Microelectronic device cleaning compositions

Abstract

The present invention provides compositions that are particularly useful in post-CMP cleaning operations of substrates that include exposed copper surfaces. The compositions of the present invention provide superior cleaning of such substrates, resulting in fewer defects due to silica and organic materials present on the surface of the substrate. Also provided are methods of cleaning microelectronic device substrates using such compositions, and kits that include the components of the compositions in two or more containers.

Description

[Technical field]

[0001] The present invention relates generally to aqueous compositions for cleaning surfaces of microelectronic device substrates. [Background technology]

[0002]

[0002] Microelectronic device substrates are used in the manufacture of integrated circuit devices. Microelectronic device substrates include a base, such as a silicon wafer, having a highly planar surface. On the flat surface of the base, regions of electronically functional features are added through a number of selective deposition and removal steps. The features are created by selectively adding and removing electronically functional materials that exhibit insulating, conductive, or semiconducting properties. These electronically functional materials are placed as required using processing materials such as photoresists, chemical etchants, and slurries that contain abrasive particles and chemicals that aid in surface preparation.

[0003]

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

[0004]

[0004] The types of materials used in the fabrication of the interconnects 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 interconnects should be of a type that does not migrate (e.g., diffuse) excessively into adjacent dielectric materials over time and during use with a voltage applied between the materials, a type of migration of the interconnect material into adjacent dielectric materials that is often referred to as "electromigration." At the same time, the structure combining the interconnects and dielectric materials must have sufficient integrity, including at the interfaces between these materials, to result in low defect levels and reliable performance. For example, there must be a strong bond at the interface to prevent the dielectric material from separating from the interconnect material during use.

[0005]

[0005] In the past, interconnects were typically made of aluminum or tungsten, but more recently, they have been made of copper. Copper has the advantage of being more electrically conductive than aluminum or tungsten. In addition, copper-based interconnects have better resistance to electromigration than aluminum, improving the long-term reliability of integrated circuits. Nevertheless, copper ions tend to diffuse into silicon dioxide (SiO2) when subjected to a sufficient electrical bias, and copper can have poor adhesion to silicon dioxide and other dielectrics.

[0006]

[0006] To prevent these adverse effects of copper on dielectric materials, modern integrated circuit structures are 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, examples of which include tantalum (Ta), tantalum nitride (TaNx), tungsten (W), titanium (Ti), titanium nitride (TiN), ruthenium (Ru), cobalt (Co), molybdenum (Mo), rhenium (Rh), and alloys thereof.

[0007]

[0007] The processes of disposing the various features of a microelectronic device on a substrate include processes for selectively disposing insulating, semiconducting, and metallic materials on the substrate surface. The selective deposition and removal of these materials may involve the use of process compositions such as photoresist, etchants, CMP slurries containing abrasives and chemicals, plasmas, and the like, in steps such as photoresist coating, etching (wet etching, plasma etching, and the like), chemical mechanical processing (also known as chemical mechanical polishing, chemical mechanical planarization, or simply "CMP"), ashing ("plasma ashing"), and the like.

[0008]

[0008] Chemical mechanical processing is a process for precisely removing very small amounts (thickness) of material from the surface of a microelectronic device substrate to polish (or "planarize") the surface in preparation for applying the next layer of material to the treated surface. Chemical mechanical processing involves very precise mechanical polishing of the surface and controlled interaction of chemicals, such as oxidation, reduction, or chelation of substances present on the surface or substances removed from the surface. In many cases, one material of the substrate surface is preferentially removed with high selectivity compared to a reduced degree of removal of one or more other materials present on the surface.

[0009]

[0009] The CMP process involves applying a "slurry" to a surface and contacting the surface with a moving CMP pad. A "slurry" is a liquid composition containing fine abrasive particles that mechanically polish the surface, along with chemicals that chemically interact with the surface material to selectively remove certain materials from the surface and often prevent the removal of other surface materials. The slurry is applied to the surface and the CMP pad is contacted with the surface with a desired pressure and movement to facilitate the polishing and chemical removal of selected materials from the surface. The combination of the mechanical action of the pad and the action of the moving abrasive particles and chemical components against the surface achieves the desired removal, planarization, and polishing of the surface while maintaining a desired low level of defects and residues. The CMP process should produce a highly planar, low defect, low residue surface to which subsequent layers of the microelectronic device can be applied.

[0010]

[0010] After a processing step (e.g., chemical mechanical processing, etching, ashing), at least some amount of residue will be present on the surface of the substrate. Residues include abrasive particles from the CMP slurry or other processing materials, active chemical components (e.g., oxidizers, catalysts, inhibitors) that are part of the CMP slurry or other processing compositions, reaction products or by-products of the processing materials or their components, chemical etchants, photoresist polymers or other solid processing components, etc. Such residues must be cleaned and removed from the surface before the next stage of the microelectronic device manufacturing process is performed to avoid defects or other potential sources of degradation in device performance or reliability.

[0011]

[0011] Specific methods and apparatuses 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 manufacture of multi-layer microelectronic devices, include methods and apparatuses that flow a cleaning liquid over the surface in combination with megasonics, jets, or brushing to remove residues and contaminants. A typical cleaning liquid is, for example, an alkaline solution containing a suitable hydroxide compound together with other chemicals that chemically interact with the residues and remove them from the surface. The cleaning liquid should be effective in removing a high percentage of the residues from the surface, but also safe with respect to the functional features of the substrate. The cleaning liquid must not damage these functions. For example, the cleaning liquid should not cause corrosion (i.e., oxidation) of the metal parts of the substrate, and should not oxidize, for example, copper metal features of the substrate that may be present as interconnects or barrier parts.

[0012]

[0012] There is a continuing need for new, useful and improved cleaning compositions and specific ingredients, particularly for use in new microelectronic device structures, such as those that may contain exposed copper surfaces. Summary of the Invention

[0013] In summary, the present invention provides compositions useful in post-CMP cleaning operations, particularly for substrates containing exposed copper surfaces. The compositions of the present invention provide superior cleaning of such substrates, resulting in fewer defects due to silica and organic materials present on the surface of the substrate. Also provided are methods of using such compositions to clean microelectronic device substrates, and kits containing the components of the compositions in two or more containers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014]

[0014] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0015]

[0015] The term "about" generally refers to a range of numbers considered equivalent to a stated value (e.g., having the same function or result). In many cases, the term "about" may include numbers that are rounded to the nearest significant figure.

[0016] 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).

[0017] In a first aspect, the present invention provides a method for producing a composition comprising: Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, and ethyl dithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; f. pH adjuster and A composition comprising:

[0018]

[0018] In one embodiment, the composition is comprised of about 60 to 90 weight percent water, about 0.01 to about 10 weight percent cleaning agent, about 0.005 to about 10 weight percent chelating additive, about 0.01 to about 5 weight percent reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid, and about 0.01 to about 3 weight percent corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine.

[0019]

[0019] In this specification, unless otherwise specified, a composition or a component of a composition described as "consisting essentially of" one or more specified items refers to a composition or component consisting only of the specified items and containing no more than a small amount of other (additional) materials, e.g., containing only the specified items and containing no more than 5, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01 weight percent of additional components based on the total weight of the composition or component. In this specification, a composition or a component of a composition described as "consisting of" one or more specific items refers to a composition or component consisting only of those specific items. In certain embodiments, the composition consists of or consists essentially of components a-f above.

[0020]

[0020] In certain embodiments, the pH of the composition is from about 8 to about 14, and the pH adjusters described herein are used in an amount sufficient to achieve such pH range.

[0021] Various pH adjusters can be used in the compositions of the present invention, including, for example, bases such as potassium hydroxide, ammonium hydroxide (i.e., aqueous ammonia), and compounds of the formula NR 4 R 5 R 6 R7OH [wherein, R 4 , R 5 , R 6 and R 7 7 may be the same or different and are selected from hydrogen, linear or branched C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, and substituted or unsubstituted C6-C 10 Examples of tetraalkylammonium hydroxides include, but are not limited to, tetraalkylammonium hydroxide compounds having an aryl group (e.g., benzyl group) selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, and combinations thereof. Alternatively, or in addition, the pH adjuster may be a compound represented by the formula (PR 8 R 9 R 10 R 11 )OH[wherein, R 8 , R 9 , R 10 , and R 11may be the same or different, and are selected from hydrogen, linear C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl) groups, branched C1-C6 alkyl, C1-C6 hydroxyalkyl (e.g., hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl) groups, substituted C6-C 10 Aryl groups, unsubstituted C6-C 10 and any combination thereof, such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide.

[0022] In certain embodiments, the composition further comprises one or more additional chelating or complexing agents. In this regard, such additional chelating or complexing agents include amino acids such as glycine, alanine, serine, arginine, histidine, lysine, glutamic acid, serine, threonine, proline, etc. Others are phosphonates (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid (NOTP), hydroxyethyl diphosphonate, nitrilotris(methylene)phosphonic acid, 2-phosphonobutane-1,2 ,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid)phenylphosphonic acid, their salts, and derivatives thereof) 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, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or sulfonic acids such as 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt. In certain embodiments, such additional complexing agents are selected from citric acid and 1-hydroxyethylidene-1,1-diphosphonic acid.

[0023]

[0023] In another embodiment, the composition further comprises one or more water-miscible solvents. Examples of water-miscible solvents include glycols and glycol ethers (including, but not limited to, methanol, ethanol, isopropanol, butanol, higher alcohols (C2-C4 diols, C2-C4 triols, etc.)), tetrahydrofurfuryl alcohol (THFA), halogenated alcohols (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, and tetrahydrofuran. N-methylpyrrolidinone (NMP), cyclohexylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, methyldiethanolamine, methyl formate, dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetramethylene sulfone (sulfolane), diethyl ether, phenoxy-2-propanol (PPh), propriophenone, ethyl lactate, ethyl acetate, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol (PG), 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 (i.e. butyl carbitol), triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, 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 (TEGDE), dibasic esters, glycerin carbonate, N-formyl morpholine, triethyl phosphate, and combinations thereof.

[0024] In another embodiment, the composition further comprises one or more water-dispersible or water-soluble polymers. When such polymers are present, they may be selected from the group consisting of methacrylic acid homopolymers and copolymers of acrylamidomethylpropanesulfonic acid and maleic acid, maleic acid / vinyl ether copolymers, poly(vinylpyrrolidone) / vinyl acetate, homopolymers such as phosphonated polyethylene glycol oligomers, polyacrylic acid (PAA), polyacrylamide, polyvinyl acetate, polyethylene glycol (PEG), polypropylene glycol (PPG), polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinyl phosphonic acid, polyvinyl phosphoric acid, polyethyleneimine, polypropyleneimine, polyallylamine, polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), PPG-PEG-PPG block copolymers, PEG-PPG-PEG block copolymers, polyvinyl alcohol, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate, hydroxyethyl cellulose, Examples of polymers that may be used include, but are not limited to, methylhydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, xanthan gum, potassium alginate, pectin, carboxymethylcellulose, glucosamine, polydiallyldimethylammonium chloride, PEGylated (i.e., polyethylene glycolated) methacrylate / acrylate copolymers, PolyMADQuat (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, and combinations thereof. The above copolymers may be random or block copolymers. When present, the amount of polymer in the composition is in the range of about 0.0001% by weight to about 5% by weight, based on the total weight of the composition.

[0025]

[0025] In another embodiment, the composition further comprises one or more surfactants. In another embodiment, the composition further comprises a non-ionic 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, typically an organic amphiphilic compound that contains a hydrophobic group (e.g., a hydrocarbon (e.g., alkyl) "tail") and a hydrophilic group. When present, these non-ionic surfactants for use in the compositions described herein 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-octylphenoxy polyethoxyethanol, 10-ethoxy-9,9-dimethyldecane-1-amine, polyoxyethylene (9) nonylphenyl ether, branched, Polyoxyethylene (40) nonylphenyl ether, branched, dinonylphenyl polyoxyethylenes, nonylphenol alkoxylates, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitol tetraoleate, polyethylene glycol sorbitan monooleate, sorbitan monooleate, alcohol alkoxylates, alkyl polyglucosides, 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.

[0026] In another embodiment, the composition further comprises a biocide. Exemplary biocides 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.

[0027]

[0027] As used herein, the term "residue" (including "contaminant") refers to any material, be it chemical or particulate matter, remaining on the surface of a microelectronic device substrate after a processing step used in the manufacture of a microelectronic device, such as plasma etching, plasma ashing (removing photoresist from an etched wafer), chemical mechanical processing, wet etching, etc. Residues may be any non-aqueous chemical that is part of the processing composition used in the processing step, such as chemical etchants, photoresists, CMP slurries, etc. Residues may also be materials derived from the materials of the processing composition during the processing step. Examples of these types of residues include non-aqueous, particulate or non-particulate chemicals or abrasives (e.g., abrasive particles, surfactants, oxidizers, corrosion inhibitors, catalysts) that remain on the surface of the substrate after processing. Residues may be originally present in materials such as CMP slurries and etching compositions, such as solid abrasive particles and chemicals present in CMP polishing slurries. Alternatively, the residue may be a by-product or reaction product (particulate (e.g., agglomerates, precipitates) or non-particulate) generated during processing, such as a by-product or reaction product of chemicals present in a processing composition, such as a CMP slurry or a wet etch composition, or chemicals present or used or generated during a plasma etch or plasma ash process.

[0028]

[0028] The term "post-CMP residue" refers to residues present at the end of a CMP processing step, such as particles or chemicals present in or derived from the CMP slurry; specific examples include abrasive particles (e.g., silica-containing or silica-based abrasive particles, metal oxide (e.g., alumina) particles, ceria or ceria-based particles, etc.); chemicals originally contained in the slurry, such as oxidizers, catalysts, surfactants, inhibitors, complexing agents, etc.; metals, metal oxides, or metal complexes derived from metallic materials removed from the substrate surface during processing; or reaction products or composites produced using substrate-derived chemicals such as; pad particles, or other materials that are products of the CMP process.

[0029]

[0029] "Post-etch residue" refers to materials remaining after gas-phase plasma etch processes, such as back-end-of-line (BEOL) dual damascene processing and wet etch processes. Post-etch residues may be organic, organometallic, organosilicon, or inorganic in nature, including, for example, silicon-containing materials, carbon-based organic materials, and etch gas residues such as oxygen and fluorine.

[0030] "Post-ash residue" refers to materials remaining after oxidizing or reducing plasma ashing to remove hardened photoresist or bottom antireflective coating (BARC) materials. Post-ash residues can be organic, organometallic, organosilicone, or inorganic.

[0031] As noted above, the present invention relates to compositions useful in cleaning methods for removing residues from the surfaces of residue-bearing microelectronic device substrates. The compositions include an aqueous carrier (i.e., water) along with a combination of non-aqueous components as described herein. In certain embodiments, the compositions, prior to use in the cleaning process, are homogenous solutions comprising, consisting of, or consisting essentially of water and dissolved non-aqueous components, free of solids or suspended matter, such as solid abrasive particles, agglomerates, coagulates, etc.

[0032]

[0032] The compositions described herein are useful for cleaning microelectronic devices and precursors thereof, specifically microelectronic device substrates, i.e., semiconductor wafers that contain one or more microelectronic devices or precursors thereof on their surfaces that are in the process of being processed into a final, completed, functional microelectronic device.

[0033]

[0033] As used herein, a microelectronic device is a device having electrical circuits and related structures formed thereon with very small (e.g., micron-scale or smaller) dimensions. Exemplary microelectronic devices include flat panel displays, integrated circuits, memory devices, solar panels, photovoltaics, 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 the final microelectronic device.

[0034] The compositions and methods described herein are useful for cleaning various forms of microelectronic devices at any stage of processing. By using the cleaning compositions and methods described herein, a majority of the residue present on the substrate surface can be effectively removed from the surface, for example, at least 70, 80, 85, 90, 95, or 99 percent of the residue can be removed (also referred to as "cleaning efficiency").

[0035]

[0035] Methods and apparatus for measuring residues on the surface of a microelectronic device substrate are well known. The cleaning effectiveness may be evaluated based on the reduction in the amount (e.g., number) of residual particles present on the microelectronic device surface after cleaning compared to the amount (e.g., number) of residual particles present before cleaning. For example, pre-cleaning and post-cleaning analysis may be performed using an atomic force microscope. The residual particles on the surface may be registered as a range of pixels. A histogram (e.g., Sigma Scan Pro) may be applied to filter pixels of a certain intensity (e.g., 231-235) and count the number of residual particles. The amount of residual particles removed, i.e., cleaning efficiency, may be calculated using the following ratio: (number of particles remaining on a surface before cleaning−number of particles remaining on the surface after cleaning) / (number of particles remaining on the surface before cleaning).

[0036] Alternatively, cleaning effectiveness can be considered as the percentage of the total amount of substrate surface covered with residual particulate matter before and after cleaning. For example, an atomic force microscope can be programmed to perform a Z-plane scan to identify areas of interest on the topography that exceed a certain height threshold and calculate the area of ​​the total surface covered by the areas of interest. A reduction in the amount of areas identified as areas of interest after cleaning indicates that the cleaning composition and cleaning process are more effective.

[0037] The compositions of the present invention may be prepared and sold in the form of concentrates containing relatively small amounts of water and therefore relatively concentrated amounts of the non-aqueous components. Concentrates may be commercially prepared to be sold and shipped containing concentrated amounts of the non-aqueous components and relatively small amounts of water, and ultimately diluted by the purchaser of the concentrate at the point of use. The amounts of the different non-aqueous components in the concentrate are such that dilution of the concentrate results in the desired amount of those non-aqueous components present in the composition ultimately utilized.

[0038] The compositions described include water as a liquid carrier, i.e., solute, for the non-aqueous components. The water can be deionized water (DIW). Water can be present in the composition from any source, such as by being included in an ingredient that is combined with other ingredients to produce a composition in the form of a concentrate, or as water combined in pure form with other ingredients of a concentrate, or as water added to a concentrate by a user, for example as dilution water, for the purpose of diluting the concentrate at the point of use to form a use composition.

[0039] The amount of water in the composition may be the amount desired for a concentrate or the amount desired for a use composition, which is usually a higher total amount compared to the amount of water in a concentrate. Exemplary amounts of water in a concentrate composition may be, but are not limited to, about 30, 40, or 50 to about 85 or 90 weight percent water, for example, about 60, 65, or 70 to about 80 weight percent water, based on the total weight of the concentrate composition. Upon dilution, these amounts decrease depending on the dilution rate. Exemplary amounts of water in a use composition may be about 70 to about 99.9 weight percent water, for example, about 90 or 99.55 to about 95 or 99 weight percent water, based on the total weight of the use composition.

[0040] The compositions of the present invention can be easily prepared by simply adding the components and mixing until a homogeneous state, such as a solution, is achieved. Furthermore, the compositions can be easily formulated as single package formulations or multi-part formulations that are mixed at or before the time of use, e.g., individual parts of a multi-part formulation can be mixed by the user either at the processing tool (cleaning equipment) or in a storage tank upstream of the processing tool.

[0041]

[0041] Thus, another aspect of the present invention relates to a kit comprising the various components of the compositions described herein in two or more containers, suitable for storing and transporting the compositions, which may include, for example, NOWPak® containers (Entegris, Inc., Billerica, Massachusetts, USA). Thus, in a third aspect, the present invention relates to a kit comprising, in two or more containers: Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, and ethyl dithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; f. pH adjuster and A kit is provided that includes two or more of the following:

[0042] The compositions and methods of the present invention are effective in removing from a surface an amount of residue that was initially present on the surface prior to the cleaning step. In one embodiment, the cleaning composition may be effective in a cleaning step to remove at least 85 percent of the residue that was initially present on the surface of the substrate prior to removal of the residue by the cleaning step, or at least 90 percent of the residue that was initially present on the surface of the substrate prior to removal of the residue by the cleaning step, or at least 95 percent of the residue, or at least 99 percent of the residue.

[0043]

[0043] In cleaning steps, such as post-CMP residue cleaning steps, the cleaning compositions can be used with any of a variety of known conventional commercially available cleaning tools, 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™ / Reflexion LK™, and Megasonic batch wet bench systems, and Ebara Technologies, Inc. products such as 300 mm models (FREX300S2 and FREX300X3SC) and 200 mm CMP systems (FREX200M).

[0044]

[0044] The conditions and timing of the cleaning step can be set as required and may vary depending on the type of substrate and residue. When using the composition to clean post-CMP residue, post-etch residue, post-ash residue or contaminants from a microelectronic device substrate having them, the cleaning composition can be contacted with the substrate surface for about 1 second to about 20 minutes, for example, about 5 seconds to about 10 minutes, or about 15 seconds to about 5 minutes, at a temperature ranging from about 20°C to about 90°C, or about 20°C to about 50°C, and such contact times and temperatures are exemplary, and other suitable time and temperature conditions may be useful as long as they are effective in at least partially cleaning the initial amount of residue from the surface.

[0045] After the desired level of cleaning of the device substrate surface, the cleaning composition used in the cleaning step can be easily removed from the device surface as desired and effective for a given end use. For example, removal can be accomplished using a cleaning solution that includes deionized water. The device can then be processed as required, such as by drying (e.g., using nitrogen or a spin dry cycle), followed by subsequent processing of the cleaned and dried device surface.

[0046] In another more general or specific method, a microelectronic device substrate is first subjected to a processing step including any one or more of CMP processing, plasma etching, wet etching, plasma ashing, etc., and then subjected to a cleaning step including cleaning the substrate surface with the 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) remain on the substrate surface. The cleaning step using the described cleaning composition is effective in removing a significant amount of the residues from the microelectronic device surface.

[0047]

[0047] Accordingly, in a third aspect, the present invention provides a method for removing residues on a microelectronic device substrate, the method comprising: A. The surface of a microelectronic device substrate is A. Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, ethyl dithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea and glycocyamine; and f. pH adjuster and contacting the composition with B. At least partially removing residue from a substrate of a microelectronic device; Includes.

[0048] The present invention can be further illustrated by the following examples of preferred embodiments, it being understood that these examples are included for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise expressly indicated.

[0049] Example - Thickened Formulation TIFF2025508194000001.tif89170

[0050]

[0050] Experimental results:

[0051] In these experiments, 300 mm copper blanket wafers were polished and cleaned on a Reflexion® LK CMP tool using appropriate consumables such as slurries, pads, and brushes. A SP-3 defect inspection tool was used to detect defect counts for 80 nm defect size. The defects were then classified in terms of organics, silica, etc. using an EDR-7380 Defect Review Tool (KLAT) including microscope, SEM, and EDX. The data in Table 1 below shows the improvement of the cleaning compositions of Examples 1-4 compared to the Comparative Example. These PCMP cleaners significantly reduced the amount of organic residue on the copper blanket wafers. Silica particle cleaning performance is comparable between the solutions tested.

[0051]

[0052] Table 1 TIFF2025508194000002.tif42170

[0052]

[0053] Comparing three corrosion inhibitors (dicyandiamide, guanylurea, and glycocyamine) added to 4.5% MEA (CAS number 141-43-5), the Cu etch rate decreased, but the effect on the Co etch rate was negligible.

[0053]

[0054] Table 2 TIFF2025508194000003.tif30170

[0054]

[0055] Alternative chelating and reducing agents tested in the following target formulations resulted in reduced Co etch rates.

[0055]

[0056] Table 3 TIFF2025508194000004.tif45170

[0056]

[0057] Aspects

[0058] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, and ethyl dithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; f. pH adjuster and A composition comprising:

[0057]

[0059] In a second aspect, the present invention provides a composition of the first aspect, wherein the nucleophile is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

[0058]

[0060] In a third aspect, the present invention provides a composition of the first or second aspect, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine, and hydroxyethylidene diphosphonic acid.

[0059]

[0061] In a fourth aspect, the present invention provides a composition of the first, second or third aspect, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid, and hypophosphorous acid.

[0060]

[0062] In a fifth aspect, the present invention provides a composition according to any one of the first to fourth aspects, wherein the corrosion inhibitor is selected from dicyandiamide, guanylurea and glycocyamine.

[0061]

[0063] In a sixth aspect, the present invention provides a composition according to any one of the first to fifth aspects, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetraethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

[0062]

[0064] In a seventh aspect, the present invention provides a composition according to any one of the first to sixth aspects, wherein the pH of the composition is 8 or greater.

[0063]

[0065] In an eighth aspect, the present invention provides a composition according to any one of the first to seventh aspects, wherein d is diethylhydroxylamine and e is dicyandiamide.

[0064]

[0066] In a ninth aspect, the present invention provides a composition comprising: Water, b. monoethanolamine; C. cysteine; d. diethylhydroxylamine; e. dicyandiamide; f. pH adjuster and A composition comprising:

[0065]

[0067] In a tenth aspect, the present invention provides a composition of the ninth aspect, wherein the pH adjusting agent is choline.

[0066]

[0068] In an eleventh aspect, the present invention provides a composition according to any one of the first to tenth aspects, the composition comprising 1-hydroxyethylidene-1,1-diphosphonic acid, 1,5,9-triazacyclododecane-N,N',N''-tris(methylene phosphonic acid), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylene phosphonic acid), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylene phosphonic acid), aminotri(methylene phosphonic acid, bis(hexamethylene)triaminepentamethylene phosphonic acid, 1,4,7-triazacyclononane-N,N',N''-tris(methylene The composition further comprises one or more chelating agents selected from phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, tricarballylic acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid, and salts thereof.

[0067]

[0069] In a twelfth aspect, the present invention provides a composition according to any one of the first to eleventh aspects, further comprising one or more water-miscible solvents.

[0068]

[0070] In a thirteenth aspect, the present invention provides a composition of the twelfth aspect, wherein the water-miscible solvent is selected from triethylene glycol monobutyl ether, propylene glycol n-butyl ether, dimethyl sulfoxide, and diethylene glycol monophenyl ether.

[0069]

[0071] In a fourteenth aspect, the present invention provides a composition according to any one of the first to thirteenth aspects, the composition further comprising one or more surfactants.

[0070]

[0072] In a fifteenth aspect, the present invention provides a composition according to any one of the first to fourteenth aspects, further comprising one or more water-dispersible or water-soluble polymers.

[0071]

[0073] In a sixteenth aspect, the present invention provides a method for removing residue on a microelectronic device substrate, the method comprising: A. The surface of a microelectronic device substrate is A. Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, ethyl dithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. A compound selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea and glycocyamine; and f. pH adjuster and contacting the composition with B. At least partially removing residue from a substrate of a microelectronic device; Includes.

[0072]

[0074] In a seventeenth aspect, the present invention provides the method of the sixteenth aspect, wherein the cleaning additive of the composition is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

[0073]

[0075] In an eighteenth aspect, the present invention provides the method of the sixteenth or seventeenth aspects, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine, and hydroxyethylidene diphosphonic acid.

[0074]

[0076] In a nineteenth aspect, the present invention provides a method of the sixteenth, seventeenth, or eighteenth aspects, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid, and hypophosphorous acid.

[0075]

[0077] In a twentieth aspect, the present invention provides the method of any one of the sixteenth to nineteenth aspects, wherein the corrosion inhibitor is selected from dicyandiamide, guanylurea, and glycocyamine.

[0076]

[0078] In a twenty-first aspect, the present invention provides the method of any one of the sixteenth to twentieth aspects, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetraethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

[0077]

[0079] In a twenty-second aspect, the present invention provides a method of the sixteenth aspect, wherein the composition comprises: Water, b. monoethanolamine; C. cysteine; d. diethylhydroxylamine; e. dicyandiamide; f. pH adjuster and Includes.

[0078]

[0080] In a twenty-third aspect, the present invention provides a method of the twenty-second aspect, wherein the pH adjuster is choline.

[0079]

[0081] In a twenty-fourth aspect, the present invention provides a method for preparing a pharmaceutical composition comprising the steps of: a. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, and ethyl dithiocarbamate, and salts thereof; b. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; c. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; d. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; f. pH adjuster and A kit is provided that includes two or more of the following:

[0080]

[0082] Although several exemplary embodiments of the present disclosure have been described above, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the claims appended hereto. Numerous advantages of the disclosure covered in this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is, in many respects, merely illustrative. The scope of the disclosure is, of course, defined in the language in which the appended claims are expressed.

Claims

1. 1. A composition comprising: a. Water; b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, ethyldithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine; diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; f. pH adjuster; A composition comprising:

2. The composition of claim 1, wherein the nucleophile is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

3. The composition of claim 1, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine and hydroxyethylidene diphosphonic acid.

4. 2. The composition of claim 1, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid and hypophosphorous acid.

5. 2. The composition of claim 1, wherein the corrosion inhibitor is dicyandiamide.

6. 2. The composition of claim 1, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

7. 2. The composition of claim 1, wherein the reducing agent is diethylhydroxylamine and the corrosion inhibitor is dicyandiamide.

8. a. Water; b. monoethanolamine; c. Cysteine, d. diethylhydroxylamine; e. dicyandiamide, f. pH adjuster; The composition of claim 1 comprising:

9. 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, nitrilotris 10. The composition of claim 1 further comprising one or more additional complexing agents selected from: (methylene)phosphonic acid, 2-phosphono-butane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate; ethylenediaminetetra(methylenephosphonic acid)phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, citric acid, tricarballylic acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid, and salts thereof.

10. The composition of claim 1 further comprising one or more water-miscible solvents.

11. The composition of claim 10, wherein the water-miscible solvent is selected from triethylene glycol monobutyl ether, propylene glycol n-butyl ether, dimethylsulfoxide and diethylene glycol monophenyl ether.

12. The composition of claim 1 further comprising one or more surfactants.

13. The composition of claim 1 further comprising one or more water-dispersible or water-soluble polymers.

14. 1. A method for removing residue on a microelectronic device substrate, comprising: A. A surface of a microelectronic device substrate is a. Water, b. a cleaning additive selected from cysteine, cystine, 2-aminothiophenol, 2-thiazoline-2-thiol, 1,3,4-thiadiazole-2-,5-dithiol, 1,3,4-thiadiazole-2-methyl-5-thiol, ethyldithiocarbamate, and salts thereof; c. a chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylene phosphonic acid), diethylenetriaminepentamethylene phosphonic acid, phosphoric acid, and triethanolamine; d. a reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid; e. a corrosion inhibitor selected from dicyandiamide, guanylurea, and glycocyamine; and f. pH adjuster and contacting the composition with B. At least partially removing residue from the microelectronic device substrate; A method comprising:

15. The method of claim 14, wherein the cleaning additive is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

16. 15. The method of claim 14, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine, and hydroxyethylidene diphosphonic acid.

17. 15. The method of claim 14, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid, and hypophosphorous acid.

18. 15. The method of claim 14, wherein the corrosion inhibitor is dicyandiamide.

19. 15. The method of claim 14, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetramethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

20. The composition comprises: a. Water; b. monoethanolamine; c. Cysteine, d. diethylhydroxylamine; e. dicyandiamide, f. pH adjuster; 15. The method of claim 14, comprising:

Images