Microelectronic device cleaning composition

Abstract

Compositions for cleaning microelectronic device substrates are provided. The compositions are useful for cleaning in-process microelectronic device substrates having exposed cobalt, molybdenum, copper, molybdenum, tungsten and dielectric surfaces. Additionally, methods for cleaning such devices and kits including one or more of the components of the compositions are provided.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates generally to aqueous compositions for cleaning the surface of a microelectronic device substrate, such as for cleaning residue from the surface of a microelectronic device substrate. [Background technology]

[0002] Microelectronic device substrates are used to fabricate integrated circuit devices. Microelectronic device substrates include base materials, such as silicon wafers, that have highly planar surfaces. Regions of electronically functional features are added to the planar surface of the substrate through multiple iterations of selective deposition and removal processes. These features are created by selectively adding and removing insulating, conductive, or semiconductive electronically functional materials. These electronically functional materials are placed as desired using processing materials, including photoresists, chemical etchants, and slurries containing abrasives and chemical materials that aid in processing the surface.

[0003] One feature of an integrated circuit is an array of conductive "interconnects," also referred to as "lines" and "vias." As part of the integrated circuit, the conductive interconnects function to conduct electrical current between various other electronic features. Each interconnect is in the form of a line or thin film of conductive material, i.e., a dielectric material, that extends into and is defined (in shape and size) by an opening formed in an insulating material. The dielectric material acts as an insulator between closely spaced interconnect structures and between the interconnect structures and other electronic features of the integrated circuit.

[0004] The types of materials used to create the interconnect and dielectric structures must be selected to function properly as part of an integrated circuit that operates efficiently and reliably. For example, the conductive material of the interconnect should be of a type that does not excessively migrate (e.g., diffuse) into adjacent dielectric materials over time and during use in the presence of a voltage between the materials; such migration of interconnect materials into adjacent dielectric materials is often referred to as "electromigration." At the same time, the combined interconnect and dielectric material structures must have sufficient integrity, including at the interfaces between these materials, to result in low levels of defects and high levels of performance reliability. For example, a strong bond must exist at the interfaces to prevent the dielectric material from separating from the interconnect material during use.

[0005] Interconnects have traditionally been made from aluminum or tungsten, and more recently from copper. Copper advantageously has higher electrical conductivity than aluminum and tungsten. Furthermore, copper-based interconnects offer better resistance to electromigration than aluminum, thereby improving the reliability of integrated circuits over time. Nevertheless, copper ions can easily diffuse into silicon dioxide (SiO2) under a sufficient electrical bias, and copper can have poor adhesion to silicon dioxide and other dielectric materials.

[0006] To prevent these negative copper-dielectric interactions, modern integrated circuit structures have been designed to include a barrier layer between the copper interconnect structure and the adjacent dielectric material. Examples of barrier layers can be conductive or non-conductive materials, such as tantalum (Ta), tantalum nitride (TaN), and the like. x ), tungsten (W), titanium (Ti), titanium nitride (TiN), ruthenium (Ru), cobalt (Co), molybdenum (Mo), rhenium (Rh), and alloys thereof.

[0007] Methods for disposing various features of microelectronic devices on substrates include selectively depositing insulating materials (e.g., dielectrics), semiconducting materials, metallic materials (e.g., conductive lines and vias (i.e., interconnects)), and the like, on substrate surfaces. The selective deposition and removal of these materials may involve the use of process compositions such as photoresists, etchants, CMP slurries, and plasmas containing abrasives and chemical materials, among others, in processes such as photoresist coating, etching (e.g., wet etching, plasma etching), chemical machining (also known as chemical mechanical polishing, chemical mechanical planarization, or simply "CMP"), and ashing ("plasma ashing").

[0008] Chemical machining is a method for precisely removing very small (thin) amounts of material from the surface of a microelectronic device substrate and polishing (or "planarizing") the surface in preparation for the deposition of a subsequent layer of material on the processed surface. Chemical machining involves highly precise mechanical abrasion of the surface combined with controlled chemical material interactions, such as oxidation, reduction, or chelation, of the material present on or being removed from the surface. In many cases, one type of material at the substrate surface (e.g., a metal overburden) is preferentially removed with high selectivity compared to the lesser extent of one or more other materials (e.g., a dielectric material) also present on the surface.

[0009] The CMP process involves depositing a "slurry" on a surface and contacting the surface with a moving CMP pad. A "slurry" is a liquid composition containing microabrasive particles that impart mechanical wear to the surface, as well as chemical materials that chemically interact with the surface material to facilitate the selective removal of certain materials from the surface and often prevent the removal of other surface materials. The slurry is deposited on the surface while the CMP pad contacts the surface with a desired amount of pressure and motion to promote the polishing and chemical removal of selected materials from the surface. The combination of the mechanical action of the moving pad and abrasive particles relative to the surface, along with the action of the chemical components, achieves the desired surface removal, surface planarization, and surface polishing with the desired reduced defects and residue. The CMP process must produce a highly planar, low-defect, low-residue surface upon which subsequent microelectronic device layers can be deposited.

[0010] After processing steps (e.g., chemical machining, etching, ashing, etc.), at least some amount of residue will be present on the surface of the substrate. Residues can include abrasive particles from the CMP slurry or other processing materials; active chemical components that are part of the CMP slurry (e.g., oxidizers, catalysts, inhibitors) or other processing compositions (e.g., etchants); reaction products or by-products of the processing materials or their components; chemical etchants; photoresist polymers or other solid processing components; etc. All such residues must be removed by cleaning the surface before subsequent steps in the microelectronic device fabrication process are performed to avoid defects or other potential sources of reduced device performance or reliability.

[0011] Certain methods and equipment commonly used to clean the surface of a microelectronic substrate, for example, after an etching process, a CMP process, or another process used in the fabrication of multilayer microelectronic devices, include flowing a cleaning solution across the surface in combination with megasonics, jetting, or brushing to remove residues and contaminants. Typical cleaning solutions are alkaline solutions containing, for example, suitable hydroxide compounds, along with other chemical materials that chemically interact with the residues, thereby removing them from the surface. The cleaning solution should be effective in removing a high percentage of residues from the surface while simultaneously being safe for the functional features of the substrate. The cleaning solution should not cause damage to these features. For example, the cleaning solution should not cause corrosion (i.e., oxidation) of metal features of the substrate, e.g., oxidize copper or cobalt metal features of the substrate, which may be present as interconnect or barrier features.

[0012] New, useful, and improved cleaning compositions and specific ingredients are continually being sought, especially for new microelectronic device structure applications such as those that may involve exposed surfaces of tungsten, copper, cobalt, molybdenum, and dielectric materials. Summary of the Invention

[0013] There is a continuing need for compositions and methods that are effective in removing residues from the surface of in-process microelectronic device substrates. The present invention provides such compositions and methods while preventing damage (i.e., corrosion) to certain metal features, such as cobalt, copper, molybdenum, and tungsten, that may be present as exposed features on microelectronic devices, as well as dielectric surface dielectric materials, including, but not limited to, silicon dioxide, silicon nitride, silicon carbide, silicon oxynitride, silicon oxycarbide, silicon, carbon, dielectrics, such as SiLK™ dielectrics (Dow Chemical), silsesquioxanes, or Black Diamond® PECVD (Applied Materials).

[0014] In one aspect, the present invention provides a method for producing a pharmaceutical composition comprising: Water, b. a complexing agent, and c. Amino (C6-C 12 Alkyl) alcohol wherein the composition does not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

[0015] Also provided are methods of using such compositions to clean microelectronic device substrates, and kits containing one or more components of the compositions in one or more containers. DETAILED DESCRIPTION OF THE INVENTION

[0016] In a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: Water, b. a complexing agent, and c. Amino (C6-C 12 Alkyl) alcohol wherein the composition does not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

[0017] In one embodiment, the composition comprises about 60 to 90 weight percent water, about 0.01 to about 10 weight percent complexing agent, and about 0.1 to about 5 weight percent, or about 0.1 to about 2 weight percent amino (C6-C 12 It is composed of alkyl alcohols.

[0018] In one embodiment, the composition consists of or consists essentially of components a through d above.

[0019] As used herein, unless otherwise specified, a composition or component of a composition described as "consisting essentially of" one or more specified items refers to a composition or component made only of those specified items and no more than insubstantial amounts of other (additional) materials, e.g., containing only the specified items and no more than 5, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01 weight percent additional components based on the total weight of the composition or component. As used herein, a composition or component of a composition described as "consisting of" one or more specified items refers to a composition or component made only of those specified items.

[0020] In certain embodiments, the pH is acidic, for example, from about 1.5 to about 6, and in other embodiments, the pH is basic, for example, from about 9 to about 14. Those of skill in the art will recognize suitable acids and bases for this purpose.

[0021] In one embodiment, pH adjuster is base.Non-limiting examples of pH adjuster for this purpose can 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 (TMAC), tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, arginine, potassium hydroxide, cesium hydroxide and combinations thereof.

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

[0023] In another embodiment, the pH adjuster is an acid and may be selected from nitric acid, citric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, lactic acid, glycolic acid, or any combination thereof.

[0024] In one embodiment, the complexing agent may be selected from the group consisting of, but not limited to, 4-(2-hydroxyethyl)morpholine (HEM), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), hydroxyethyldiethylenetriaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), m-xylenediamine (MXDA), iminodiacetic acid (IDA), trimethylamine, isopropanolamine, diisopropanolamine, piperazine, hydroxyethylpiperazine, dihydroxyethylpiperidine, glucamine, N The amino acids are selected from amines, amino acids and quaternized amino acids including 1,1,3,3-tetramethylurea, 1,1,3,3-tetramethylglucamine, 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, taurine, betaine and combinations thereof.

[0025] Alternatively, or in addition to the aforementioned complexing agents, additional complexing agents include phosphonates (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N"-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid) (DET AP), aminotri(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N',N"-tris(methylenephosphonic acid) (NOTP), hydroxyethyl diphosphonate, nitrilotris(methylene)phosphonic acid, 2-phosphonobutane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid), phenylphosphonic acid, and their derivatives) and / or carboxylic acids (e.g., oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, trimethylolpropionic acid, picolinic acid, dipicolinic acid, salicylic acid, sulfosalicylic acid, sulfophthalic acid, sulfosuccinic acid, betaine anhydride, gluconic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or (4,5-dihydroxy-1,3-benzene In certain embodiments, the complexing agent may include a sulfonic acid such as nitrilo(tris-methylenephosphonic acid) and iminodiacetic acid. In certain embodiments, the at least one complexing agent comprises a species selected from monoethanolamine, triethanolamine, sulfuric acid, citric acid, and combinations thereof. The amount of complexing agent in the composition, in one embodiment, ranges from about 0.01 wt % to about 10 wt %, based on the total weight of the removal composition.

[0026] In one embodiment, the complexing agent is selected from 1-hydroxyethylidene-1,1-diphosphonic acid; 1,5,9-triazacyclododecane-N,N',N"-tris(methylenephosphonic acid; 1,4,7,10-tetraazacyclododecane-N,N',N",N"'-tetrakis(methylenephosphonic acid); nitrilotris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid); succinic acid, citric acid, ammonium citrate, tartaric acid, iminodiacetic acid, aminotri(methylenephosphonic acid), bis(hexamethylene)triaminephosphonic acid; 1,4,7-triazacyclononane-N,N',N"-tris(methylenephosphonic acid); salts thereof, and derivatives thereof. In one embodiment, the complexing agent is 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof.

[0027] In one embodiment, amino (C-C 12 In one embodiment, the amino (C6-C alkyl) alcohol is selected from 3-amino-4-octanol; DL-2-amino-1-hexanol; 2-(butylamino)ethanol; 1-aminocyclohexanol; and 8-amino-1-octanol. 10 Alkyl) alcohols include 3-amino-4-octanol.

[0028] As described above, the compositions of the present invention do not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound. In another embodiment, the compositions of the present invention also do not include a corrosion inhibitor selected from oxalic acid, succinic acid, L-tartaric acid, and combinations thereof. In another embodiment, the compositions do not include any corrosion inhibitors.

[0029] In another aspect, the present invention provides a method for producing a pharmaceutical composition comprising: Water, b. Choline hydroxide, c. 1-hydroxyethylidene-1,1-diphosphonic acid, or d. monoethanolamine, and e. Amino (C6-C 10 Alkyl) alcohol wherein the composition does not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

[0030] In one embodiment, amino (C-C 12 In another embodiment, the amino (C8-C alkyl) alcohol is selected from 3-amino-4-octanol; DL-2-amino-1-hexanol; 2-(butylamino)ethanol; 1-aminocyclohexanol; and 8-amino-1-octanol. 12 The alkyl) alcohol comprises 3-amino-4-octanol. In another embodiment, the composition consists essentially of components a through e above.

[0031] In further embodiments of this aspect of the invention, the composition further comprises a water-dispersible or water-soluble polymer, when present, including, but not limited to, homopolymers of methacrylic acid and copolymers thereof, such as acrylamidomethylpropanesulfonic acid and maleic acid; maleic acid / vinyl ether copolymers; poly(vinylpyrrolidone) / vinyl acetate; phosphonated polyethylene glycol oligomers, homopolymers such as poly(acrylic acid) (PAA), poly(acrylamide), poly(vinyl acetate), poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(styrenesulfonic acid), poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinyl phosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, and the like. Examples of suitable polymers include methacrylate copolymers, poly(vinyl alcohol), poly(hydroxyethyl)acrylate, poly(hydroxyethyl)methacrylate, hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, xanthan gum, potassium alginate, pectin, carboxymethylcellulose, glucosamine, poly(diallyldimethylammonium) chloride, PEGylated (i.e., polyethylene glycol) methacrylate / acrylate copolymers, polyMADQuat (poly(2-methacryloxyethyltrimethylammonium chloride) CAS No. 26161-33-1) 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 in the composition ranges from about 0.0001% to about 5% by weight, based on the total weight of the composition.

[0032] In a further embodiment, the composition further comprises a surfactant. As used herein, the term "surfactant" refers to an organic compound that reduces the surface tension (or interfacial tension) between two liquids or between a liquid and a solid, and typically refers to an organic amphiphilic compound containing a hydrophobic group (e.g., a hydrocarbon (e.g., alkyl) "tail") and a hydrophilic group. When present, surfactants for use in the compositions described herein include, but are not limited to, amphoteric salts, cationic surfactants, anionic surfactants, zwitterionic surfactants, nonionic surfactants, and combinations thereof, including, but not limited to, decylphosphonic acid, dodecylphosphonic acid (DDPA), tetradecylphosphonic acid, hexadecylphosphonic acid, bis(2-ethylhexyl)phosphate, octadecylphosphonic acid, perfluoroheptanoic acid, prefluorodecanoic acid, trifluoromethanesulfonic acid, phosphonoacetic acid, dodecylbenzenesulfonic acid (DDBSA), benzenesulfonic acid, or salts thereof (including one or more C8-C6 18Examples of the alkyl groups include octadecyl phosphate, dodecyl succinic acid, dioctadecyl hydrogen phosphate, octadecyl dihydrogen phosphate, dodecylamine, dodecenyl succinic acid monodiethanolamide, lauric acid, palmitic acid, oleic acid, juniper acid, 12-hydroxystearic acid, octadecylphosphonic acid (ODPA), and dodecyl phosphate. Contemplated nonionic surfactants include, but are not limited to, polyoxyethylene lauryl ether, dodecenyl succinic acid monodiethanolamide, ethylenediamine tetrakis(ethoxylate-block-propoxylate) tetrol, polyethylene glycol, polypropylene glycol, polyethylene or polypropylene glycol ether, block copolymers based on ethylene oxide and propylene oxide, polyoxypropylene sucrose ether, t-octylphenoxypolyethoxyethanol, 10-ethoxy-9,9-dimethyldecan-1-amine, polyoxyethylene(9) nonylphenyl ether, branched polyoxyethylene( 40) Nonylphenyl ether, branched dinonylphenyl polyoxyethylene, nonylphenol alkoxylate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitol tetraoleate, polyethylene glycol sorbitan monooleate, sorbitan monooleate, alcohol alkoxylate, alkyl-polyglucoside, ethyl perfluorobutyrate, 1,1,3,3,5,5-hexamethyl-1,5-bis[2-(5-norbornen-2-yl)ethyl]trisiloxane, monomeric octadecylsilane derivatives, siloxane-modified polysilazanes, silicone-polyether copolymers, and ethoxylated fluorosurfactants.Contemplated cationic surfactants include, but are not limited to, cetyltrimethylammonium bromide (CTAB), heptadecanefluorooctanesulfonic acid, tetraethylammonium, stearyltrimethylammonium chloride, 4-(4-diethylaminophenylazo)-1-(4-nitrobenzyl)pyridinium bromide, cetylpyridinium chloride monohydrate, benzalkonium chloride, benzethonium chloride, benzyldimethyldodecylammonium chloride, benzyldimethylhexadecylammonium chloride, hexadecyltrimethylammonium bromide, dimethyldioctadecylammonium chloride, dodecyltrimethylammonium chloride, ammonium chloride, hexadecyltrimethylammonium p-toluenesulfonate, didodecyldimethylammonium bromide, di(hydrogenated tallow)dimethylammonium chloride, tetraheptylammonium bromide, tetrakis(decyl)ammonium bromide, and oxyphenonium bromides, guanidine hydrochloride (C(NH)Cl) or triflate salts such as tetrabutylammonium trifluoromethanesulfonate, dimethyldioctadecylammonium chloride, dimethyldihexadecylammonium bromide, di(hydrogenated tallow)dimethylammonium chloride, and polyoxyethylene(16) tallow ethylmonium ethosulfate. Contemplated anionic surfactants include, but are not limited to, poly(acrylic acid sodium salt), ammonium polyacrylate, sodium polyoxyethylene lauryl ether, sodium dihexyl sulfosuccinate, sodium dodecyl sulfate, dioctyl sulfosuccinate salt, 2-sulfosuccinate salt, 2,3-dimercapto-1-propanesulfonate, dicyclohexyl sulfosuccinate sodium salt, sodium 7-ethyl-2-methyl-4-undecyl sulfate, phosphate fluorosurfactants, fluorosurfactants, and polyacrylates.Zwitterionic surfactants can include, but are not limited to, acetylenic diols or modified acetylenic diols, ethylene oxide alkylamines, N,N-dimethyldodecylamine N-oxide, sodium cocaminopropionate, 3-(N,N-dimethylmyristylammonio)propanesulfonate, and (3-(4-heptyl)phenyl-3-hydroxypropyl)dimethylammoniopropanesulfonate.

[0033] In another embodiment, the composition further comprises a water-miscible solvent and / or an adjuvant.

[0034] In one embodiment, the water-miscible solvent is a glycol, a glycol ether, methanol, ethanol, isopropanol, butanol, and a higher alcohol selected from C2-C4 diols and C2-C4 triols, tetrahydrofurfuryl alcohol, such as 3-chloro-1,2-propanediol, 3-chloro-1-propanethiol, 1-chloro-2-propanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1,2-propanediol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-iodo-1-propanol, 4 -chloro-1-butanol, 2-chloroethanol, etc.), dichloromethane, chloroform, acetic acid, propionic acid, trifluoroacetic acid, tetrahydrofuran, N-methylpyrrolidinone, cyclohexylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, methyldiethanolamine, methyl formate, dimethylformamide, dimethyl sulfoxide, tetramethylene sulfone, diethyl ether, phenoxy-2-propanol, propriophenone, ethyl lactate, ethyl acetate, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol, 1,3-Propanediol, dioxane, butyryllactone, butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, 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, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, The sugars may be selected from the group consisting of 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, propylene glycol phenyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, hexaethylene glycol monophenyl ether, dipropylene glycol methyl ether acetate, tetraethylene glycol dimethyl ether, dibasic acid esters, glycerin carbonate, N-formylmorpholine, triethyl phosphate, monosaccharides and disaccharides, including, but not limited to, xylitol, fructose, sucrose, glucose, inositol, galactose, maltose, and combinations thereof.

[0035] Further typical adjuvants and / or solvents may include glycerol, sorbitol, glycol ethers, urea and dicyandiamide.

[0036] In one embodiment, the adjuvant is selected from compounds that function as hydrogen-bonding additives and serve to reduce the adhesion of silica particles to brushes used to clean microelectronic devices after CMP. See, for example, U.S. Patent Publication No. 2019 / 0168265, incorporated herein by reference. Exemplary compounds can 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 can 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), styrene sulfonic acid (or salts), vinyl sulfonic acid (or salts), allyl sulfonic acid (or salts), acrylamidopropyl sulfonic acid (or salts), and the like, where the salts of carboxylic and sulfonic acids are preferably neutralized with ammonium or alkylammonium cations. In one embodiment, the cation of the anionic polymer of the polyelectrolyte is an ammonium cation (NH + ), Corinium + N(CH3)3(CH2CH2OH) and + N(CH3)4. Thus, examples of conjugated 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.

[0037] Cationic polymers and cationic polyelectrolytes may 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 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 ammonium salts. and homopolymers or copolymers of quaternary salts, diethylaminoethyl (meth)acrylate acid addition salts and quaternary salts, 7-amino-3,7-dimethyloctyl (meth)acrylate acid addition salts and quaternary salts, N,N'-dimethylaminopropylacrylamide acid addition salts and quaternary salts, where the quaternary salts include alkyl quaternary salts and benzyl quaternary salts; allylamine, diallylamine, vinylamine (obtained by hydrolysis of vinyl alkylamide polymers), vinylpyridine, chitosan, cationic starch, polylysine, and salts thereof.

[0038] 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.

[0039] Alternatively or additionally, the hydrogen bonding additive may be 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 analogs of polyacrylates, polyamino acids (e.g., polyalanine, polyleucine, polyglycine), polyamide hydroxyurethanes, polylactones, polyacrylamides, xanthan gum, chitosan, polyethylene oxide, polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic acid, poly Sugar alcohols such as polyethyleneimine, sorbitol, sucrose, fructose, lactose, galactose, maltose, erythritol, maltitol, threitol, arabinol, ribitol, mannitol, galactitol, inositol, xylitol, esters of sorbitol anhydrides, secondary alcohol ethoxylates such as TERGITOL™ surfactants, polyfunctional alcohols such as pentaerythritol, dipentaerythitol, trimethylolpropane, dimethylpropionic acid, and xylonic acid, nucleobases such as uracil, cytosine, guanine, thymine, and combinations thereof.

[0040] Still other examples of hydrogen bonding additives can include lactic acid, maleic acid, urea, glycolic acid, sorbitol, borax (i.e., sodium borate), proline, betaine, glycine, histidine, TRIS (tris(hydroxymethyl)aminomethane), dimethyl sulfoxide, sulfolane, glycerol, SDS (sodium dodecyl sulfate), dodecylphosphonic acid, or combinations thereof.

[0041] In another embodiment, the composition further comprises a biocide. Exemplary biocides can include 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.

[0042] In another embodiment, the composition of the present invention comprises: A. For microelectronic devices with tungsten surfaces: 3-amino-4-octanol, sorbitol, glycerol, poly(styrene sulfonic acid), polyacrylic acid, ethanolamine, etidronic acid, citric acid, Hydroxyethyl cellulose, ethanolamine, choline hydroxide, triethanolamine, Benzisothiazolinone, and phosphoric acid; B. For microelectronic devices with cobalt surfaces and hydrophobic dielectric surfaces: 3-amino-4-octanol, Poly(vinylpyrrolidone), ethanolamine, choline hydroxide, KOH, Etidronic acid triethylene glycol monobutyl ether, and Brij23 (ethoxylated C 12 alcohol); and C. For microelectronic devices with copper surfaces: 3-amino-4-octanol, Poly(vinylpyrrolidone), ethanolamine, choline hydroxide, KOH, etidronic acid, triethylene glycol monobutyl ether, cysteine, morpholine, succinic acid, oxalic acid, tartaric acid, dicyandiamide, propylene glycol monobutyl ether, and Diethylene glycol monobutyl ether Includes.

[0043] As used herein, the term "residue" (including "contaminant") refers to any material, chemical or particulate, that remains on the surface of a microelectronic device substrate after a processing step used to fabricate the microelectronic device; exemplary processing steps include plasma etching, plasma ashing (to remove photoresist from an etched wafer), chemical machining, wet etching, and the like. Residues can be any non-aqueous chemical material that is part of the processing composition used in the processing step, such as a chemical etchant, photoresist, or CMP slurry. Alternatively, residues can be substances that arise from the materials of the processing composition during the processing step. Examples of these types of residues can include non-aqueous, particulate or non-particulate chemicals or abrasives (e.g., abrasives, surfactants, oxidizers, corrosion inhibitors, catalysts) that remain on the surface of the substrate after processing. Residues can be originally present in materials such as CMP slurries or etching compositions, such as solid abrasives or chemical materials present in CMP abrasive slurries. Alternatively, the residue may be a by-product or reaction product (in particulate (e.g., agglomerates, precipitates) or non-particulate form) generated during processing, for example, a by-product or reaction product of a chemical present in a processing composition such as a CMP slurry or wet etching composition, or a chemical present, used, or produced during a plasma etching or plasma ashing process.

[0044] The term "post-CMP residue" refers to residues present at the end of a CMP processing step, such as particles or chemical materials present in or resulting from a CMP slurry; specific examples can include abrasive grains (e.g., silica-containing or silica-based abrasive grains, metal oxide (e.g., alumina) particles, ceria or ceria-based particles, etc.); chemicals originally present in the slurry, such as oxidizers, catalysts, surfactants, inhibitors, complexing agents, etc.; metals (e.g., ions), metal oxides, or metal complexes resulting from metallic materials removed from the substrate surface being processed; or reaction products or complexes formed using a chemical in the slurry with another chemical in the slurry or with a chemical material originating from the substrate, such as metal ions; pad particles; or any other material that is a product of the CMP process.

[0045] "Post-etch residue" refers to materials remaining after a gas-phase plasma etching process, such as back end of line ("BEOL") dual damascene processing, or a wet etching process. The post-etch residue may be organic, organometallic, organosilicon, or essentially inorganic materials, such as silicon-containing materials, carbon-based organic materials, and etching gas residues such as oxygen and fluorine.

[0046] "Post-ash residue" refers to material remaining after oxidizing or reducing plasma ashing to remove solidified photoresist and / or bottom antireflective coating (BARC) material. The post-ash residue may be organic, organometallic, organosilicone, or inorganic in nature.

[0047] As used herein, a "low-k dielectric material" is a material used as a dielectric material in multilayer microelectronic devices and having a dielectric constant less than about 3.5. Exemplary low-k dielectric materials can include silicon-containing organic polymers, silicon-containing hybrid organic-inorganic materials, low-polarity materials such as organosilicate glass (OSG), tetraethyl orthosilicate (TEOS), fluorosilicate glass (FSG), and carbon-doped oxide (CDO) glass. Low-k dielectric materials can have densities and porosities within useful density ranges and useful porosity ranges.

[0048] As noted above, the present invention relates to compositions ("cleaning compositions" or "cleaning solutions") useful in cleaning methods for removing residue from the surface of a microelectronic device substrate having residue thereon. The described compositions comprise a complexing agent and an amino (C6-C 12 The alkaline composition contains an aqueous carrier (i.e., water) along with a combination of non-aqueous components, including a (alkyl) alcohol. In certain embodiments, the composition prior to use in a cleaning process is a homogeneous solution containing, consisting of, or consisting essentially of water and dissolved non-aqueous components, in the absence of any solid or suspended materials, such as solid abrasives, agglomerates, coagulates, etc.

[0049] The described compositions are particularly useful for cleaning microelectronic devices and precursors thereof, including microelectronic device substrates, i.e., semiconductor wafers containing one or more microelectronic devices or precursors thereof on their surfaces that are in the process of being fabricated into a final, completed, and functional microelectronic device. As used herein, a microelectronic device is a device that contains electrical circuitry and associated structures of very small dimensions (e.g., micron-scale or smaller) formed thereon. Exemplary microelectronic devices can include flat panel displays, integrated circuits, memory devices, solar panels, solar cells, and microelectromechanical systems (MEMS). A microelectronic device substrate is a structure such as a wafer (e.g., a semiconductor wafer) that contains one or more microelectronic devices or precursors thereof in preparation for forming a final microelectronic device.

[0050] The compositions and methods described herein are useful for cleaning any of a variety of forms of microelectronic devices at any stage of processing. Microelectronic device substrates (or simply "substrates" for short herein) that can be cleaned with particular utility and benefit can include substrates that contain cobalt, tungsten, molybdenum, or a dielectric, or all three, exposed on the surface of the substrate.

[0051] According to the present invention, compositions can be used to clean these general and specific types of microelectronic device substrates to remove residues, such as, but not limited to, post-CMP residues, post-ash residues, post-etch residues, or other residues present on the substrate surface after processing steps of the microelectronic device substrate. The cleaning compositions provide useful or beneficial cleaning properties, i.e., the cleaning compositions can be used with known equipment (e.g., post-CMP cleaning equipment) to substantially reduce the amount of residue, contaminants, or both on the surface of the microelectronic device substrate while improving the level of adverse effects on cobalt, tungsten, and dielectric surfaces. By using the cleaning compositions and methods described herein, a high percentage of residues present on the substrate surface can be successfully removed from the surface, e.g., at least 70, 80, 85, 90, 95, or 99 percent of the residue can be removed (also referred to as "cleaning efficiency").

[0052] Methods and instruments for measuring residues on the surface of a microelectronic device substrate are well known. Cleaning effectiveness may be assessed based on the reduction in the amount (e.g., number) of residue particles present on the surface of the microelectronic device after cleaning compared to the amount (e.g., number) of residue particles present before cleaning. For example, an atomic force microscope may be used to perform pre- and post-cleaning analysis. The residue particles on the surface may be recorded as a range of pixels. A histogram (e.g., Sigma Scan Pro) may be applied to filter for pixels of a certain intensity, e.g., 231-235, and the number of residue particles may be counted. The amount of residue particles removed, i.e., cleaning efficiency, may be determined by the ratio: (Number of pre-cleaning residue particles on the surface - Number of post-cleaning residue particles on the surface) / (Number of pre-cleaning residue particles on the surface) can be calculated using

[0053] Alternatively, cleaning effectiveness can be considered as the percentage of the total amount of substrate surface covered by residual particulate matter before cleaning compared to after cleaning.For example, an atomic force microscope can be programmed to perform a scan in the z-plane to identify topographical regions of interest above a certain height threshold, and calculate the total surface area covered by the regions of interest.A reduction in the amount of the area determined to be the region of interest after cleaning indicates that the cleaning composition and cleaning process are more effective.

[0054] In addition to good cleaning effectiveness, the described cleaning processes and cleaning compositions also produce cleaned substrate surfaces that are subject to advantageously low amounts of corrosion of exposed metal surfaces, such as exposed metallic tungsten, molybdenum, exposed metallic cobalt, or exposed dielectrics. Exemplary substrates that may be cleaned by such processes are those having metallic tungsten or metallic cobalt on their surfaces, for example, as metal interconnects (e.g., tungsten or cobalt interconnects) or as barrier layer materials (e.g., cobalt) located between the metal interconnects and dielectric or dielectric materials. Certain examples of microelectronic device substrates that may be cleaned with particularly useful or advantageous results include those that include exposed structures on their surfaces that include metallic tungsten (e.g., tungsten or its alloys), metallic cobalt (e.g., cobalt or its alloys), and dielectric materials. Corrosion protection of cleaning compositions can be reflected in measurements of metal etch rates, such as static etch rates, which can be performed by known methods using known equipment.

[0055] The compositions of the present invention can be prepared and then sold in the form of concentrates containing relatively small amounts of water and, as a result, relatively concentrated amounts of non-aqueous components. The concentrates are commercially prepared, sold, and shipped containing concentrated amounts of non-aqueous components and relatively reduced amounts of water, and are ultimately diluted at the time of use by the purchaser of the concentrate. The amounts of the various non-aqueous components in the concentrate are such that, upon dilution of the concentrate, the desired amounts of those non-aqueous components will result in the use composition.

[0056] The compositions described include water as a liquid carrier, i.e., a solute, for the non-aqueous components. The water may be deionized (DIW) water. Water may be present in the composition from any source, such as by being included in an ingredient that is combined with other ingredients to form a composition in the form of a concentrate; or as water in pure form combined with other ingredients in a concentrate; or as dilution water for diluting a concentrate to form a use composition, e.g., water added by a user to a concentrate at the time of use.

[0057] The amount of water in the composition may be the amount desired for a concentrate or the amount desired for a use composition, which generally has a higher total amount compared to the amount of water in a concentrate. The amount of water in an exemplary concentrate composition, while not intended to be limiting, may be from about 30, 40, or 50 to about 85 or 90 weight percent water, e.g., from about 60, 65, or 70 to about 80 weight percent water, based on the total weight of the concentrate composition. Upon dilution, these amounts will be reduced by a dilution factor. The amount of water in an exemplary use composition may be from about 75 to about 95 weight percent water, e.g., from about 82 or 85 to about 90 or 93 weight percent water, based on the total weight of the use composition.

[0058] The compositions of the present invention contain an amino (C6-C 12 As a second cleaning compound, the composition may optionally further contain a C2-C4 alkanolamine, such as monoethanolamine, as the second cleaning compound.

[0059] In another embodiment, the composition further comprises an additional cleaning compound. Some specific examples of such additional cleaning compounds include: a. morpholine, L-cysteine, dicyandiamide, hydroxyethyl cellulose, polyvinylpyrrolidone, polyamines, and combinations thereof; and b. Alginic acid and its salts; carboxymethylcellulose; dextran sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; copolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; chitosan; cationic starch; polylysine and its salts; diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium chloride (DADMAC), ammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, acid addition salts and quaternary salts of dimethylaminoethyl (meth)acrylate, acid addition salts and quaternary salts of diethylaminoethyl (meth)acrylate, acid addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl (meth)acrylate, acid addition salts and quaternary salts of N,N'-dimethylaminopropylacrylamide, homopolymers of allylamine, diallylamine, vinylamine, vinylpyridine;Diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldimethylammonium sulfate, diallyldimethylammonium phosphate, dimethallyldimethylammonium chloride, diethylallyldimethylammonium chloride, diallyldi(beta-hydroxyethyl)ammonium chloride, diallyldi(beta-ethoxyethyl)ammonium chloride, acid addition salts and quaternary salts of dimethylaminoethyl (meth)acrylate, acid addition salts and quaternary salts of diethylaminoethyl (meth)acrylate, acid addition salts and quaternary salts of 7-amino-3,7-dimethyloctyl (meth)acrylate, acid addition salts and quaternary salts of N,N'-dimethylaminopropylacrylamide, copolymers of allylamine, diallylamine, vinylamine, and vinylpyridine; Cocodimethylcarboxymethyl betaine; Lauryldimethylcarboxymethyl betaine ;Lauryl dimethyl alpha-carboxyethyl betaine;Cetyl dimethyl carboxymethyl betaine;Lauryl bis-(2-hydroxyethyl) carboxymethyl betaine;Stearyl bis-(2-hydroxypropyl) 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;Sodium dodecyl sulfate;Dioctyl sulfosuccinate sodium salt;Sodium lauryl ether sulfate;Polyethylene glycol branched-nonylphenyl ether sulfate ammonium salt;2-dodecyl-3-(2-sulfonatophenoxy) disodium;PEG25-PABA;Polyethylene glycol mono-C; 10 ~ 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;Ethylenediaminetetrakis(ethoxylate-block-propoxylate);2-Pyrrolidinone, and 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), Examples include:

[0060] The compositions of the present invention can be easily prepared by simply adding and mixing the individual components until a uniform state, such as a solution, is achieved. Additionally, the compositions can be easily formulated as individually packaged formulations or multi-part formulations that are mixed at the time of use or before use, for example, the individual parts of a multi-part formulation may be mixed by the user either in the process tool (cleaning equipment) or in a storage tank upstream of the process tool.

[0061] Accordingly, another aspect of the present invention relates to a kit comprising, in one or more containers, one or more components of the compositions described herein. The kit may further comprise, in one or more containers, for combination with additional solvent (e.g., water) at the factory of manufacture or at the point of use, (i) a pH adjusting agent; (ii) a complexing agent; (iii) an amino (C6-C 10 The kit may further include any of the other components listed herein. The container of the kit should be suitable for storing and transporting the composition and may be, for example, a NOWPak® container (Entegris, Inc., Billerica, Massachusetts, USA).

[0062] Additionally, the compositions described herein may be commercially prepared for sale in the form of a concentrate that can be diluted with an appropriate amount of water at the time of use. In concentrate form, the composition (concentrate) includes non-aqueous components that will be present in the concentrate in amounts such that, when the concentrate is diluted with a desired amount of water (e.g., DI water), each component of the cleaning composition will be present in the diluted use composition in the amount desired for use in a cleaning process, such as a post-CMP cleaning process. The amount of water added to the concentrate to form the use composition may be one or multiple volumes of water per volume of concentrate, for example, two volumes of water (e.g., three, four, five, or ten volumes of water) per volume of concentrate. When the concentrate is diluted with such an amount of water, each of the solid components of the concentrate will be present in the use composition at a reduced concentration relative to the number of volumes of water added to dilute the concentrate.

[0063] The cleaning compositions described may be useful in microelectronic device fabrication applications, including processes for cleaning substrate surfaces by methods such as post-etch residue removal, post-ash residue removal surface preparation, post-CMP residue removal, etc. Exemplary substrates that may be cleaned by such processes may include substrates comprising metallic tungsten, metallic cobalt, low-k dielectric materials, or all three.

[0064] The cleaning compositions and methods are effective in removing substantial amounts of residue from surfaces, including amounts initially present on the surface prior to the cleaning process. At the same time, the compositions and methods are effective without causing undue damage to dielectric materials that may be present on the surface and without causing undue corrosion to materials, such as metallic molybdenum, tungsten, copper, or cobalt, present on the surface of select substrates. In one embodiment, the cleaning composition may be effective in the cleaning process to remove at least 85 percent of the residue present on the surface of the substrate prior to residue removal by the cleaning process, or at least 90 percent of the residue, or at least 95 percent of the residue, or at least 99 percent of the residue initially present on the surface prior to the cleaning process.

[0065] In cleaning processes such as post-CMP residue cleaning processes, the cleaning compositions may be used with any of a variety of known, conventional, commercially available cleaning tools, such as, but not limited to, Verteq's single wafer megasonic Goldfinger, OnTrak systems' DDS (double sided scrubber), SEZ or other single wafer spray rinse, Applied Materials' Mirra-Mesa™ / Reflexion™ / Reflexion LK™ and Megasonic batch wet bench systems, and megasonic and brush scrubbing processes including those from Ebara Technologies, Inc., such as their 300 mm models (FREX300S2 and FREX300X3SC) and 200 mm CMP system (FREX200M).

[0066] The conditions and timing of the cleaning step may be as desired and may vary depending on the type of substrate and residue. In using the composition to clean post-CMP residue, post-etch residue, post-ash residue, or contaminants from a microelectronic device substrate having such thereon, the cleaning composition may be contacted with the substrate surface for a time period of from about 1 second to about 20 minutes, e.g., from about 5 seconds to 10 minutes, or from about 15 seconds to about 5 minutes, at a temperature ranging from about 20°C to about 90°C, or from about 20°C to about 50°C. Such contact times and temperatures are exemplary, and any other suitable time and temperature conditions may be useful so long as they are effective to at least partially, preferably substantially, clean the initial amount of residue from the surface.

[0067] Following the desired level of cleaning of the device substrate surface, the cleaning composition used in the cleaning step can be easily removed from the surface of the device as desired and effective for a given end-use application. For example, removal may be accomplished by using a rinse solution including deionized water. The device may then be processed as desired, such as by drying (e.g., using nitrogen or a spin-dry cycle) followed by subsequent processing of the cleaned and dried device surface.

[0068] In other more general or specific methods, a microelectronic device substrate may first be subjected to a processing step including any one or more of CMP processing, plasma etching, wet etching, plasma ashing, etc., followed by a cleaning step including cleaning the substrate surface with a composition of the present invention. At the end of the first processing step, residues (e.g., post-etch residues, post-CMP residues, post-ash residues, etc.) will be present on the substrate surface. The cleaning step using the described cleaning compositions will be effective in cleaning a substantial amount of the residues from the surface of the microelectronic device.

[0069] Accordingly, in another aspect, the present invention provides a method for removing residue from a microelectronic device substrate having said residue thereon, wherein the substrate has at least one surface comprising a material selected from copper, cobalt, tungsten, or a dielectric composition, the method comprising: The surface of the microelectronic device substrate Water, b. a complexing agent, and c. Amino (C6-C 12 Alkyl) alcohol wherein the composition does not comprise a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound; and at least partially removing the residue from the substrate.

[0070] The present invention can be further illustrated by the following examples of preferred embodiments thereof, although it should be understood that these examples are given for illustrative purposes only and are not intended to limit the scope of the invention unless specifically stated. [Example]

[0071] To evaluate the relative etch rates, solutions 1 through 10 referenced in Table 1 were prepared and used to treat microelectronic device substrates having either copper or cobalt surfaces.

[0072] The etch rate is a measure of the amount of metal removed from a metal surface when the surface is exposed to a particular electrolyte, such as a cleaning composition. Metal film thickness was measured using X-ray fluorescence (XRF) before and after a 15-minute cleaning process at a temperature of 30°C and an agitation of 500 rpm. TIFF0007735399000001.tif141170

[0073] Additionally, as shown in Table 2, cleaning compositions of the present invention containing the corrosion inhibitors described herein and including specific substrates Cu and Co exhibit reduced etch rates compared to the control solution. TIFF0007735399000002.tif122170

[0074] Example 2 The following compositions shown in Table 3 were prepared and tested according to the following procedures.

[0075] Etch Rate Procedure: Preparation of coupons: · Cut the wafer into square coupons with sides measuring 22-24 mm. Blow off the wafer with clean compressed nitrogen to remove any cleavage powder. The nozzle should be 1-2 inches from the wafer surface.

[0076] Beaker Treatment: Pre-measure the coupons if pre-measurement is specified. Use the etched fiducials to orient the coupons in a reproducible manner. Set the desired processing temperature on the hotplate. Once the hotplate temperature indicator has stopped flashing (indicating temperature has been reached), wait an additional 30 minutes before processing the coupons. Prepare two 400 mL beakers containing 250-350 mL of DIW each for rinsing. One (for the initial rinse) should be placed near the hot plate in the hood, and the other (for the overflow rinse) should be placed in the sink below the DIW supply. Use the blue clip to place the coupon into the beaker with the active side facing the chemical stream. Remove all coupons at the desired time. Immerse the clips and coupons in a 400 ml Teflon beaker filled with 250-350 ml of DIW for 1-3 seconds. The purpose of this step is to remove most of the compound from the wafer and clips before overflow rinsing. Transfer the clips and coupons to a beaker in the sink and run continuous streams of Cu for 2 minutes and Co for 10 seconds (overflow rinse). Blow the DIW off the coupon. Hold the nozzle 1-2 inches away from the coupon and blow with compressed N2. Starting on the opposite side of the clip, move the N2 stream under the wafer. Avoid allowing droplets to dry on the wafer surface; move the water as a sheet as much as possible. · Measure coupons after the fact. TIFF0007735399000003.tif80170

[0077] Example 3 Polishing Data Samples A and B, shown in Table 3, were diluted with 99 parts water and 1 part sample. TEOS (silicon dioxide) and / or silicon nitride wafers were polished with a silica-based commercial slurry on a Reflexion LK and then cleaned for 120 seconds in an integrated PVP brush station using Entegris Planarcore® brushes. The wafers were then analyzed on a KLA-TENCORE SP3 at a 65 nm threshold and graded on a SEMVISION SEM. Scratches and pits were removed as they are not related to the cleaning process. Total defects are the sum of silica defects and any organic residue defects.

[0078] The invention has been described in detail with particular reference to certain embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. TIFF0007735399000004.tif123170

Claims

1. a. water, b. Choline hydroxide, c. a complexing agent, and d. Amino (C ６ ~C １２ Alkyl) alcohol A composition comprising: The composition does not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

2. Amino (C ６ ~C １２ Alkyl) alcohol is amino (C ８ ~C １０ 2. The composition of claim 1, wherein the alcohol is a hydroxybenzoate.

3. C ２ ~C ４ The composition of claim 1 further comprising an alkanolamine.

4. The complexing agent is a. 4-(2-hydroxyethyl)morpholine; 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid, hydroxyethyldiethylenetriaminetriacetic acid; ethylenediaminetetraacetic acid; m-xylenediamine; iminodiacetic acid; trimethylamine; isopropanolamine; diisopropanolamine; piperazine; hydroxyethylpiperazine; dihydroxyethylpiperidine; glucamine; N-methylglucamine; 2-(hydroxyethyl)iminodiacetic acid; nitrilotriacetic acid; Thiourea; 1,1,3,3-tetramethylurea; urea; uric acid, b. An amino acid selected from alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, taurine, and betaine; c. Compounds containing a phosphonic acid moiety selected from 1-hydroxyethylidene-1,1-diphosphonic acid; 1,5,9-triazacyclododecane-N,N',N"-tris(methylenephosphonic acid); 1,4,7,10-tetraazacyclododecane-N,N',N",N'"-tetrakis(methylenephosphonic acid); nitrilotris(methylene)triphosphonic acid; diethylenetriaminepentakis(methylenephosphonic acid); aminotri(methylenephosphonic acid); bis(hexamethylene)triaminepentamethylenephosphonic acid; 1,4,7-triazacyclononane-N,N',N"-tris(methylenephosphonic acid); hydroxyethyl diphosphonate; and nitrilotris(methylene)phosphonic acid; d. 2-phosphonobutane-1,2,3,4-tetracarboxylic acid; Carboxyethylphosphonic acid; Carboxylic acids selected from aminoethylphosphonic acid; glyphosate; ethylenediaminetetra(methylenephosphonic acid); phenylphosphonic acid; carboxylic acids selected from oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, trimethylolpropionic acid, picolinic acid, dipicolinic acid, salicylic acid, sulfosalicylic acid, sulfophthalic acid, sulfosuccinic acid, gluconic acid, tartaric acid, glucuronic acid, 2-carboxypyridine), and / or sulfonic acids selected from 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt. The composition of claim 1 selected from:

5. Amino (C ６ ~C １２ 2. The composition of claim 1, wherein the (alkyl) alcohol is selected from 3-amino-4-octanol; DL-2-amino-1-hexanol; 1-aminocyclohexanol; and 8-amino-1-octanol.

6. Amino (C ６ ~C １２ 2. The composition of claim 1, wherein the (alkyl) alcohol comprises 3-amino-4-octanol.

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

8. The composition of claim 1 further comprising a biocide.

9. The composition of claim 1 further comprising a surfactant.

10. The composition of claim 1 further comprising a water-miscible solvent and / or an adjuvant.

11. 11. The composition of claim 10, wherein the water-miscible solvent and / or adjuvant is selected from glycerol, sorbitol, glycol ethers and urea.

12. a. water, b. Choline hydroxide, c. 1-hydroxyethylidene-1,1-diphosphonic acid, d. monoethanolamine, and e. Amino (C ６ ~C １２ Alkyl) alcohol and is free of a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

13. Amino (C ６ ~C １２ 13. The composition of claim 12, wherein the (alkyl) alcohol is selected from 3-amino-4-octanol; DL-2-amino-1-hexanol; 1-aminocyclohexanol; and 8-amino-1-octanol.

14. 14. The composition of claim 13, further comprising sorbitol.

15. 10. The composition of claim 1 which is a concentrate containing less than 80 weight percent water.

16. 10. The composition of claim 1, further comprising a compound selected from morpholine, L-cysteine, dicyandiamide, hydroxyethyl cellulose, polyvinylpyrrolidone, polyamines, and combinations thereof.

17. 1. A method of removing residue from a microelectronic device substrate having said residue thereon, wherein the substrate has at least one surface comprising a material selected from copper, cobalt, tungsten, molybdenum, or a dielectric composition, the method comprising: The surface of the microelectronic device substrate a. water, b. Choline hydroxide, c. 1-hydroxyethylidene-1,1-diphosphonic acid, d. monoethanolamine, and e. Amino(C 6 -C 12 alkyl) alcohol contacting the composition comprising: at least partially removing the residue from the substrate; Including, The method, wherein the composition does not include a corrosion inhibitor selected from a guanidine-functional compound, a pyrazolone-functional compound, or a hydroxyquinoline compound.

18. 18. The method of claim 17, wherein the surface comprises at least one of cobalt, copper, tungsten, and / or molybdenum.

19. 18. The method of claim 17, wherein the surface is a dielectric selected from tetraethyl orthosilicate, silicon-containing organic polymers, silicon-containing hybrid organic-inorganic materials, organosilicate glasses, fluorosilicate glasses, and carbon-doped oxide glasses.

Images