Microelectronics device cleaning composition

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]

[0001] The present invention generally relates to aqueous compositions for cleaning the surface 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, which has a highly flat surface. Regions of electronically functional features are added to the plane of the base through a number of selective placement and removal steps. These features are made by selectively adding and removing electronically functional materials that exhibit insulating, conductive, or semiconductor properties. These electronically functional materials are placed as needed using processing materials such as photoresists, chemical etchants, and slurries containing abrasive particles and chemicals to aid in surface treatment.

[0003]

[0003] One of the features of an integrated circuit is an array of conductive "interconnections," also called "lines" or "vias." As part of an integrated circuit, conductive interconnects play a role in conducting electric current between various other electronic functions. Each interconnection is defined (in shape and size) by an opening formed in an insulating material such as a dielectric, and takes the form of a line or thin film of conductive material extending inside. The dielectric material acts as an insulator between very close interconnection structures and between the interconnection structures and other electronic functions of the integrated circuit.

[0004]

[0004] The types of materials used in the manufacture of interconnects and dielectric structures must be selected to function appropriately as part of an integrated circuit that operates with high efficiency and reliability. For example, the conductive material of the interconnect should be of a type that does not excessively migrate (e.g., diffuse) to adjacent dielectric materials over time and during use with voltage applied between the materials, such migration of interconnect material to adjacent dielectric material is often called "electromigration". At the same time, the structure combining the interconnect and dielectric materials must have sufficient integrity, including the interface between these materials, resulting in a low defect level and high performance reliability. For example, a strong bond must exist at the interface to prevent the dielectric material from separating from the interconnect material during use.

[0005]

[0005] In the past, interconnects were generally made of aluminum or tungsten, but recently they are made of copper. Copper has the advantage of being more electrically conductive than aluminum or tungsten. Furthermore, copper-based interconnects have better resistance to electromigration than aluminum, thus improving the reliability of integrated circuits over the long term. Nevertheless, under sufficient electrical bias, copper ions tend to diffuse into silicon dioxide (SiO2), which can reduce the adhesion between copper and silicon dioxide and other dielectrics.

[0006]

[0006] To prevent these adverse effects between copper and dielectric materials, recent integrated circuit structures are designed to include a barrier layer between the copper interconnect structure and the adjacent dielectric material. Examples of barrier layers may be conductive or nonconductive materials, including 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] Processes for arranging various functions of microelectronic devices on a substrate include processes for selectively arranging insulating materials, semiconductor materials, and metallic materials on the substrate surface. Selective arrangement and removal of these materials may include the use of process compositions such as CMP slurries containing photoresists, etchants, abrasives, and chemicals, and plasma in steps such as photoresist coating, etching (wet etching, plasma etching, etc.), chemical mechanical processing (also known as chemical mechanical polishing, chemical mechanical planarization, or simply "CMP"), and ashing ("plasma ashing").

[0008]

[0008] Chemical mechanical processing is a process of polishing (or "planarizing") a surface by precisely removing a very small amount (thickness) of material from the surface of a substrate for a microelectronic device 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 interactions of chemicals such as oxidation, reduction, and chelation of substances present on the surface or substances removed from the surface. Often, one material on the substrate surface is preferentially removed with high selectivity compared to the 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 bringing a moving CMP pad into contact with the surface. The “slurry” is a liquid composition containing fine abrasive particles that perform mechanical polishing of the surface, along with chemicals that chemically interact with the surface material to selectively remove specific materials from the surface, often preventing the removal of other surface materials. As the slurry is applied to the surface and the CMP pad comes into contact with the surface with the desired pressure and movement, the polishing and chemical removal of selected materials from the surface is facilitated. The combination of the mechanical action of the pad and the action of the moving abrasive particles and chemical components on the surface results in the desired removal, planarization, and polishing of the surface while maintaining the desired low levels of defects and residues. The CMP process should produce a highly planar, low-defect, low-residue surface to which subsequent layers of microelectronic devices 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. The residue includes abrasive particles from the CMP slurry or other processing materials, activating chemical components (e.g., oxidizing agents, catalysts, inhibitors) or other processing compositions that are part of the CMP slurry, reaction products or by-products of the processing material or its components, chemical etching agents, photoresist polymers or other solid processing components. Such residue must be cleaned and removed from the surface before performing the next step of the microelectronic device manufacturing process in order to avoid defects or other potential causes that may reduce the performance or reliability of the device.

[0011]

[0011] For example, certain methods and apparatus commonly used to clean the surface of a microelectronic substrate after an etching process, a CMP process, or another process used in the manufacture of multilayer microelectronic devices include methods and apparatus for applying a cleaning solution to the surface in combination with megasonic, jet, or brushing to remove residues and contaminants. Typical cleaning solutions are, for example, alkaline solutions containing a suitable hydroxide compound together with other chemicals that chemically interact with the residues to remove them from the surface. The cleaning solution should be effective in removing a high percentage of residues from the surface, but it must also be safe with respect to the functional features of the substrate. The cleaning solution must not damage these features. For example, the cleaning solution must not cause corrosion (i.e., oxidation) of the metallic parts of the substrate, for example, it must not oxidize copper metal features of the substrate that may be present as interconnect or barrier parts.

[0012]

[0012] There is a continuous need for new, useful, and improved cleaning compositions and specific components, particularly for use in new microelectronic device structures, such as those that may include exposed copper surfaces. [Overview of the project]

[0013]

[0013] In summary, the present invention provides compositions useful for post-CMP cleaning operations of substrates, particularly those containing exposed copper surfaces. The compositions of the present invention provide excellent cleaning of such substrates and reduce defects caused by silica and organic materials present on the substrate surface. Methods for cleaning microelectronic device substrates using such compositions and kits containing components of the compositions in two or more containers are also provided. [Modes for carrying out the invention]

[0014]

[0014] Where used in this specification and the appended claims, the singular forms “a,” “an,” and “the” refer to multiple subjects unless the context clearly indicates otherwise. Where used in this specification and the appended claims, the term “or” is used in general to mean “and / or” unless the context clearly indicates otherwise.

[0015]

[0015] The term “approximately” usually refers to a range of numbers that are considered equivalent to the stated value (for example, having the same function or result). Often, the term “approximately” may include numbers rounded to the nearest significant figure.

[0016]

[0016] A numerical range expressed using an endpoint includes all numbers within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0017]

[0017] In a first embodiment, the present invention is a. Water and, b. A washing 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 ethyldithiocarbamate and their salts, c. A chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidene diphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriamine pentamethylene phosphonic acid, phosphoric acid, and triethanolamine, and d. A reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfurous acid, and e. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glucosamine, and f. A pH adjuster and A composition containing the above is provided.

[0018]

[0018] In one embodiment, the composition consists of about 60 to 90 weight percent water, about 0.01 to about 10 weight percent detergent, 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 glucosamine.

[0019]

[0019] As used herein, unless otherwise specified, a composition or a component of a composition described as "consisting essentially of" one or more specified items consists of only the specified items and other (additional) materials are present in trace amounts, for example, it contains only the specified items and contains additional components of 5, 3, 2, 1, 0.5, 0.1, 0.05, or 0.01 weight percent or less based on the total weight of the composition or component. As used herein, a composition or a component of a composition described as "consisting of" one or more specific items refers to a composition or component consisting of only those specific items. In certain embodiments, the composition consists of, or consists essentially of, components a - f as described above.

[0020]

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

[0021]

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

[0022]

[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, and proline. Others 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) (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 This includes ,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, tricarbaryl acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or sulfonic acids such as disodium 4,5-dihydroxy-1,3-benzenedisulfonic acid. In certain embodiments, such additional complexing agents are selected from citric acid and 1-hydroxyethylidene-1,1-diphosphonic acid.

[0023]

[0023] In other embodiments, 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-propanthol, 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 (NMP), cyclohexylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, methyldiethanolamine, methyl formate, dimethylformamide (DMF), dimethyl sulfoxide (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, Butyryl Lactone, 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 This includes 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-formylmorpholine, triethyl phosphate, and combinations thereof.

[0024]

[0024] In other embodiments, the composition further comprises one or more water-dispersible or water-soluble polymers. If such polymers are present, they may include methacrylic acid homopolymers, and copolymers of acrylamide methylpropanesulfonic acid and maleic acid, maleic acid / vinyl ether copolymers, poly(vinylpyrrolidone) / vinyl acetate homopolymers, for example phosphonized polyethylene glycol oligomers, polyacrylic acid (PAA), polyacrylamide, polyvinyl acetate, polyethylene glycol (PEG), polypropylene glycol (PPG), polystyrene sulfonic acid, polyvinyl sulfonic acid, polyvinylphosphonic 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, This includes, but is 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 its copolymers), dimethylaminomethacrylate polymer and its copolymers, trimethylammonium methyl methacrylate polymer and its copolymers, and combinations thereof. The copolymers may be random copolymers or block copolymers. If present, the amount of polymer in the composition is in the range of about 0.0001% to about 5% by weight, based on the total weight of the composition.

[0025]

[0025] In other embodiments, the composition further comprises one or more surfactants. In yet another embodiment, the composition further comprises a nonionic surfactant. As used herein, the term “surfactant” refers to an organic compound that reduces surface tension (or interfacial tension) between two liquids or between a liquid and a solid, and typically refers to an organic amphiphilic compound having a hydrophobic group (e.g., the “terminus” of a hydrocarbon (e.g., alkyl)) and a hydrophilic group. Where present, these nonionic surfactants for use in the compositions described herein are, 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, ethylene oxide and propylene oxide-based block copolymer, polyoxypropylene sucrose ether, t-octylphenoxypolyethoxyethanol, 10-ethoxy-9,9-dimethyldecane-1-amine, polyoxyethylene(9) nonylphenyl ether, branched, The product contains 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-norbornene-2-yl)ethyl]trisiloxane, monomer octadecylsilane derivatives, siloxane-modified polysilazane, silicone polyether copolymer, and ethoxylated fluorinated surfactants.

[0026]

[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, benzisothiazolon, 1,2-benzisothiazol-3[2H]-one, methylisothiazolinone, methylchloroisothiazolinone, and combinations thereof.

[0027]

[0027] As used herein, the term “residue” (including “contaminant”) refers to any substance that is a chemical or particulate matter remaining on the surface of a microelectronic device substrate after processing steps used in the manufacture of microelectronic devices, such as plasma etching, plasma ashing (removing photoresist from an etched wafer), chemical mechanical processing, or wet etching. Residue may be any non-aqueous chemical that is part of the processing composition used in the processing step, such as a chemical etchant, photoresist, or CMP slurry. Residue may also be a substance obtained from the materials of the processing composition during the processing step. Examples of these types of residue include non-aqueous, particulate or non-particulate chemicals or abrasives (e.g., abrasive particles, surfactants, oxidizing agents, corrosion inhibitors, catalysts) that remain on the surface of the substrate after processing. Residue may be originally present in the material, such as CMP slurry or etching composition, for example, solid abrasive particles or chemicals present in CMP abrasive slurry. Alternatively, the residue may be by-products or reaction products (particulate (e.g., aggregates, precipitates) or non-particulate) generated during processing, for example, by-products or reaction products of chemicals present in the processing composition, such as a CMP slurry or a wet etching composition, or chemicals present, used, or generated during the plasma etching or plasma ashing process.

[0028]

[0028] The term “post-CMP residue” refers to residues present at the end of the CMP processing step, such as particles or chemicals present in or obtained 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 such as oxidizing agents, catalysts, surfactants, inhibitors, and complexing agents originally present in the slurry; metals, metal oxides, or metal complexes obtained from metallic materials removed from the substrate surface during processing; or reaction products or complexes produced using substrate-derived chemicals such as; pad particles, or other materials that are products of the CMP process.

[0029]

[0029] "Etching residue" refers to the material remaining after a gas-phase plasma etching process, such as back-end-of-line (BEOL) dual damascene or wet etching process. Etching residue may have organic, organometallic, organosilicon, or inorganic properties, and may include, for example, silicon-containing materials, carbon-based organic materials, and etching gas residues such as oxygen and fluorine.

[0030]

[0030] "Post-ashing residue" refers to the material remaining after oxidation plasma or reduction plasma ashing to remove the cured photoresist or lower anti-reflective coating (BARC) material. The residue after ashing may be organic, organometallic, organosilicon, or inorganic.

[0031]

[0031] As described above, the present invention relates to a composition useful for a cleaning method to remove residue from the surface of a microelectronic device substrate having residue. The composition comprises an aqueous carrier (i.e., water) together with a combination of non-aqueous components described herein. In certain embodiments, the composition is a homogeneous solution containing, or consisting of, or essentially consisting of, water and dissolved non-aqueous components, and is free of solid or suspended substances such as solid abrasive particles, aggregates, or coagulations before being used in the cleaning process.

[0032]

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

[0033]

[0033] The microelectronic devices used herein are devices on which electrical circuits and related structures with very small dimensions (e.g., on a micron scale or less) are formed. Exemplary microelectronic devices include flat panel displays, integrated circuits, memory devices, solar panels, photovoltaic power generation, and microelectromechanical systems (MEMS). A microelectronic device substrate is a structure such as a wafer (e.g., a semiconductor wafer) containing one or more microelectronic devices or their precursors in a state prepared for forming the final microelectronic device.

[0034]

[0034] The compositions and methods described herein are useful for cleaning various forms of microelectronic devices at every stage of processing. By using the cleaning compositions and methods described herein, the majority of 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 known as “cleaning efficiency”).

[0035]

[0035] Methods and apparatus for measuring residues on the surface of microelectronic device substrates are well known. The cleaning effect 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- and post-cleaning analysis may be performed using an atomic force microscope. Residual particles on the surface may be registered as a range of pixels. A histogram (e.g., Sigma Scan Pro) can be applied to filter pixels of a specific intensity (e.g., 231-235) and count the number of residual particles. The amount of residual particles removed, i.e., the cleaning efficiency, can be calculated using the following ratio: (Number of particles remaining on the surface before cleaning - Number of particles remaining on the surface after cleaning) / (Number of particles remaining on the surface before cleaning).

[0036]

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

[0037]

[0037] The compositions of the present invention may be prepared and sold in the form of concentrates containing a relatively small amount of water, and therefore a relatively concentrated amount of non-aqueous components. The concentrates may be commercially prepared to be sold and transported containing a concentrated amount of non-aqueous components and a relatively small amount of water, and ultimately diluted by the purchaser of the concentrate at the time of use. The amounts of different non-aqueous components in the concentrate are such that, when the concentrate is diluted, the desired amount of those non-aqueous components will be present in the composition that is ultimately used.

[0038]

[0038] The compositions described contain water as a liquid carrier for non-aqueous components, i.e., a solute. The water may be deionized water (DIW). The water may be present in the composition from any source, such as by being included in a component that is combined with other components to produce a composition in the form of a concentrate, or as water combined in pure form with other components of the concentrate, or as water added to the concentrate by the user as diluent water for the purpose of diluting the concentrate at the time of use to form a composition for use.

[0039]

[0039] The amount of water in the composition may be a desirable amount for the concentrate or a desirable amount for the composition to be used, which is usually higher in total than in the concentrate. Exemplary amounts of water in a concentrated composition may be about 30, 40, or 50 to about 85 or 90 weight percent, for example, about 60, 65, or 70 to about 80 weight percent, based on the total weight of the concentrated composition. When diluted, these amounts decrease according to the dilution ratio. An example of the amount of water in a composition to be used may be about 70 to about 99.9 weight percent, for example, about 90 or 99.55 to about 95 or 99 weight percent, based on the total weight of the composition to be used.

[0040]

[0040] The compositions of the present invention can be easily prepared by simply adding each component and mixing until a homogeneous state such as a solution is reached. Furthermore, the compositions can be easily formulated as single-package 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 can be mixed by the user in either a processing tool (washing device) or a storage tank upstream of the processing tool.

[0041]

[0041] Accordingly, another aspect of the present invention relates to a kit that contains various components of the compositions described herein in two or more containers suitable for storage and transport of the compositions, and which may include, for example, NOWPak® containers (Entegris, Inc., Billerica, Massachusetts, USA). Accordingly, in a third aspect, the present invention relates to a kit that contains two or more containers, a. Water and, b. A washing 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 ethyldithiocarbamate and their salts, c. A chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine, d. A reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfite, e. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glycosiamine, f. pH adjuster and Provide a kit that includes two or more of these items.

[0042]

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

[0043]

[0043] In cleaning steps such as the residue cleaning step after CMP, the cleaning composition may be used with any of the following known conventional commercial cleaning tools, including, but not limited to, the Verteq single wafer megasonic Goldfinger, OnTrak system DDS (double-sided scrubber), SEZ or other single wafer spray rinses, Applied Materials Mirra-Mesa® / Reflexion® / Reflexion LK®, and Megasonic batch wet bench systems, and Ebara Technologies, Inc. products such as 300mm models (FREX300S2 and FREX300X3SC) and 200mm CMP systems (FREX200M).

[0044]

[0044] The conditions and timing of the cleaning step can be set as needed and may vary depending on the type of substrate and residue. When using a composition for cleaning CMP residue, etching residue, ashing residue, or contaminants from a microelectronic device substrate having them, the cleaning composition can be brought into contact 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 in the range of about 20°C to about 90°C, or about 20°C to about 50°C. Such contact times and temperatures are illustrative, and other suitable times and temperature conditions may be useful as long as they are effective in at least partially cleaning an initial amount of residue from the surface.

[0045]

[0045] After cleaning the device substrate surface to the desired level, the cleaning composition used in the cleaning step can be easily removed from the device surface so as to be desirable and effective in a given end use. For example, removal can be performed using a cleaning solution containing deionized water. The device is then treated as necessary, such as by drying (e.g., using nitrogen or a spin drying cycle), followed by further treatment of the cleaned and dried device surface.

[0046]

[0046] In other, more general or specific methods, a microelectronic device substrate is first subjected to a processing step which includes one or more of the following: CMP treatment, plasma etching, wet etching, plasma ashing, etc., and then subjected to a cleaning step which includes cleaning the substrate surface with the composition of the present invention. At the end of the first processing step, residues (e.g., residues after etching, residues after CMP, residues after ashing) remain on the surface of the substrate. A cleaning step using the cleaning composition described is effective in removing a considerable amount of residue from the surface of a microelectronic device.

[0047]

[0047] Accordingly, in a third embodiment, the present invention provides a method for removing residue on a microelectronic device substrate, the method being A. The surface of the microelectronic device substrate, a. Water, b. Washing additives 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, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine. d. A reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfite. e. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glycosiamine, and f. pH adjuster Contacting with a composition containing, B. To remove at least partially the residue from the substrate of the microelectronic device. Includes.

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

[0049]

[0049] Example - Concentrated formulation TIFF0007862587000001.tif89170

[0050]

[0050] Experimental results:

[0051] In these experiments, 300mm copper blanket wafers were polished and cleaned with Reflexion® LK CMP tools using appropriate consumables such as slurry, pads, and brushes. The number of defects with a defect size of 80nm was detected using the SP-3 defect inspection tool. Next, defects were classified in terms of organic matter, silica, etc., using the EDR-7380 defect review tool (KLAT), which includes a microscope, SEM, and EDX. The data in Table 1 below shows that the cleaning compositions of Examples 1-4 are improved compared to the comparative examples. These PCMP cleaning agents significantly reduced the amount of organic residue on the copper blanket wafers. The silica particle cleaning performance was comparable among the tested solutions.

[0051]

[0052] Table 1 TIFF0007862587000002.tif42170

[0052]

[0053] When three types of corrosion inhibitors (dicyandiamide, guanylurea, and glycosiamine) were added to 4.5% MEA (CAS number 141-43-5), the Cu etching rate decreased, but the effect on the Co etching rate was negligible.

[0053]

[0054] Table 2 TIFF0007862587000003.tif30170

[0054]

[0055] The alternative chelating and reducing agents tested with the following formulations resulted in a decrease in the Co etching rate.

[0055]

[0056] Table 3 TIFF0007862587000004.tif45170

[0056]

[0057] manner

[0058] In the first embodiment, the present invention is a. Water and, b. A washing 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 ethyldithiocarbamate and their salts, c. A chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine, d. A reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfite, e. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glycosiamine, f. pH adjuster and The present invention provides a composition containing the following:

[0057]

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

[0058]

[0060] In a third embodiment, the present invention provides compositions according to the first or second embodiment, 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 embodiment, the present invention provides compositions according to the first, second, or third embodiment, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid, and hypophosphorous acid.

[0060]

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

[0061]

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

[0062]

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

[0063]

[0065] In the eighth embodiment, the present invention provides a composition according to any one of the first to seventh embodiments, where d is diethylhydroxylamine and e is dicyandiamide.

[0064]

[0066] In a ninth embodiment, the present invention relates to a composition, a. Water and, b. Monoethanolamine and, c. Cysteine ​​and, d. Diethylhydroxylamine and, e. Dicyandiamide, f. pH adjuster and The present invention provides a composition containing the following:

[0065]

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

[0066]

[0068] In the eleventh embodiment, the present invention provides a composition of any one of the first to tenth embodiments, the composition comprising 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(meth The mixture further comprises one or more chelating agents selected from lenophosphonic acid, hydroxyethyl diphosphonate, nitrilotris(methylene)phosphonic acid; 2-phosphonobutane-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, tricarbaryl acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid and its salts.

[0067]

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

[0068]

[0070] In a thirteenth aspect, the present invention provides a composition according to a 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 embodiments, 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 embodiments, the composition further comprising one or more water-dispersible or water-soluble polymers.

[0071]

[0073] In a sixteenth embodiment, the present invention provides a method for removing residue from a microelectronic device substrate, the method being: A. The surface of the microelectronic device substrate, a. Water, b. Washing additives 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, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine. d. Compounds selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfite, e. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glycosiamine, and f. pH adjuster Contacting with a composition containing, B. To remove at least partially the residue from the substrate of the microelectronic device. Includes.

[0072]

[0074] In a 17th aspect, the present invention provides a method according to a 16th 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 the eighteenth embodiment, the present invention provides a method according to the sixteenth or seventeenth embodiment, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine, and hydroxyethylidenediphosphonic acid.

[0074]

[0076] In a 19th embodiment, the present invention provides a method according to the 16th, 17th, or 18th embodiment, wherein the reducing agent is selected from diethylhydroxylamine, ascorbic acid, and hypophosphorous acid.

[0075]

[0077] In the 20th embodiment, the present invention provides a method according to any one of the 16th to 19th embodiments, wherein the corrosion inhibitor is selected from dicyandiamide, guanylurea, and glycosiamine.

[0076]

[0078] In a 21st embodiment, the present invention provides a method according to any one of the 16th to 20th embodiments, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetraethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

[0077]

[0079] In the 22nd embodiment, the present invention provides a method according to the 16th embodiment, wherein the composition is a. Water and, b. Monoethanolamine and, c. Cysteine ​​and, d. Diethylhydroxylamine and, e. Dicyandiamide, f. pH adjuster and Includes.

[0078]

[0080] In a 23rd embodiment, the present invention provides a method according to a 22nd embodiment in which the pH adjusting agent is choline.

[0079]

[0081] In a 24th embodiment, the present invention provides a container for one or more containers. a. A washing 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 ethyldithiocarbamate and their salts, b. A chelating agent selected from monoethanolamine, ethanolamine, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine, c. A reducing agent selected from diethylhydroxylamine, ascorbic acid, hypophosphorous acid, and sulfite, d. A corrosion inhibitor selected from dicyandiamide, guanylurea, and glycosiamine, f. pH adjuster and Provide a kit that includes two or more of these items.

[0080]

[0082] While several exemplary embodiments of this disclosure have been described above, those skilled in the art will readily understand that further embodiments can be created and used within the scope of the claims appended herein. Many of the advantages of the disclosures covered in this document have been stated above. However, it will be understood that in many respects this disclosure is merely illustrative. Naturally, the scope of the disclosure is defined in the language in which the appended claims are expressed.

Claims

1. A composition for cleaning a substrate including a copper surface, a. Water and, b. A washing 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, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine; diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine, d. A reducing agent that is diethylhydroxylamine, e. A corrosion inhibitor that is dicyandiamide, f. pH adjusters and A composition containing the following:

2. The composition according to claim 1, wherein the cleaning additive is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

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

4. The composition according to claim 1, wherein the pH adjusting agent is selected from choline hydroxide, potassium hydroxide, tetraethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

5. a. Water and, b. Monoethanolamine and, c. Cysteine ​​and, d. Diethylhydroxylamine and, e. Dicyandiamide and f. pH adjusters and The composition according to claim 1, comprising:

6. 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), Hydroxyethyldiphosphonate, Nitrilotris The composition according to claim 1, further comprising one or more additional complexing agents selected from (methylene)phosphonic acid, 2-phosphonobutane-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, tricarbaryl acid, dimethylolpropionic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, 4,5-dihydroxy-1,3-benzenedisulfonic acid and salts thereof.

7. The composition according to claim 1, further comprising one or more water-miscible solvents.

8. The composition according to claim 7, wherein the water-miscible solvent is selected from triethylene glycol monobutyl ether, propylene glycol n-butyl ether, dimethyl sulfoxide, and diethylene glycol monophenyl ether.

9. The composition according to claim 1, further comprising one or more surfactants.

10. The composition according to claim 1, further comprising one or more water-dispersible or water-soluble polymers.

11. A method for removing residue from a microelectronic device substrate, A. The surface of the microelectronic device substrate a. Water, b. Washing additives 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, hydroxyethylidenediphosphonic acid, 2-amino-2-(hydroxymethyl)-1,3-propanediol, diglycolamine, diisopropanolamine, isopropanolamine, nitrilotris-(methylenephosphonic acid), diethylenetriaminepentamethylenephosphonic acid, phosphoric acid, and triethanolamine. d. A reducing agent that is diethylhydroxylamine, e. A corrosion inhibitor that is dicyandiamide, and f. pH adjusters Contacting a composition for cleaning a substrate including a copper surface, which includes, B. To remove at least partially any residue from the microelectronic device substrate. Methods that include...

12. The method according to claim 11, wherein the cleaning additive is selected from cysteine, cystine, and 1,3,4-thiadiazole-2-methyl-5-thiol.

13. The method according to claim 11, wherein the chelating agent is selected from monoethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, triethanolamine, and hydroxyethylidenediphosphonic acid.

14. The method according to claim 11, wherein the pH adjuster is selected from choline hydroxide, potassium hydroxide, tetraethylammonium hydroxide, and methyltris(hydroxyethyl)ammonium hydroxide.

15. The composition is a. Water and, b. Monoethanolamine and, c. Cysteine ​​and, d. Diethylhydroxylamine and, e. Dicyandiamide and f. pH adjusters and The method according to claim 11, including the method described in claim 11.

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