect. Sample X series: Mixing sequence raw material CAS number 1 Deionized water 7732-18-5 2 monoethanolamine 141-43-5 3 * Surfactant additives (see table below) 4 Diethylene glycol monobutyl ether 112-34-5 5 D-sorbitol 50-70-4 6 Proxel GXL (BIT) 1,2-Benzisothiazol-3(2H)-one 2634-33-5 7 Choline hydroxide 123-41-1 *Surface active additives CAS number Cleaning agent sample number butyric acid 107-92-6 Sample X BA bitter 124-07-2 Sample X OA nonanoic acid 112-05-0 Sample X NA Decanoic acid 334-48-5 Sample X DA sebacic acid 111-20-6 Sample X SA Oleic acid 505-48-6 Sample X SBA Citric acid – (Comparative example) 77-92-9 Sample X CA

[0066] Figure 3 shows the particle area results for various surfactant additive series used to compare the cleaning effects of formulations. Each formulation possesses different characteristics of surfactant additives (such as the alkyl chain length or number of functional groups) to identify the most effective structure for cleaning wafers. Samples XOA and XNA show the best results. serial number sample TEOS wafers Particle area (%) Standard deviation (%) 1 Sample X Control 0.11 0.04 2 Sample X BA 0.14 0.10 3 Sample X OA 0.04 0.01 4 Sample X NA 0.09 0.03 5 Sample X DA 0.14 0.08 6 Sample X DDA 0.18 0.05 7 Sample X SA 0.21 0.10 8 Sample X SBA 0.95 0.40 9 Sample X CA (Comparative Example) 1.27 0.40

[0067] The present invention has been described in detail with particular reference to certain embodiments thereof; however, it should be understood that variations and modifications may be made within the spirit and scope of the present invention.

Claims

1. A post-chemical mechanical polishing (POST CMP) composition comprising: a. water; b. an alkanolamine having 2 to 7 carbon atoms; c. a glycol ether; d. a pH adjuster; and e. a surface-active hydrophobic acid.

2. The composition of claim 1, wherein the alkanolamine is selected from aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, aminoethoxyethoxyethanol, methoxypropylamine, butoxyisopropylamine, 2-ethylhexylisopropoxyamine, ethanolpropylamine, ethylethanolamine, N-hydroxyethylmorpholine, aminopropyldiethanolamine, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 3-aminopropanol, diisopropylamine, and aminomethylpropylene glycol. N,N-dimethylaminomethylpropylene glycol, aminoethylpropylene glycol, N,N-dimethylaminoethylpropylene glycol, isopropylamine, 2-amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino-4-hydroxyoctane, 2-aminobutanol, hydroxymethylaminomethane, N,N-dimethylhydroxymethylaminomethane, hydroxypropylamine, benzylamine, hydroxyethylamine, hydroxyethylaminomethane, diethylene glycolamine, and combinations thereof.

3. The composition of claim 2, wherein the alkanolamine is selected from monoethanolamine, isopropanolamine and diisopropanolamine.

4. The composition of claim 1, wherein the glycol ether has a methylene linking group of formula -(CH2)x-, wherein x is an integer from 2 to 6.

5. The composition of claim 1, wherein the glycol ether is selected from 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, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, diethylene glycol phenyl ether, hexaethylene glycol monophenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, and dipropylene glycol phenyl ether, propylene glycol phenyl ether.

6. The composition of claim 1, wherein the pH adjuster is selected from choline hydroxide and tetraethylammonium hydroxide.

7. The composition of claim 1, wherein the surfactant hydrophobic acid is selected from sodium dodecyl sulfate, decylphosphonic acid, dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, bis(2-ethylhexyl)phosphate, octadecylphosphonic acid, perfluoroheptanoic acid, perfluorodecanoic acid, trifluoromethanesulfonic acid, phosphonoacetic acid, dodecylbenzenesulfonic acid, other benzenesulfonic acids or their salts substituted with a group R' (wherein R' is a straight-chain or branched C8-C18 alkyl group), myristyl sulfonic acid, tridecyl sulfonic acid, lauryl sulfonic acid, decyl sulfonic acid, undecyl sulfonic acid, dodecenyl succinic acid, di-(octadecyl)hydrogen phosphate. Salts, octadecyl dihydrogen phosphate, dodecenyl succinic acid, lauric acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, palmitic acid, oleic acid, juniperic acid, 12-hydroxystearic acid, sodium lauryl sarcosinate, C1-C6 alkylaryl phosphates, octadecylphosphonic acid, dodecyl phosphate, sodium lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate, bis(2-ethylhexyl)sulfosuccinate, sodium lauryl sarcosinate, alkylaryl phosphates, stearyl sarcosinate, stearic acid, arachidic acid (C20H40O2), carboxylic acid (C22H44O2), decanoic acid (C10H20O2), 2- Ethylhexanoic acid (C8H16O2), heptadecanoic acid (C17H34O2), heptanoic acid (C7H14O2), heptadecanoic acid (C37H74O2), hexanoic acid (C6H12O2), hexadecanoic acid (C36H72O2), lauric acid (C12H24O2), triacontacid (C30H60O2), 13-methyltetradecanoic acid (C15H30O2), octadecanoic acid (C28H56O2), myristic acid (C14H28O2), neodecanoic acid (C10H20O2), nonacontadecanoic acid (C29H58O2), nonacontadecanoic acid (CH3(CH 2) 17COOH), nonanoic acid (C9H18O2), palmitic acid (C16H32O2), pentacosic acid (C25H50O2), pentadecanoic acid (C15H30O2), phytic acid (C20H40O2), folinic acid (C33H66O2), stearic acid (C18H36O2), tetradecanoic acid (C34H68O2), tridecanoic acid (C23H46O2), tridecanoic acid (C13H26O2), tuberculinic stearic acid (C19H38O2), undecanoic acid (C11H22O2), octanoic acid, nonanoic acid, decanoic acid, sebacic acid, and octanoic acid.

8. The composition of claim 1, further comprising a corrosion inhibitor.

9. The composition of claim 1, further comprising a miscibility agent.

10. The composition of claim 1, further comprising a water-soluble or water-dispersible polymer.

11. The composition of claim 1, further comprising a biocidal agent.

12. The composition of claim 1, further comprising a hydrogen-bonded compound.

13. A method for removing residues and contaminants from a microelectronic device having residues and contaminants thereon, the method comprising contacting the microelectronic device with a cleaning composition for a time sufficient to at least partially clean the residues and contaminants from the microelectronic device, wherein the cleaning composition comprises: a. water; b. an alkanolamine having 2 to 7 carbon atoms; c. a glycol ether; d. a pH adjuster; and e. a surface-active hydrophobic acid.

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