Post-CMP Cleaning Compositions

Abstract

The present invention provides compositions useful for post-CMP cleaning operations in which ceria is present. In one embodiment, the present invention provides a composition having a pH of less than about 8, comprising a reducing agent; a chelating agent; an amino (C6-C 12 and water. The compositions of the invention have been found to exhibit improved ceria removal, for example on polysilicon (poly-Si) substrates. Also provided are methods of cleaning microelectronic device substrates using such compositions, and kits containing selected components of the compositions of the invention in one or more containers.

Description

[Technical field]

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

[0002]

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

[0003]

[0003] To obtain correct patterning, excess material used in forming layers on a substrate must be removed. Furthermore, to produce functional and reliable circuits, it is important to prepare a flat or planar microelectronic wafer surface prior to subsequent processing. Therefore, certain surfaces of microelectronic device wafers need to be removed and / or polished.

[0004] Chemical mechanical polishing or planarization ("CMP") is a process that removes material from the surface of a microelectronic device wafer and polishes (e.g., makes the surface flat) by combining physical processes, such as abrasion, with chemical processes, such as oxidation or chelation. In its most basic form, CMP involves the application of an abrasive slurry containing active chemicals to a polishing pad that buffs the surface of the microelectronic device wafer during the removal, planarization, and polishing process. To achieve rapid and uniform removal, removal or polishing processes that utilize purely physical or purely chemical actions are not as effective as a synergistic combination of the two. Furthermore, in the manufacture of integrated circuits, CMP slurries must be able to preferentially remove films, including composite layers of metals and other materials, so that highly planar surfaces can be produced for subsequent photolithography, or patterning, etching, and thin film processing.

[0005]

[0005] CMP slurries using ceria particles generally achieve higher dielectric polishing rates compared to silica-containing slurries. In addition, ceria-based slurries are the most widely used because they achieve planarization of shallow trench isolation (STI) patterns while minimizing oxide erosion. Ceria-based slurries have the disadvantage that they are difficult to remove from STI structures due to the oppositely charged zeta potential of the ceria particles relative to the silicon oxide and silicon nitride surfaces. If such residues remain on the wafer during device fabrication, the residues will lead to short circuits and increased electrical resistance. Ceria particles are also problematic in FinFET structures after CMP processing with ceria slurries.

[0006]

[0006] Therefore, a need exists for improved post-CMP cleaning compositions that effectively remove both residual particles and residues adhering to the dielectric wafer surface. Summary of the Invention

[0007] In summary, the present invention provides a composition useful for post-CMP cleaning operations in the presence of ceria. In a first aspect, the present invention provides a composition comprising: A reducing agent; b. Chelating agents; c. Amino (C6-C 12 (alkyl) alcohols; and d.Water wherein the composition has a pH of less than about 8.

[0008] The compositions of the present invention have been found to exhibit improved ceria removal, for example, on polysilicon (poly-Si) substrates.

[0009] Also provided are methods for cleaning microelectronic device substrates using the compositions, and kits comprising one or more components of the compositions of the invention in one or more containers. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010]

[0010] 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 typically used in its sense including "and / or" unless the content clearly dictates otherwise.

[0011]

[0011] 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.

[0012] Numerical ranges expressed using endpoints include all numbers within that range (eg 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0013] In a first aspect, the present invention provides a method for producing a composition comprising: A reducing agent; b. Chelating agents; c. Amino (C6-C 12 (alkyl) alcohols; and d.Water wherein the composition has a pH of less than about 8.

[0014] In one embodiment, the composition comprises about 60 to 90 weight percent water, about 0.01 to about 10 weight percent chelating agent, about 0.1 to about 5 weight percent or about 0.1 to about 2 weight percent amino (C6-C 12 It is composed of alkyl alcohols.

[0015]

[0015] In certain embodiments, the composition consists or consists essentially of the above a to b components, optionally in combination with one or more other components described herein. In this specification, unless otherwise specified, a composition or a component of a composition described as "consisting essentially of" one or more specific items refers to a composition or component consisting of only those specific items with only minor amounts of other (additional) materials, for example, containing the specific items and 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 of only those specific items.

[0016] As stated above, the pH of the compositions of the present invention is less than about 8. In certain embodiments, the pH is neutral or acidic, for example, from about 1 to about 7, and in other embodiments, the pH is from about 1.5 to about 6.5. Those skilled in the art will be aware of suitable acids and bases (i.e., pH adjusters) for this purpose.

[0017] In some embodiments, the pH adjuster is a base.Exemplary pH adjusters for this purpose include choline hydroxide, tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, triphenylphosphonium methyl hydroxide, triphenylphosphonium ethyl hydroxide, N-propyltriphenylphosphonium hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), trimethylethylammonium hydroxide, diethyldimethylammonium hydroxide, tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), tetramethylammonium hydrochloride (TMAH), tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, arginine, potassium hydroxide, cesium hydroxide, and combinations thereof.

[0018] In certain embodiments, the pH adjuster is selected from choline hydroxide and tetraethylammonium hydroxide (TEAH).

[0019] In another embodiment, the pH adjuster is an acid and can be selected from, for example, nitric acid, citric acid, sulfuric acid, phosphoric acid, hydrochloric acid, hydrobromic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, lactic acid, glycolic acid, or any combination thereof. In one embodiment, the pH adjuster is nitric acid.

[0020]

[0020] In certain embodiments, the compositions of the present invention further comprise one or more buffers. In some embodiments, the compositions further comprise N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid).

[0021]

[0021] Exemplary reducing agents include compounds such as hypophosphorous acid (H3PO2), ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, DEHA (diethylhydroxylamine), reducing sugars (galactose), and combinations thereof. In addition, phosphoric acid, sulfurous acid, ammonium and potassium thiosulfate, xylose, sorbitol. N-aminomorpholine, N-aminopiperazine, hydroquinone, catechol, tetrahydrofulvalene, N,N-dimethylaniline benzylamine, hydroxylamine, and other sulfur-based reducing agents may be used. In some embodiments, the reducing agent is selected from hypophosphorous acid and L-ascorbic acid.

[0022]

[0022] As used herein, "chelating agent" includes compounds understood by those skilled in the art to be complexing agents, chelating agents and / or sequestering agents. Chelating agents chemically bind, coordinate, or physically retain metal atoms and / or metal ions to be removed using the compositions described herein. Exemplary chelating agents include phosphonates (e.g., 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), 1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,N',N'',N'' '-Tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepentakis(methylenephosphonic acid) (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-phosphono-butane-1,2,3,4-tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid)phenylphosphonic acid, salts thereof, and derivatives thereof) and / or carboxylic acid ( For example, chelating agents include 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, tritylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine) and / or 4,5-dihydroxy-1,3-benzenedisulfonic acid disodium salt. In other embodiments, chelating agents include amino acids such as glycine, alanine, histidine, leucine, isoleucine, lysine, cysteine, methionine, phenylalanine, serine, valine, threonine, arginine, asparagine, aspartic acid, glutamic acid, glutamine, proline, tryptophan, and tyrosine.In other embodiments, the chelating agent includes an aminosulfonic acid, such as 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid. In certain embodiments, the complexing agent is selected from at least one of HEDP and citric acid.

[0023] The amount of chelating agent in the cleaning composition of the present invention ranges from about 0.01% to about 20% by weight, based on the total weight of the cleaning composition. In certain embodiments, the complexing agent is present in an amount of about 0.01% to about 10% by weight, and in other embodiments, from about 0.01% to about 5% by weight, based on the total weight of the cleaning composition.

[0024]

[0024] The amino (C6-C 12 An amino (C6-C alkyl) alcohol is a compound having at least one amine and at least one hydroxyl functional group in any combination of 6 to 12 carbon atoms. 12 In one embodiment, the amino (C6-C alkyl) alcohol is selected from 3-amino-4-octanol; DL-2-amino-1-hexanol; 2-(butylamino)ethanol; 1-aminocyclohexanol; and 8-amino-1-octanol. 10 Alkyl) alcohols include 3-amino-4-octanol.

[0025]

[0025] In certain embodiments, the compositions of the present invention further comprise one or more fluoride sources. As used herein, a "fluoride" source includes, but is not limited to, ionic fluoride (F - ) and HF2 -or a species containing a salt thereof. The fluoride source may be included as a fluoride species or may be generated in situ from a fluoride source. Fluoride sources include hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid, tetrafluoroboric acid, tetrabutylammonium tetrafluoroborate (TBA-BF4), hexafluorotantalic acid, hexafluorotitanic acid, ammonium hexafluorotantalate, hexafluorotantalic acid having the formula [NR 1 R 2 R 3 R 4 ]F, a tetraalkylammonium fluoride having the formula 1 , R 2 , R 3 , and R 4 are the same or different, for example, C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl) and C6-C 10 aryl (e.g., benzyl), or combinations thereof. In some embodiments, the fluoride source comprises HF.

[0026] In a further embodiment, the composition of the present invention further comprises at least one water-dispersible or water-soluble polymer, when present, including, but not limited to, homopolymers of acrylic acid and methacrylic acid, and copolymers of acrylamidomethylpropanesulfonic acid and maleic acid, maleic acid / vinyl ether copolymers, poly(vinylpyrrolidone) / vinyl acetate, homopolymers such as phosphonated polyethylene glycol oligomers, poly(acrylamide), poly(acrylic acid) (PAA), poly(methacrylic acid), poly(methacrylic acid) ammonium salt, poly(acrylic acid) ammonium salt poly(vinyl acetate), poly(ethylene glycol) (PEG), poly(propylene glycol) (PPG), poly(styrenesulfonic acid), poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinyl phosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide (PEO), polyvinylpyrrolidone (PVP), PPG-PEG-PPG block copolymers. , PEG-PPG-PEG block copolymers, poly(vinyl alcohol), poly(hydroxyethyl)acrylate (and copolymers thereof), poly(hydroxyethyl)methacrylate (and copolymers thereof), hydroxyethylcellulose, methylhydroxyethylcellulose, hydroxypropylcellulose, methylhydroxypropylcellulose, xanthan gum, potassium alginate, pectin, carboxymethylcellulose, glucosamine, poly(diallyldimethylammonium) 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 copolymers may be random or block copolymers.The amount of polymer (if present) in the composition of the present invention ranges from about 0.0001% to about 5% by weight, based on the total weight of the composition.

[0027] 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, and typically refers to an organic amphiphilic compound that contains a hydrophobic group (e.g., a hydrocarbon (e.g., alkyl) "tail") and a hydrophilic group. These non-ionic surfactants (if present) for use in the compositions described herein include linear, branched, saturated or unsaturated, alkyl or aromatic ethoxylated alcohols. Exemplary surfactants include polyoxyethylene lauryl ether, dodecenyl succinic acid monodiethanolamide, ethylenediamine tetrakis(ethoxylate-block-propoxylate) tetrol, polyethylene glycol, polypropylene glycol, polyethylene or polypropylene glycol ether, block copolymers based on ethylene oxide and propylene oxide, polyoxypropylene sucrose ether, t-octylphenoxypolyethoxyethanol, 10-ethoxy-9,9-dimethyldecan-1-amine, polyoxyethylene(9) nonylphenyl ether, branched polyoxyethylene(40) nonylphenyl ether, and the like. ethers, 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.

[0028] In another embodiment, the composition of the present invention further comprises one or more water-miscible solvents, such as glycols and glycol ethers, methanol, ethanol, isopropanol, butanol, and higher alcohols selected from C2-C4 diols and C2-C4 triols, tetrahydrofurfuryl alcohol, such as 3-chloro-1,2-propanediol, 3-chloro-1-propanethiol, 1-chloro-2-propanol, 2-chloro-1-propanol, 3-chloro-1-propanol, 3-bromo-1,2-propanediol, 1-bromo-2-propanol, 3-bromo-1-propanol, 3-iodo ... ethanol, 4-chloro-1-butanol, 2-chloroethanol), dichloromethane, chloroform, acetic acid, propionic acid, trifluoroacetic acid, tetrahydrofuran, N-methylpyrrolidinone, cyclohexylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, methyldiethanolamine, methyl formate, dimethylformamide, dimethylsulfoxide, tetramethylene sulfone, diethyl ether, phenoxy-2-propanol, propiophenone, ethyl lactate, ethyl acetate, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol, 1,3-Propanediol, dioxane, butyryllactone, butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene Examples of the ethylene glycol dimethyl ether include dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether hexaethylene glycol monophenyl ether, dipropylene glycol methyl ether acetate, tetraethylene glycol dimethyl ether dibasic ester, glycerin carbonate, N-formyl morpholine, triethyl phosphate, and combinations thereof.

[0029]

[0029] In other embodiments, the compositions of the present invention further comprise one or more auxiliary agents. In an embodiment, the auxiliary agent is selected from compounds that function as hydrogen bonding additives and serve to reduce the adhesion of silica particles to brushes utilized in cleaning microelectronic devices after CMP. See, for example, US Patent Application Publication No. 2019 / 0168265265, incorporated herein by reference. Exemplary compounds include nonionic, anionic, cationic, and zwitterionic small molecules and polymers that can behave as polyelectrolytes at neutral pH. Anionic polymers or anionic polyelectrolytes are natural polymers, modified natural polymers, or synthetic polymers. Exemplary natural anionic polymers and modified natural anionic polymers that can be included in the compositions of the present invention include, but are not limited to, alginic acid (or salts thereof), carboxymethylcellulose, dextran sulfate, poly(galacturonic acid), and salts thereof. Exemplary synthetic anionic polyelectrolytes include, but are not limited to, homopolymers or copolymers of maleic acid (or anhydride), styrenesulfonic acid (or salts thereof), vinylsulfonic acid (or salts thereof), allylsulfonic acid (or salts thereof), acrylamidopropylsulfonic acid (or salts thereof), and the like, with the salts of carboxylic and sulfonic acids preferably being neutralized with ammonium or alkylammonium cations. In certain embodiments, the cation of the polyelectrolyte anionic polymer is an ammonium cation (NH + ), choline (cholinium) ( + N(CH3)3(CH2CH2OH)), and + N(CH3)4. Thus, examples of combinations of synthetic and natural polyelectrolyte anionic polymers are homopolymers or copolymers of (meth)acrylic acid, maleic acid (or anhydride), styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, acrylamidopropylsulfonic acid, alginic acid, carboxymethylcellulose, dextran sulfate, poly(galacturonic acid), and salts thereof.

[0030] In another embodiment, the composition of the present invention 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.

[0031]

[0031] 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 process step used in the manufacture of a microelectronic device, such as plasma etching, plasma ashing (removing photoresist from an etched wafer), chemical machining, wet etching, etc. The residue may be any non-aqueous chemical material that is part of the processing composition used in the process, such as a chemical etchant, photoresist, CMP slurry, etc. The residue may also be material derived from the materials of the processing composition during the processing step. Examples of these types of residue include non-aqueous, particulate or non-particulate chemical materials or abrasives (e.g., abrasive particles, surfactants, oxidizers, corrosion inhibitors, catalysts) that remain on the surface of the substrate after processing. The residue may be originally present in a material such as a CMP slurry or etching composition, such as solid abrasive particles or chemical materials present in a CMP polishing slurry. Alternatively, the residue may be a by-product or reaction product (particulate or non-particulate) generated during processing, for example, a by-product or reaction product of a chemical present in a processing composition such as a CMP slurry or a wet etching composition, or a chemical present or used or produced during a plasma etching or plasma ashing process.

[0032]

[0032] The term "post-CMP residue" refers to residues present at the end of a CMP processing step, such as particles or chemical materials present in or derived from a 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 oxidizers, catalysts, surfactants, inhibitors, complexing agents, etc. originally contained in the slurry; metals (e.g., ions), metal oxides, or metal complexes derived from metallic materials removed from the substrate surface during processing; or reaction products or complexes formed using slurry chemicals and other chemicals in the slurry, or using slurry chemicals and substrate-derived chemicals such as metal ions; pad particles; or other materials that are products of the CMP process.

[0033] "Post-etch residue" refers to materials remaining after a gas-phase plasma etch process, such as, for example, back-end interconnect ("BEOL") dual damascene processing or wet etch processes. Post-etch residues may be organic, organometallic, organosilicon, or inorganic in nature, such as silicon-containing materials, carbon-based organic materials, and etch gas residues such as oxygen and fluorine.

[0034] "Post-ash residue" refers to materials remaining after oxidizing or reducing plasma ashing to remove hardened photoresist and / or bottom antireflective coating (BARC) materials. Post-ash residues may be organic, organometallic, organosilicone, or inorganic in nature.

[0035]

[0035] As used herein, a "low-k dielectric material" is a material used as a dielectric material in layered microelectronic devices and has a relative dielectric constant of less than about 3.5. Exemplary low-k dielectric materials include silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, low polarity materials such as organosilicate glass (OSG), tetraethyl orthosilicate (TEOS), fluorinated silicate glass (FSG), and carbon-doped oxide (CDO) glass. Low-k dielectric materials can have densities and porosities from a range of useful densities and a range of useful porosities.

[0036] As noted above, the present invention relates to compositions ("cleaning compositions" or "cleaning solutions") useful in cleaning methods for removing residues from the surfaces of residue-bearing microelectronic device substrates. The compositions comprise a reducing agent, a chelating agent, and an amino (C6-C 12 The composition contains an aqueous carrier (i.e., water) together with a combination of non-aqueous components, including a (alkyl) alcohol. In certain embodiments, the composition, prior to use in a cleaning process, is a homogeneous solution that is free of solid or suspended matter, such as solid abrasive particles, agglomerates, coagulates, etc., and comprises, consists of, or consists essentially of water and dissolved non-aqueous components.

[0037]

[0037] The compositions as described are useful for cleaning microelectronic devices and precursors thereof, particularly 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 fabricated into a final, completed, functional microelectronic device.

[0038]

[0038] As used herein, a microelectronic device is a device that includes electrical circuitry and related structures of very small (e.g., micron-scale or smaller) dimensions formed thereon. Exemplary microelectronic devices include flat panel displays, integrated circuits, memory devices, solar panels, solar cells, and microelectromechanical systems (MEMS). A microelectronic device substrate is a structure, such as a wafer (e.g., a semiconductor wafer), that includes one or more microelectronic devices or precursors thereof, in preparation for forming a final microelectronic device.

[0039]

[0039] The compositions and methods described herein are useful for cleaning various forms of microelectronic devices at any stage of processing. Particularly useful and beneficial cleanable microelectronic device substrates (abbreviated herein simply as "substrates") include substrates having an exposed surface comprising aluminum oxide, TEOS, thermal silicon oxide, borosilicate silicon dioxide glass or phosphate silicon dioxide glass, polysilicon amorphous silicon, single crystal silicon, silicon carbide, silicon nitride, silicon oxycarbide, silicon oxynitride, tungsten, molybdenum, organic polymers, low-k dielectrics, spin-on glass, siloxane-based dielectrics, and organic hybrid glass. By using the cleaning compositions and methods described herein, the majority of the residue present on the substrate surface can be successfully 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").

[0040]

[0040] Some cleaning compositions can remove multiple types of particulate residues. For example, some cleaning compositions with a pH of 2 to 4 that effectively remove ceria particles from an alumina substrate surface can disperse the alumina particles and prevent them from redepositing on the alumina surface without attacking the substrate. These compositions can also have a low but appreciable etch rate (e.g., less than 10 Å / min) to provide a controlled undercut to release these particles.

[0041] Methods and apparatus for measuring residues on the surface of a microelectronic device substrate are well known. Cleaning efficiency 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. Residual particles on the surface can be registered as a range of pixels. A histogram (e.g., Sigma Scan Pro) can 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, can be calculated using the following ratio: (Number of particles remaining on surface before cleaning - Number of particles remaining on surface after cleaning) / (Number of particles remaining on surface before cleaning).

[0042] Alternatively, cleaning efficiency can be considered as the percentage of the total amount of substrate surface covered with residual particulate matter before cleaning compared to 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 determined to be areas of interest after cleaning indicates a more effective cleaning composition and cleaning process.

[0043] 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. The concentrates are 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 time 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 use composition.

[0044] The compositions as described contain water as the 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 contained 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 a concentrate, or as water added by the user to the concentrate at the time of use, e.g., as dilution water for the purpose of diluting the concentrate to form a use composition.

[0045] The amount of water in the composition can be the desired amount for the concentrate or the desired amount for the use composition, which is generally a greater total amount relative to the amount of water in the concentrate. Exemplary amounts of water in the concentrate composition can 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 factor. Exemplary amounts of water in the use composition can 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.

[0046]

[0046] The composition of the present invention contains an amino (C6-C 12 Contains alkyl alcohol.

[0047] As a secondary cleaning compound, the composition may optionally further comprise a C2-C4 alkanolamine, such as monoethanolamine. Additional optional ingredients include morpholine, alginic acid, carboxymethylcellulose, poly(vinylpyrrolidone), poly(4-styrenesulfonic acid) (PSSA), ethoxylated fatty alcohols, and (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid).

[0048] The compositions of the present invention can be easily prepared by simply adding and mixing the components to a homogeneous state such as a solution. 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, for example, the individual parts of a multi-part formulation can be mixed by the user either at the processing tool (cleaning device) or in a storage tank upstream of the processing tool.

[0049]

[0049] Accordingly, another aspect of the present invention relates to a kit comprising one or more components of the compositions described herein in one or more containers, for combination with additional solvent (e.g., water) at the fab or at the point of use, (i) a reducing agent; (ii) a chelating agent; (iii) an amino (C6-C 10 The kit may also include any other components described herein. The container of the kit should be suitable for storing and shipping the composition, such as NOWPak® containers (Entegris, Billerica, Massachusetts, USA).

[0050]

[0050] Additionally, the compositions described herein can be provided on the market in the form of concentrates that can be diluted with an appropriate amount of water at the time of use. In concentrate form, the compositions (concentrates) include the non-aqueous components described herein, and are present in the concentrate in amounts such that when the concentrate is diluted with a desired amount of water (e.g., deionized water), each component of the cleaning composition of the present invention is present in the diluted use composition in an amount desired for use in a cleaning process, such as a post-CMP cleaning process. The amount of water added to the concentrate to form the use composition can be one or more volumes of water per volume of concentrate, for example, 2 volumes of water per volume of concentrate (e.g., 3, 4, 5, or 10 volumes of water). When the concentrate is diluted with such an amount of water, each of the solid components of the concentrate will be present in the use composition at a reduced concentration relative to the number of volumes of water added to dilute the concentrate.

[0051]

[0051] The cleaning compositions as described may be useful in microelectronic device processing applications including processes for cleaning substrate surfaces by methods such as post-etch residue removal, post-ash residue removal surface treatment, post-CMP residue removal, and the like.

[0052] The compositions and methods of the present invention are effective in removing a substantial amount of the residue from a surface that was initially present on the surface prior to the cleaning step, without significantly damaging the substrate. In some embodiments, the cleaning compositions may be effective in the cleaning step to remove at least 85 percent of the residue, or at least 95 percent of the residue, or at least 99 percent of the residue that was present on the surface of the substrate prior to removal of the residue by the cleaning step.

[0053]

[0053] In cleaning processes such as post-CMP residue cleaning processes, 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, as well as Ebara Technologies products such as 300 mm models (FREX300S2 and FREX300X3SC) and 200 mm CMP systems (FREX200M).

[0054]

[0054] 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 residues, post-etch residues, post-ash residues 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 0°C to about 90°C, or about 20°C to about 50°C. Such contact times and temperatures are exemplary, and any other suitable time and temperature conditions may be useful as long as they are effective to at least partially, preferably substantially, remove the initial amount of residue from the surface.

[0055] 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, if desired and effective for a given end use. For example, removal can be accomplished using a cleaning solution that includes deionized water. The device of the present invention can then be processed as desired, such as by drying (e.g., using nitrogen or a spin dry cycle), followed by subsequent processing of the cleaned and dried device surface.

[0056] 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 a composition of the present invention. At the end of the first processing step, residues (e.g., post-etch residues, post-CMP residues, post-ash residues, etc.) are present on the substrate surface. The cleaning step using the cleaning composition as described is effective to remove a substantial amount of the residues from the microelectronic device surface.

[0057]

[0057] Thus, in a further aspect, the present invention provides a method for removing residue on a microelectronic device substrate, the method comprising: The surface of the microelectronic device substrate A reducing agent; b. Chelating agents; c. Amino (C6-C 12 (alkyl) alcohols; and d.Water contacting the composition comprising The composition has a pH of less than about 8; and The residue is at least partially removed from the substrate. EXAMPLES

[0058]

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

[0059] The following compositions were prepared, amounts are given in weight percent: TIFF2025510755000001.tif151170

[0060]

[0060] Implementation Overview

[0061] The compositions shown above as Comparative Example 1 and Examples 1-5 were subjected to the following tests.

[0061]

[0062] General procedure for etch rate experiments:

[0063] The coupons were cut to a size of approximately 2.3 cm x 2.3 cm. Thickness measurements before and after etching were performed by XRF (metallic films: Rikagu ZSX-400) or ellipsometer (non-metallic or metal oxide films: JA Woollam M-2000D). For poly-Si samples, the surface was pretreated in a Teflon beaker (1% HF solution) and the coupons were immersed in this solution for 15 min, then rinsed with deionized water and immediately dried with nitrogen. The coupons were then placed in the beaker and stirred with a stir bar for a certain time (approximately 500 rpm), after which they were immediately washed with deionized water and dried with a nitrogen stream. The average etch rate is therefore: AER = [(thickness before) - (thickness after)] / (time required for immersion in chemical (HF solution)) In this experiment, a lower average value indicates less damage to the membrane.

[0062]

[0064] General procedure for poly-Si-DIW C / A (contact angle) experiments:

[0065] The coupons were cut to approximately 2.3 cm x 2.3 cm. Surface cleaning pretreatment and detergent immersion were performed as in Part A and dried under nitrogen flow. Contact angles were determined using a Kruss Scientific DAS100 contact angle meter. The coupons were placed in the contact angle meter holder for water drop application and contact angle measurement. The as-pretreated coupons were placed in the holder for "pre" measurements, which are the wettability of pure poly-Si unaffected by surface contamination. In this experiment, the smaller the contact angle, the better the deionized water wettability / hydrophilicity.

[0063]

[0066] Zeta potential measurements were determined for commercial ceria particles in various cleaning solutions.

[0067] The ceria particles were stirred with a mixer to ensure that the particles were well dispersed in the washing solution, and then transferred to the holder of a zeta potential instrument (Beckman Coulter, Delsa Nano C) for automated zeta potential measurement. In this experiment, the larger the absolute value of the zeta potential (regardless of the + / - sign) is, the better, since it means that there is a higher charge density that repels the particles from each other.

[0064]

[0068] General procedure for measuring the zeta potential of polySi / TEOS in detergents.

[0069] The coupons were cut to approximately 2.3 cm x 2.3 cm. These poly-Si coupons were pretreated with dilute HF according to the method described in step A above. The coupons were placed in a surface potential measurement holder (Anton Paar, SurPASS3) that automatically measures the zeta potential. In this experiment, the larger the absolute value of the zeta potential (regardless of the + / - sign) is, the better, because it means that there is a higher charge density that repels the particles from each other.

[0065]

[0070] General Procedure for Dissolving Ceria by Composition

[0071] Commercially available ceria particles were mechanically mixed to ensure the particles were well dispersed and then added to various cleaning solutions (in Teflon beakers). The samples were then stirred for 5 minutes. The solutions were transferred to centrifuge tubes and centrifuged at 15,000 for 15 minutes. A 2ml sample was taken from the supernatant (i.e. top layer) to determine the cerium concentration by ICP-OES analysis (Inductively Coupled Optical Emission Spectroscopy). In this experiment, the higher the ICP-OES cerium concentration, the better, as this indicates more ceria dissolved / dispersed in the solution.

[0066]

[0072] General procedure for defect evaluation

[0073] The purpose of this measurement is to evaluate how well the composition can clean TEOS wafer substrates. The composition was prepared and filtered. TEOS wafers (8 inch diameter), commercial ceria slurry, and appropriate post-CMP / clean parts and consumables were used for whole wafer polishing experiments. 200 mm wafers were in-process polished with Mirra® and cleaned with OnTrak® from Advanced Materials and Technology, Inc., and defects were measured by SP1 with a threshold of >0.11 μm (to count how many particles were found on the processed wafer). TIFF2025510755000002.tif150170

[0067] Aspects In a first aspect, the present invention provides a method for producing a composition comprising the steps of: A reducing agent; b. Chelating agents; c. Amino (C6-C 12 (alkyl) alcohols; and d.Water wherein the composition has a pH of less than about 8.

[0068] In a second aspect, the present invention provides a composition of the first aspect, wherein the reducing agent is selected from hypophosphorous acid, diethylhydroxylamine, sulfurous acid, and L-ascorbic acid.

[0069]

[0061] In a third aspect, the present invention provides a composition of the first or second aspect, wherein the chelating agent is selected from aspartic acid, glutamic acid, citric acid, phosphoric acid, nitrile-tris(methylene phosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid.

[0070] In a fourth aspect, the present invention provides an amino (C6-C 12 The composition of the first, second or third aspect is provided, wherein the (alkyl) alcohol comprises 3-amino-4-octanol.

[0071] In a fifth aspect, the present invention provides a composition according to any one of the first to fourth aspects, further comprising a fluoride source.

[0072] In a sixth aspect, the present invention provides a composition according to any one of the first to fifth aspects, further comprising a non-ionic surfactant.

[0073] In a seventh aspect, the present invention provides a composition according to any one of the first to sixth aspects, further comprising a water-miscible solvent.

[0074] In an eighth aspect, the present invention provides a composition according to any one of the first to seventh aspects, further comprising a water-soluble or water-dispersible polymer.

[0075]

[0067] In a ninth aspect, the present invention provides a composition of any one of the first, second, fourth, fifth or seventh aspects, further comprising at least one of poly(styrene sulfonic acid); polyoxyethylene (23) lauryl ether; glutamic acid, and aspartic acid.

[0076] In a tenth aspect, the present invention provides a composition according to any one of the first to ninth aspects, further comprising N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid) or a salt thereof.

[0077]

[0069] In an eleventh aspect, the present invention provides a composition according to any one of the first to tenth aspects, which is devoid of a corrosion inhibitor, the term "devoid" being intended to correspond to less than 0.001% by weight or less than a concentration having an effective effect.

[0078] In a twelfth aspect, the present invention provides a method for removing residues on a microelectronic device substrate, comprising the steps of: A surface of the microelectronic device substrate is A reducing agent; b. Chelating agents; c. Amino (C6-C 12 (alkyl) alcohols; and d.Water having a pH of less than about 8; At least partially removing the residue from the substrate; The present invention provides a method comprising:

[0079] In a thirteenth aspect, the present invention provides a method of the twelfth aspect, wherein the reducing agent is selected from hypophosphorous acid, diethylhydroxylamine, sulfurous acid, and L-ascorbic acid.

[0080] In a fourteenth aspect, the present invention provides the method of the twelfth or thirteenth aspects, wherein the chelating agent is selected from aspartic acid, glutamic acid, citric acid, phosphoric acid, nitrile-tris(methylene phosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid. 12 2. The composition of claim 1, wherein the alkyl) alcohol comprises 3-amino-4-octanol.

[0081] In a fifteenth aspect, the present invention provides a method according to any one of the twelfth through fourteenth aspects, wherein the composition further comprises a fluoride source.

[0082] In a sixteenth aspect, the present invention provides a method according to any one of the twelfth to fifteenth aspects, wherein the composition further comprises a non-ionic surfactant.

[0083] In a seventeenth aspect, the present invention provides the method of any one of the twelfth through sixteenth aspects, wherein the composition further comprises a water-miscible solvent.

[0084] In an eighteenth embodiment, the present invention provides a method according to any one of the twelfth through seventeenth embodiments, wherein the composition further comprises a water-soluble or water-dispersible polymer.

[0085]

[0077] In a nineteenth aspect, the present invention provides a method according to any one of the twelfth to eighteenth aspects, wherein the composition further comprises at least one of poly(styrene sulfonic acid); polyoxyethylene (23) lauryl ether; glutamic acid, and aspartic acid.

[0086] In a twentieth embodiment, the present invention provides a method according to any one of the twelfth through nineteenth embodiments, wherein the composition further comprises 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid or a salt thereof.

[0087] In a twenty-first embodiment, the present invention provides the method of any one of the twelfth through twentieth embodiments, wherein the composition lacks a corrosion inhibitor.

[0088] In a twenty-second aspect, the present invention provides a method for producing a medicament for treating a cancer, comprising: in one or more containers: (i) a reducing agent; (ii) a chelating agent; (iii) an amino (C6-C 10 and water.

[0089]

[0081] In a twenty-third aspect, the present invention provides a kit according to the twenty-second aspect, wherein the composition is according to any one of the first to eleventh aspects.

[0090]

[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 contained herein have been set forth in the foregoing description. However, it will be understood that this disclosure is, in many respects, merely illustrative. It is to be understood that the scope of the present disclosure is defined in the language in which the appended claims are expressed.

Claims

1. has a pH of less than about 8; a. a reducing agent; b. a chelating agent; c. Amino (C ６ ~C １２ (alkyl) alcohol; and d. water A composition comprising:

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

3. 2. The composition of claim 1, wherein the chelating agent is selected from aspartic acid, glutamic acid, citric acid, phosphoric acid, nitrile-tris(methylene phosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid.

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

5. The composition of claim 1 further comprising a fluoride source.

6. The composition of claim 1 further comprising a non-ionic surfactant.

7. The composition of claim 1 further comprising a water-miscible solvent.

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

9. 10. The composition of claim 1, further comprising at least one of poly(styrene sulfonic acid); polyoxyethylene (23) lauryl ether; glutamic acid, and aspartic acid.

10. The composition of claim 1 further comprising N-(2-hydroxyethyl)piperazine-N'-(2-ethanesulfonic acid).

11. 10. The composition of claim 1 lacking a corrosion inhibitor.

12. 1. A method for removing residue on a microelectronic device substrate, comprising: A surface of the microelectronic device substrate is a. a reducing agent; b. a chelating agent; c. Amino (C ６ ~C １２ (alkyl) alcohol; and d. water with a composition having a pH of less than about 8 comprising: at least partially removing residue from the substrate; A method comprising:

13. 13. The method of claim 12, wherein the reducing agent is selected from hypophosphorous acid, diethylhydroxylamine, sulfurous acid, and L-ascorbic acid.

14. 13. The method of claim 12, wherein the chelating agent is selected from aspartic acid, glutamic acid, citric acid, phosphoric acid, nitrile-tris(methylene phosphonic acid), and 1-hydroxyethylidene-1,1-diphosphonic acid.

15. The method of claim 12 , wherein the composition further comprises a fluoride source.

16. The method of claim 1 , wherein the composition further comprises a non-ionic surfactant.

17. The method of claim 12 , wherein the composition further comprises a water-miscible solvent.

18. The method of claim 12 , wherein the composition further comprises a water-soluble or water-dispersible polymer.

19. 13. The method of claim 12, further comprising at least one of poly(styrene sulfonic acid); polyoxyethylene (23) lauryl ether; glutamic acid, and aspartic acid.

20. The method of claim 12, wherein the composition further comprises 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid or a salt thereof.

21. The method of claim 12 , wherein the composition lacks a corrosion inhibitor.

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