Post-CMP Cleaning Compositions

Abstract

Generally, the present invention provides high pH cleaning compositions for dielectric surfaces such as PETEOS, SiO2, thermal oxide, silicon nitride, silicon, etc. The compositions of the present invention provide better surface wetting, dispersion of particles and organic residues, and prevent redeposition and reagglomeration of dispersed residues during cleaning, providing better cleaning and lower defectivity.

Description

[Technical field]

[0001] The present invention relates generally to compositions for removing post-CMP residues from surfaces of microelectronic devices. [Background technology]

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

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

[0004] Chemical mechanical polishing or chemical mechanical planarization ("CMP") is a method in which material is removed from the surface of a microelectronic device wafer and the surface is polished (e.g., planarized) by a combination of physical processes, such as abrasion, and chemical processes, such as oxidation or chelation. In its most basic form, CMP involves applying an abrasive slurry having active chemicals to a polishing pad that buffs the surface of the microelectronic device wafer during the removal, planarization, and polishing process. Removal or polishing using purely physical or purely chemical action is not as effective as a synergistic combination of both to achieve rapid, uniform removal. Furthermore, in the fabrication of integrated circuits, the CMP slurry should also be capable of selectively removing films, including multiple layers of metals and other materials, so that a highly planar surface can be produced for subsequent photolithography, or patterning, etching, and thin film processing.

[0005] In a front-end (FEOL) method for forming an isolation region in a silicon substrate using a shallow trench isolation (STI) method, a pad oxide film and a pad nitride film are deposited on a semiconductor substrate and patterned to expose a portion of the substrate corresponding to the isolation region. The exposed region of the substrate is then etched to form a trench. The substrate is then subjected to a sacrificial oxidation process to remove damage caused by the etching process of the substrate, and then a wall oxide film is formed on the surface of the trench. Next, a trench fill oxide film (e.g., an oxide film formed by high density plasma chemical vapor deposition, called HDP-oxide film) is deposited on the surface of the substrate so as to be embedded in the trench. 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 washed to remove the pad nitride film used as an etching barrier during the etching of the trench, completing the formation of the isolation region.

[0006] CMP slurries using ceria particles generally achieve higher polishing speeds on insulators compared to silica-containing slurries. Furthermore, ceria-based slurries are most often used because they achieve STI pattern planarization with minimal oxide erosion. Unfortunately, ceria-based slurries are difficult to remove from STI structures due to the oppositely charged zeta potential of ceria particles relative to silicon oxide and silicon nitride surfaces. When devices are fabricated with these residues remaining on the wafer, the residues will cause shorts and increase electrical resistance. Ceria particles are also an issue with FinFET structures after CMP processing using ceria slurries.

[0007] Dielectric substrates polished with slurries containing surface hydroxylated silica and other metal oxides as abrasive particles (PETEOS, SiO 2Post-CMP cleaning of dielectric surfaces (such as silicon oxide, thermal oxide, silicon nitride, silicon, etc.) is difficult and results in high residues and high defectivity due to strong interactions between the abrasive particles and the dielectric surface due to hydrogen bonding and van der Waals forces at low and moderate pH and particle aggregation and reprecipitation at high pH. Theoretically, at a pH above the IEP (isoelectric point), both the abrasive residue particles and the dielectric surface should be strongly negatively charged, so particle-substrate electrostatic repulsion should result in lower defectivity. In practice, the majority of organic additives in CMP slurries can inhibit and neutralize these strong repulsive forces, contributing to higher adhesion of particles to the wafer surface, an undesirable effect that leads to high defectivity. Thus, there is a need for improved post-CMP cleaning compositions that effectively remove both the residue particles as well as the residue adhering to the dielectric wafer surface. Summary of the Invention

[0008] In general, the present invention relates to PETEOS, SiO 2 The present invention provides a high pH cleaning composition for dielectric surfaces such as thermal oxide, silicon nitride, silicon, etc. The compositions of the present invention provide better surface wetting, dispersion of particles and organic residues, and prevent redeposition and reagglomeration of dispersed residues during cleaning to provide better cleaning and lower defectivity. In one aspect, the present invention provides a method for cleaning a dielectric surface such as a SiO 2 -based ... a water; b. alkanolamines having 2 to 7 carbon atoms; c. glycol ethers; d. pH adjusters; e. Surface active hydrophobic acid and The present invention provides a composition comprising: [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 shows the results of particle area for each formulation obtained by particle counting program followed by immersion test and SEM measurement, comparing sample 1 (comparative) with samples 2, 3, and 4. [Diagram 2]FIG. 2 is a graph of the surface tension and water contact angle (WCA) of Sample 1 (comparative) and the improved composition of the present invention. [Diagram 3] FIG. 1 shows particle area results for a series of different compositions. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention relates generally to compositions useful for removing residues and contaminants from microelectronic devices having such material(s). The compositions remove post-CMP, post-etch, or post-ash residues from a variety of substrates, including PETEOS, SiO 2 It is particularly useful for removing oxides from dielectric surfaces such as thermal oxide, silicon nitride, silicon, and the like.

[0011] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is used generally in its sense including "and / or" unless the context clearly dictates otherwise.

[0012] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (e.g., having the same function or result). In many instances, the term "about" can include numbers that are rounded to the nearest significant figure.

[0013] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0014] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: a water; b. alkanolamines having 2 to 7 carbon atoms; c. glycol ethers; d. pH adjusters; e. Surface active hydrophobic acid and The present invention provides a composition comprising:

[0015] In one embodiment, the alkanolamine is selected from the group consisting of 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-amino-1-propanol, diisopropylamine, aminomethylpropanediol, N,N-dimethylaminomethylpropanediol, The preferred amines are selected from amines selected from amines having the formula: amine, aminoethylpropanediol, N,N-dimethylaminoethylpropanediol, isopropylamine, 2-amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino,4-hydroxyoctane, 2-aminobutyranol, tris(hydroxymethyl)aminomethane (TRIS), N,N-dimethyltris(hydroxymethyl)aminomethane, hydroxypropylamine, benzylamine, hydroxyethylamine, tris(hydroxyethyl)aminomethane, diglycolamine, and combinations thereof.

[0016] In one embodiment, the glycol ether has the formula -(CH 2 ) x-, where x is an integer from 2 to 6, and optionally an aromatic group such as phenyl. In another embodiment, the glycol ether is 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, di ... The glycol ether is preferably selected from 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 glycol phenyl ether).

[0017] In one embodiment, the pH adjusting agent is a base in an amount effective to raise the pH of the composition to a desired pH upon use, in certain embodiments, the pH will be greater than 7, or between about 8 and 14, or between about 9 and 14.

[0018] The base may be any base that is useful for controlling the pH of the composition as specified, and many different basic compounds are known for use in cleaning solutions adapted to clean the surfaces of microelectronic device substrates, for example as post-CMP cleaning solutions. Bases include, but are not limited to, potassium hydroxide, ammonium hydroxide (i.e., ammonia), and bases of the formula NR 1 R 2 R 3 R 4 OH [wherein, R 1 , R 2 , R 3 , and R 4 may be the same or different, and are hydrogen, linear or branched C 1 ~C 6 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, C 1 ~C 6 Hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, and substituted or unsubstituted C 6 ~C 10and aryl groups (e.g., benzyl groups). 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.

[0019] Alternatively or additionally, the pH adjuster may be represented by the formula (PR 5 R 6 R 7 R 8 )OH[wherein, R 5 , R 6 , R 7 , and R 8 may be the same or different, and may be hydrogen, linear C 1 ~C 6 Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, branched C 1 ~C 6 Alkyl group, C 1 ~C 6Hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, substituted C 6 ~C 10 Aryl Group, Unsubstituted C 6 ~C 10 and any combination thereof, such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and the like.

[0020] In another embodiment, the pH adjuster (ie, base) is selected from choline hydroxide and tetraethylammonium hydroxide (TEAH).

[0021] These basic compounds may be included individually (e.g., alone) as the only basic compound in the composition; in combination with one another in the composition, i.e., as the only two basic compounds in the composition; or in combination with one or more additional (e.g., secondary) bases in the composition.

[0022] The term "surface active hydrophobic acid" as used herein corresponds to an acidic chemical species having a hydrophobic group, as will be readily understood by one of ordinary skill in the art, but does not include polymeric surfactants. Exemplary surface active hydrophobic acids or salts for use 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, a group R' (wherein R' is a linear or branched C 8~C 18 Other benzenesulfonic acids or their salts substituted with alkyl groups, myristylsulfonic acid, tridecylsulfonic acid, laurylsulfonic acid, decylsulfonic acid, undecylsulfonic acid, dodecenylsuccinic acid, dioctadecyl hydrogen phosphate, octadecyl dihydrogen phosphate, dodecenylsuccinic acid, lauric acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, palmitic acid, oleic acid, juniper acid, 12-hydroxystearic acid, sodium lauryl sarcosinate, C 1 ~C 6 Alkylaryl phosphate, octadecylphosphonic acid, dodecyl phosphate, sodium lauryl sulfate, ammonium lauryl sulfate, potassium lauryl sulfate, bis-(2-ethylhexyl) sulfosuccinate, sodium lauryl sarcosinate, alkylaryl phosphate, stearoyl sarcosine, stearic acid, arachidic acid, C 20 H 40 O 2 , behenic acid, C 22 H 44 O 2 , Decanoic acid, C 10 H 20 O 2 , 2-ethylhexanoic acid, C 8 H 16 O 2 , heptadecanoic acid, C 17 H 34 O 2 , heptanoic acid, C 7 H 14 O 2 , heptatriacontanoic acid, C 37 H 74 O 2 , hexanoic acid, C 6 H 12 O 2 , Hexatriacontanoic acid, C 36 H 72 O 2 , lauric acid, C 12 H 24 O 2 , melissic acid, C 30 H 60 O 2 , 13-methyltetradecanoic acid, C 15H 30 O 2 , Montanic acid, C 28 H 56 O 2 , myristic acid, C 14 H 28 O 2、 Neodecanoic acid, C 10 H 20 O 2 , nonacosylic acid, C 29 H 58 O 2 , nonadecylic acid, CH 3 (CH 2 ) 17 COOH, Nonanoic acid, C 9 H 18 O 2 , Palmitic acid, C 16 H 32 O 2 , Pentacosylic acid, C 25 H 50 O 2 , Pentadecanoic acid, C 15 H 30 O 2 , phytanic acid, C 20 H 40 O 2 , Psilicate, C 33 H 66 O 2 , stearic acid, C 18 H 36 O 2 , tetratriacontanoic acid, C 34 H 68 O 2 , Tricosylic acid, C 23 H 46 O 2 , Tridecylic acid, C 13 H 26 O 2 , tuberculostearic acid, C 19 H 38 O 2 , undecylic acid, C 11 H 22 O 2 , octanoic acid, sebacic acid, and suberic acid.

[0023] In one embodiment, the surface active hydrophobic acid is selected from octanoic acid, dodecylbenzenesulfonic acid, and nonanoic acid.

[0024] In one embodiment, the composition further comprises a corrosion inhibitor. Exemplary corrosion inhibitors include, but are not limited to, phosphorous acid, hypophosphorous acid, 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, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutaric acid, glyceric acid, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocalin, ethyl ... Tecol, pyromellitic acid, quinic acid, serine, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamic acid, 2,5-dicarboxypyridine (dica rboxypryidine), 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (HEdTA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropargyl alcohol, saccharin, and combinations thereof.

[0025] In another embodiment, the corrosion inhibitor is a compound that functions 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, phosphorous acid, phosphinic acid, hypophosphorous acid, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, potassium pyruvate, sodium pyruvate, ammonium pyruvate, formic acid, sodium formate, potassium formate, ammonium formate, dopamine, sulfur dioxide solution, and any combination thereof. For example, the corrosion inhibitor / reducing agent may include at least one sulfite ion and at least one of the other reductants listed, such as sulfurous acid, potassium sulfite, ammonium sulfite, phosphinic acid, diethylhydroxylamine sulfate, diethylhydroxylamine phosphate, and any combination thereof. It should be appreciated that in situ generation of ammonium sulfite is possible where ammonium sulfite is present and certain combinations of components result in the formation of ammonium sulfite to aid in the removal of residuals.

[0026] In another embodiment, the corrosion inhibitor is selected from ascorbic acid, phosphorous acid, hypophosphorous acid, sulfurous acid, diethylhydroxylamine, hydroxylamine sulfate, sodium / ammonium / potassium metabisulfite, and sodium / ammonium / potassium sulfite, as well as quaternary surfactants including N-alkyl-N-benzyl-N,N-dimethylammonium chloride (benzalkonium chloride) and 4-(3-phenylpropyl)pyridine.

[0027] In various embodiments, when present, the amount of corrosion inhibitor in the composition is in the range of 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 of about 0.0001 wt% to about 0.2 wt%, and in another embodiment, about 0.01 wt% to about 0.2 wt%, based on the total weight of the composition. In certain embodiments, the cleaning composition does not contain a corrosion inhibitor / reducing agent.

[0028] In other embodiments, the composition includes compounds that function as hydrogen bonding additives, which help reduce silica particles from adhering to brushes utilized in cleaning post-CMP microelectronic devices. 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, as well as polymers that can behave as polyelectrolytes at neutral pH. Anionic polymers or anionic polyelectrolytes may be natural, 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 salts), carboxymethylcellulose, dextran sulfate, poly(galacturonic acid), and salts thereof. Exemplary synthetic anionic polyelectrolytes include, but are not limited to, homopolymers or copolymers of (meth)acrylic acid (or salts), poly(acrylic acid), maleic acid (or anhydride), styrenesulfonic acid (or salts), vinylsulfonic acid (or salts), allylsulfonic acid (or salts), acrylamidopropylsulfonic acid (or salts), and the like, with the salts of carboxylic and sulfonic acids preferably being neutralized with ammonium or alkylammonium cations. In one embodiment, the cation of the polyelectrolyte anionic polymer is an ammonium cation (NH 4 + ), Corinium + N(CH 3 ) 3 (CH 2 CH 2 OH), and + N(CH 3 ) 4 Thus, examples of combined synthetic and natural polyelectrolyte anionic polymers are homopolymers or copolymers of (meth)acrylic acid, maleic acid (or anhydride), styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, acrylamidopropylsulfonic acid, alginic acid, carboxymethylcellulose, dextran sulfate, poly(galacturonic acid), and salts thereof.

[0029] Cationic polymers and cationic polyelectrolytes may be natural, modified natural polymers, or synthetic polymers. Exemplary natural and modified natural cationic polymers include, but are not limited to, chitosan, cationic starch, polylysine, and salts thereof. Exemplary cationic synthetic polyelectrolytes include, but are not limited to, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl(meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl(meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl(meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamido acid addition salts and quaternary salts (quaternary salts include alkyl and benzyl quaternary salts); homopolymers or copolymers of allylamine, diallylamine, vinylamine (obtained by hydrolysis of vinyl alkylamide polymers), vinylpyridine, chitosan, cationic starch, polylysine, and salts thereof.

[0030] Other examples include 2-pyrrolidinone, 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraglyme, and diglyme.

[0031] Alternatively, or in addition, hydrogen bonding additives include hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidone (PVP), any polymer made using N-vinylpyrrolidone monomer, polyacrylates and polyacrylate analogs, polyamino acids (e.g., polyalanine, polyleucine, polyglycine), polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic acid, polyethyleneimine, sugar alcohols such as sorbitol, sucrose, fructose, lactose, galactose, maltose, glycerol ... esters of anhydrosorbitol, such as erythritol, maltitol, threitol, arabinol, ribitol, mannitol, galactitol, inositol, and xylitol; secondary alcohol ethoxylates, such as the TERGITOL™ surfactants; polyfunctional alcohols, including pentaerythritol, dipentaerythitol, trimethylolpropane, dimethylpropionic acid, and xylonic acid; nucleopbases, such as uracil, cytosine, guanine, thymine, and the like, and combinations thereof.

[0032] Still 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), dimethylsulfoxide, sulfolane, glycerol, SDS (sodium dodecyl sulfate), dodecylphosphonic acid, or combinations thereof. Among these, certain particle removers, such as maleic acid, borax (i.e., sodium borate), dimethylsulfoxide, glycerol, or combinations thereof, may be preferred for use in post-CMP cleaning steps of microelectronic device substrates. When present, such additives will be present at about 0.0001 to 15 weight percent, or about 0.001 to about 10 weight percent, about 1 to about 10 weight percent, or about 1 to about 9 weight percent.

[0033] In one embodiment, the composition further comprises a complexing agent. In general, complexing agents used in post-CMP cleaning compositions are compounds that typically form complex molecules with metal ions, often iron ions, to inactivate the ions in the cleaning solution and inhibit chemical reactions or activity with the ions. A variety of complexing agents are known for use in post-CMP cleaning compositions and may be used in the cleaning compositions and methods described herein. Specific examples include acid-containing organic molecules, particularly carboxylic acid-containing organic molecules, such as linear or branched C carboxylic acids, including phthalic acid, succinic acid, citric acid, tartaric acid, malic acid, gluconic acid, aspartic acid, or combinations thereof. 1 ~C 6 Carboxylic acid compounds, glycine, amino acids, etc. Citric acid is a ferric ion (e.g., Fe +2 , Fe +3 In certain embodiments, sugar alcohols such as arabitol, erythritol, glycerol, hydrogenated starch hydrolysates (HSH), isomalt, lactitol, maltitol, mannitol, sorbitol, and xylitol are utilized as complexing agents for metal ions.

[0034] Other metal complexing agents contemplated herein 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, glutaric acid, glyceric acid, glycerin, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4 -Pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, ethylenediamine, oxalic acid, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, Benzohydroxamic acid, tetraethylenepentamine (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), nitrilotriacetic acid, aminotris(methylene phosphate), hydroxyethyldiamine hydroxyethylidine diphosphonic acid, ethylenediaminotetrakis(methylene phosphate), ethylenediaminopentakis(methylene phosphate), thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, dipicolinic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid, and combinations thereof.

[0035] Other examples of useful complexing agents include carboxylic acid group-containing oligomers and polymers derived from monomers that may include one or more of acrylic acid, methacrylic acid, maleic acid, succinic acid, aspartic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide, phosphonate methacrylamidopropyl trimethylammonium chloride, allyl halide, or combinations thereof. Polyacrylic acid may be a preferred complexing agent for complexing silica nitride (SiN). Still 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, trimesic acid, pyromellitic acid, mellitic acid, and combinations thereof.

[0036] In general, the complexing agent may be included in the cleaning solution in any useful amount such that the complexing agent is effective in the methods described herein. The particular type and amount of complexing agent to be 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, the complexing agent is utilized at about 0.5 to about 20 weight percent, about 0.5 to about 10 weight percent, or about 0.8 to about 6 weight percent.

[0037] The cleaning compositions of the present invention may further comprise other ingredients or adjuvants, including polymers and surfactants, to improve the cleaning effectiveness or efficiency of post-CMP steps using the cleaning solution. Such ingredients include surfactants and biocides.

[0038] Exemplary surfactants and polymers include anionic, nonionic, cationic, and / or zwitterionic surfactants. When present, such surfactants and polymers will be present in an amount of about 0.0001 to about 10 weight percent. Examples include alginic acid and its salts; hydroxyl or carboxyalkyl cellulose; dextran sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, 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 dimethyl ammonium chloride (DADMAC), Diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamido acid addition salts and quaternary salts, homopolymers of allylamine, diallylamine, vinylamine, vinylpyridine;Diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, dimethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, diethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, 7-Amino-3,7-dimethyloctyl (meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamido acid addition salts and quaternary salts, copolymers of allylamine, diallylamine, vinylamine, vinylpyridine; Cocodimethylcarboxymethyl betaine; Lauryldimethylcarboxymethyl betaine; Lauryldimethyl-alpha-carboxyethyl betaine; Cetyldimethylcarboxymethyl betaine; Lauryl-bis-(2-hydroxyethyl)carboxymethyl betaine; Stearyl-bis-(2-hydroxypropyl (yl) carboxymethyl betaine;Oleyl dimethyl-gamma-carboxypropyl betaine;Lauryl-bis-(2-hydroxypropyl) alpha-carboxyethyl betaine;Coco dimethyl sulfopropyl betaine;Stearyl dimethyl sulfopropyl betaine;Lauryl-bis-(2-hydroxyethyl) sulfopropyl betaine;Surfynol 104, (and its ethoxylated derivatives);Dioctyl sulfosuccinic acid sodium salt;Sodium lauryl ether sulfate;Polyethylene glycol Branched nonylphenyl ether sulfate ammonium salt;2-dodecyl-3-(2-sulfonatophenoxy) disodium salt;PEG25-PABA;Polyethylene glycol mono-C10-16-alkyl ether sulfate sodium salt;(2-N-butoxyethoxy)acetic acid;Hexadecylbenzenesulfonic acid;Cetyltrimethylammonium hydroxide;Dodecyltrimethylammonium hydroxide;Dodecyltrimethylammonium chloride;Cetyltrimethylammonium chloride;N-Alkyl-N-benzyl-N,N-dimethylammonium chloride;dodecylamine; polyoxyethylene lauryl ether; dodecenylsuccinic acid monodiethanolamide; ethylenediamine tetrakis(ethoxylate-block-propoxylate); and combinations thereof.

[0039] In further embodiments, the composition further comprises a water-soluble or water-dispersible polymer, including, but not limited to, homopolymers of methacrylic acid and copolymers of methacrylic acid with acrylamidomethylpropanesulfonic acid and maleic acid, when present; 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(styrenesulfonic acid), poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinyl phosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide, polyvinylpyrrolidone, PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, poly(vinyl alcohol), poly(hydroxyethyl)acrylate, poly(hydroxyethyl)methacrylate, hydroxyethylcellulose, methylhydroxyethylcellulose, hydrobromide, hydroxyethylcellulose ... Examples of the copolymers include hydroxypropyl cellulose, methylhydroxypropyl cellulose, xanthan gum, potassium alginate, pectin, carboxymethyl cellulose, glucosamine, poly(diallyldimethylammonium) chloride, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(styrenesulfonic acid), polyvinylpyrrolidone, PVA-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) copolymer, polyethylene glycol-methacrylate / acrylate copolymer, poly(2-methacryloxyethyltrimethylammonium chloride) CAS number 26161-33-1 and copolymers thereof, dimethylamino methacrylate polymers and copolymers thereof, trimethylammonium methyl methacrylate polymers and copolymers thereof, dimethylamino methacrylate polymers and copolymers thereof, trimethylammonium methyl methacrylate polymers and copolymers thereof, and combinations thereof. The copolymers may be random or block copolymers.When present, the amount of polymer(s) in the composition ranges from about 0.0001% by weight to about 5% by weight, based on the total weight of the composition.

[0040] 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, benzisothiazolone, 1,2-benzisothiazol-3[2H]-one, methylisothiazolinone, methylchloroisothiazolinone, and combinations thereof. In an embodiment, a biocide may be included. One example of a biocide is Proxel® GXL (BIT) 1,2-benzisothiazol-3(2H)-one.

[0041] In certain embodiments, the components of the composition are: a. 60 to 80 weight percent water, e.g., deionized water; b. 0.1 to 20 weight percent, or 0.1 to 10 weight percent, or 1 to 6 weight percent of an alkanolamine having 2 to 7 carbon atoms; c. 0.01 to 30 weight percent, or 1 to 15 weight percent, or 1 to 10 weight percent of a glycol ether; d. 0.001 to 10 weight percent of a pH adjuster; e. 0.00001 to 10 weight percent, or 0.0001 to 8 weight percent, or 0.005 to 5 weight percent of a surface active hydrophobic acid; and the sum of a., b., c., d., and e. is 100 percent.

[0042] The amount of pH adjuster will depend on the desired final pH in the preparation of the removal composition used, based on the pH values ​​disclosed herein and the knowledge of one of ordinary skill in the art. In certain embodiments, the pH will be greater than 7, or between about 8 and 14, or between about 9 and 14.

[0043] The weight percentage ratio ranges of the components are intended to cover all possible concentrated or diluted embodiments of the composition. To that end, in one embodiment, a concentrated composition is provided that can be diluted as a cleaning solution. The concentrated composition, or "concentrate," advantageously allows the user (e.g., a CMP process engineer) to dilute the concentrate to a desired concentration and pH at the time of use. The dilution of the concentrated aqueous removal composition may range from about 1:1 to about 2500:1, about 5:1 to about 200:1, or about 20:1 to about 120:1, and the aqueous removal composition is diluted with a solvent, such as deionized water, at or immediately before tool use. It should be recognized by those skilled in the art that after dilution, the weight percentage ratio ranges of the components disclosed herein should remain unchanged.

[0044] According to certain exemplary cleaning solutions that are in concentrated form, the compositions may be up to 20%, or in the range of 0.5-10%, or 0.8-6% concentrate, in certain embodiments, prior to dilution of the composition at the time of use.

[0045] The compositions described herein may have utility in applications including, but not limited to, post-etch residue removal, post-ash residue removal surface preparation, post-plating cleaning, and post-CMP residue removal.In addition, it is believed that the cleaning compositions described herein may be useful for cleaning and protecting other metal (e.g., copper-containing, tungsten-containing, ruthenium-containing, cobalt-containing) products, including, but not limited to, decorative metal, metal wire bonding, printed wiring board, and other electronic packages using metal or metal alloy with dielectric materials, such as plasma-enhanced tetraethyl orthosilicate (PETEOS), silicon nitride, silicon oxynitride, silicon carbide, CVD carbon, porous organosilicate glass, CSOD, diamond-like carbon, silsesquioxane-based dielectrics such as hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ), silicon, BPSG, and HDP.

[0046] The removal composition is easily formulated by simply adding each component and mixing to a homogeneous condition. Furthermore, the composition can be easily formulated as a single package formulation or as a multi-part formulation that is mixed at or immediately before use, for example, the individual parts of the multi-part formulation can be mixed at the time of use of the tool or in a storage tank upstream of the tool. It will be understood that the concentration of each component can vary widely in a particular portion of the composition, i.e., it can be at a lower or higher concentration, and the compositions described herein can variously and alternatively comprise, consist of, or consist essentially of any combination of components in accordance with the disclosure herein.

[0047] Accordingly, another aspect relates to a kit comprising one or more containers having components therein suitable for removing ceria particles and chemical mechanical polishing contaminants from a microelectronic device on which said particles and contaminants are deposited, said one or more containers of said kit comprising: a. Water; b. alkanolamines having 2 to 7 carbon atoms; c. glycol ethers; d. pH adjusters; e. Surface active hydrophobic acids The composition comprises:

[0048] The containers of the kit should be suitable for storing and shipping the compositions and may be, for example, NOWPak® containers (Entegris, Inc., Billerica, Mass., USA).

[0049] In one embodiment, the one or more containers that contain the components of the composition include a means for fluidly communicating the components in said 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 said one or more containers to release at least a portion of the contents of the liner, thereby enabling fluid communication for blending and dispensing. Alternatively, gas pressure can be applied to the head space of a conventional pressurizable container, or a pump can be used to enable fluid communication. Furthermore, in certain embodiments, the system includes a dispensing port for dispensing the blended removal composition to a processing tool.

[0050] When applied to microelectronic manufacturing operations, the removal compositions described herein are typically used to clean residues and / or CMP contaminants (e.g., post-CMP residues and contaminants) from the surface of a microelectronic device. The 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.

[0051] Thus, in a further aspect, the present invention provides a method for removing residues and / or contaminants from a microelectronic device having residues and contaminants deposited thereon, comprising: (i) contacting the microelectronic device with a composition of the present invention; and (ii) at least partially removing said particles and contaminants from said microelectronic device, said microelectronic device comprising a substrate selected from copper-, tungsten-, ruthenium-, cobalt-containing products including decorative metals, metal wire bonding, printed wiring boards, and other electronic packages using metals or metal alloys with dielectric materials such as plasma enhanced tetraethyl orthosilicate (PETEOS), silicon nitride, silicon oxynitride, silicon carbide, CVD carbon, porous organosilicate glass, CSOD, diamond-like carbon, silsesquioxane-based dielectrics such as hydrogen silsesquioxane (HSQ) and methyl silsesquioxane (MSQ), silicon, BPSG, and HDP.

[0052] In post CMP particle and contaminant removal applications, the aqueous removal compositions described herein may be used with a variety of conventional cleaning tools such as megasonic and brush cleaning, including, but not limited to, Verteq single wafer megasonic Goldfinger, OnTrak systems DDS (double sided scrubber), SEZ, or other single wafer spray rinse, Applied Materials Mirra-Mesa™ / Reflexion™ / ReflexionLK™, megasonic batch wet bench systems, EBARA Technologies, Inc. 300 mm models (FREX300S2 and FREX300X3SC) and 200 mm CMP system (FREX200M).

[0053] In using the compositions described herein to remove residues and / or contaminants from a microelectronic device having residues and / or contaminants deposited thereon, the aqueous removal composition is typically contacted with the device for a time of about 5 seconds to about 10 minutes, or about 1 second to about 20 minutes, or about 15 seconds to about 5 minutes, at a temperature in the range of about 20° C. to about 90° C., or about 20° C. to about 50° C. Such contact times and temperatures are exemplary, and any other suitable time and temperature conditions effective to at least partially remove the residues and / or contaminants from the device may be employed within the broad practice of the method. Both "at least partially clean" and "substantially remove" correspond in certain embodiments to 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.

[0054] After obtaining the desired particle removal effect, the aqueous removal composition may be easily removed from the device to which it was previously applied, as desired and effective in the specified end use of the composition described herein. In one embodiment, the rinse solution comprises deionized water. The device may then be dried using nitrogen or a spin dry cycle.

[0055] Still other aspects relate to improved microelectronic devices made according to the methods described herein, and to products including such microelectronic devices.

[0056] Another embodiment relates to a recycled aqueous removal composition, which can be recycled until the residual and / or contaminant load reaches a maximum that the aqueous removal composition can tolerate, as readily determined by one of skill in the art.

[0057] Yet further aspects relate to methods of making an article comprising a microelectronic device, the method comprising contacting the microelectronic device with a composition of the invention for a time sufficient to remove residue and / or contaminants from the microelectronic device having residue and / or contaminants deposited thereon, and incorporating the microelectronic device into the article using a composition described herein.

[0058] The present invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that, unless specifically indicated otherwise, these examples are included for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLES

[0059] Referring to FIG. 1, samples 1, 2, 3, and 4 were prepared and subjected to beaker immersion testing for PETEOS. Generally, the procedure involved exposing the test wafers to the contaminated slurry at room temperature for about 5 minutes using a magnetic stir bar at 100 rpm. The wafers were then placed in the composition of the present invention at room temperature for about 30 seconds using a magnetic stir bar at 550 rpm. The wafers were then rinsed in a beaker with deionized water for about 20 seconds, followed by drying with dry nitrogen. After the immersion testing, the wafer samples were screened with a particle counting program for SEM measurement and conversion to compare cleaning performance with a numerically based graph.

[0060] As shown in FIG. 1, Sample 1 served as a comparative example and the composition of the present invention demonstrated significant residue removal results. TIFF0007620702000001.tif123170TIFF0007620702000002.tif102170

[0061] Sample 3 is the same as Example 2, except that 4-dodecylbenzenesulfonic acid is omitted.

[0062] Sample 4 is the same as Example 2, except that ethylene glycol monohexyl ether is omitted. TIFF0007620702000003.tif93170TIFF0007620702000004.tif59170

[0063] Figure 2 shows the surface tension and water contact angle (WCA) of sample 1 (comparative) and the improved formulation. The newly introduced surface active hydrophobic acid in sample 2 shows a reduction in surface tension which helps in the cleaning effect of the wafer. Sample X series: TIFF0007620702000005.tif85170TIFF0007620702000006.tif77170

[0064] Figure 3 shows the particle area results of a series of various surface active additives for the comparison of the cleaning effect of the formulations. Each formulation has different properties of the surface active additives, such as alkyl chain length or number of functional groups, to find the most effective structure for cleaning the wafer. Sample XOA and Sample XNA showed the best results. TIFF0007620702000007.tif103170

[0065] Although the invention has been described in detail with particular reference to certain embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. a. water; b. an alkanolamine having 2 to 7 carbon atoms; c. a glycol ether; d. a pH adjuster; e. a surface active hydrophobic acid selected from octanoic acid and nonanoic acid; A post-CMP cleaning composition comprising:

2. Alkanolamines include 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, aminomethylpropanediol, and N,N-dimethylaminomethylpropanediol; 2. The post-CMP cleaning composition of claim 1, wherein the cleaning agent is selected from aminoethylpropanediol, N,N-dimethylaminoethylpropanediol, isopropylamine, 2-amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino, 4-hydroxyoctane, 2-aminobutyranol, tris(hydroxymethyl)aminomethane, N,N-dimethyltris(hydroxymethyl)aminomethane, hydroxypropylamine, benzylamine, hydroxyethylamine, tris(hydroxyethyl)aminomethane, diglycolamine, and combinations thereof.

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

4. The glycol ether is represented by the formula -(CH ２ ) ｘ 2. The post-CMP cleaning composition of claim 1, having methylene linking groups of: -wherein x is an integer from 2 to 6.

5. 2. The post-CMP cleaning 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. 6. The post-CMP cleaning composition of claim 5, wherein the glycol ether is selected from triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, triethylene glycol monohexyl ether, diethylene glycol monohexyl ether, and ethylene glycol monohexyl ether.

7. 6. The post-CMP cleaning composition of claim 5, wherein the glycol ether is ethylene glycol monohexyl ether.

8. 2. The post-CMP cleaning composition of claim 1, wherein the pH adjuster is selected from choline hydroxide and tetraethylammonium hydroxide.

9. The post-CMP cleaning composition of claim 1 further comprising a corrosion inhibitor.

10. The corrosion inhibitor is a quaternary surfactant selected from phosphorous acid, hypophosphorous acid, sulfurous acid, diethylhydroxylamine, hydroxylamine sulfate, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, N-alkyl-N-benzyl-N,N-dimethylammonium chloride, and 4-(3-phenylpropyl)pyridine, acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid. , glutamine, glutaric acid, glyceric acid, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocatechol, pyromellitic acid, quinic acid, serine, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, picolinic acid, 1,3- Cyclopentanedione, catechol, pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamic acid, 2,5-dicarboxypyridine, 4-(2-hydroxyethyl)morpholine, N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, N-(hydroxyethyl)-ethylenediaminetriacetic acid, iminodiacetic acid, 2-(hydroxyethyl)isopropyl ether, 10. The post-CMP cleaning composition of claim 9, wherein the active ingredient is selected from aminodiacetic acid, nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxamic acid, 5-sulfosalicylic acid, triazole, aminotriazole, dimethylpropargyl alcohol, saccharin, and combinations thereof.

11. 10. The post-CMP cleaning composition of claim 9, wherein the corrosion inhibitor is selected from ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, sulfurous acid, ammonium sulfite, potassium sulfite, sodium sulfite, dopamine HCl, phosphorous acid, phosphinic acid, hypophosphorous acid, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, potassium pyruvate, sodium pyruvate, ammonium pyruvate, formic acid, sodium formate, potassium formate, ammonium formate, dopamine, sulfur dioxide solution, and any combination thereof.

12. 10. The post-CMP cleaning composition of claim 9, wherein the corrosion inhibitor is selected from ascorbic acid, phosphorous acid, hypophosphorous acid, sulfurous acid, diethylhydroxylamine, hydroxylamine sulfate, sodium / ammonium / potassium metabisulfite, and sodium / ammonium / potassium sulfite, and quaternary surfactants selected from N-alkyl-N-benzyl-N,N-dimethylammonium chloride and 4-(3-phenylpropyl)pyridine.

13. The post-CMP cleaning composition of claim 1, further comprising a complexing agent different from the corrosion inhibitor.

14. The complexing agent may be phthalic acid, succinic acid, citric acid, tartaric acid, malic acid, gluconic acid, aspartic acid, arabitol, erythritol, glycerol, hydrogenated starch hydrolysate, isomalt, lactitol, maltitol, mannitol, sorbitol, xylitol, acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, glyceryl, glyceryl, glycerol, glyceryl ... dextrin, iminodiacetic acid, isophthalic 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, pyrocatechol, pyromellitic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, trimesic acid, tyrosine, valine, xylitol, ethylenediamine, oxalic acid, tannic acid, picolinic acid, 1,3-cyclopentanedione, catechol, pyrogallol, resorcinol, hyaluronic acid ... Hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxamic acid, tetraethylenepentamine, 4-(2-hydroxyethyl)morpholine, N-aminoethylpiperazine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, N-(hydroxyethyl)-ethylenediaminetriacetic acid, iminodiacetic acid, 2-(hydroxyethyl)iminodiacetic acid, nitrilotriacetic acid, aminotris(methylene phosphate), hydroxyethylidine dine) diphosphonic acid, ethylenediaminotetrakis (methylene phosphoric acid), ethylenediaminopentakis (methylene phosphoric acid), thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperazine, N-(2-aminoethyl)piperazine, pyrrolidine, threonine, tryptophan, salicylic acid, dipicolinic acid, p-toluenesulfonic acid, 5-sulfosalicylic acid, propane-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, pentane-1,2,3,4,5-pentacarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, mellitic acid, Carboxylic acid group-containing oligomers and polymers derived from monomers including one or more of acrylic acid, methacrylic acid, maleic acid, succinic acid, aspartic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide, phosphonate methacrylamidopropyltrimethylammonium chloride, and allyl halides; 14. The post-CMP cleaning composition of claim 13 selected from the group consisting of dimethylformamide, dimethyl ether ...

15. The post-CMP cleaning composition of claim 1 further comprising a water-soluble or water-dispersible polymer.

16. The water-soluble or water-dispersible polymers include homopolymers of methacrylic acid and copolymers of methacrylic acid with acrylamidomethylpropanesulfonic 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), poly(propylene glycol), poly(styrenesulfonic acid), poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinyl phosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide, polyvinylpyrrolidone, PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, poly(vinyl alcohol), poly(hydroxyethyl)acrylate, poly(hydroxyethyl)methacrylate, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose, methyl ...

16. The post-CMP cleaning composition of claim 15, wherein the cleaning agent is selected from pyrulose, methylhydroxypropylcellulose, xanthan gum, potassium alginate, pectin, carboxymethylcellulose, glucosamine, poly(diallyldimethylammonium) chloride, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(styrenesulfonic acid), polyvinylpyrrolidone, PVA-poly(2-acrylamido-2-methyl-1-propanesulfonic acid) copolymers, polyethylene glycolated) methacrylate / acrylate copolymers, poly(2-methacryloxyethyltrimethylammonium chloride) and copolymers thereof, dimethylamino methacrylate polymers and copolymers thereof, trimethylammonium methyl methacrylate polymers and copolymers thereof, dimethylamino methacrylate polymers and copolymers thereof, trimethylammonium methyl methacrylate polymers and copolymers thereof, and combinations thereof.

17. The post-CMP cleaning composition of claim 1 further comprising a biocide.

18. The post-CMP cleaning composition of claim 1, further comprising a hydrogen bonding compound that is different from the corrosion inhibitor and different from the complexing agent.

19. 1. A method for removing residue and contaminants from a microelectronic device having residue and contaminants deposited thereon, comprising contacting the microelectronic device with a post-CMP cleaning composition for a time sufficient to at least partially clean the residue and contaminants from the microelectronic device, the post-CMP cleaning composition comprising: a. water; b. an alkanolamine having 2 to 7 carbon atoms; c. a glycol ether; d. a pH adjuster; e. a surface active hydrophobic acid selected from octanoic acid and nonanoic acid; A method comprising:

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