Cleaning composition containing a molybdenum etching inhibitor

Abstract

The present disclosure relates to a removal composition for at least partially removing post-chemical mechanical polishing (CMP) residues from the surface of a microelectronic device. The removal composition includes an aqueous base composition and various molybdenum etching inhibitors that reduce the amount of molybdenum removed from the surface of the microelectronic device as compared to the aqueous base composition.

Description

Technical Field

[0001] The present disclosure relates to a removal composition for at least partially removing post-chemical mechanical polishing (CMP) residues from the surface of a microelectronic device. The removal composition includes an aqueous base composition and various molybdenum etching inhibitors that reduce the amount of molybdenum removed from the surface of the microelectronic device as compared to the aqueous base composition.

Background Art

[0002] Microelectronic device wafers are used to form integrated circuits and include a substrate such as silicon having regions patterned thereon for depositing different materials having insulating, conductive, or semiconductive properties. In order to obtain correct patterning, excess material used in forming the layer on the substrate must be removed. Further, in order to fabricate functional and reliable circuits, it is important to flatten or planarize the surface of the microelectronic wafer prior to subsequent processing. Therefore, it is necessary to remove and / or polish a particular surface of the microelectronic device wafer.

[0003] Chemical mechanical polishing or planarization ("CMP") is a process in which material is removed physically and chemically from the surface of a microelectronic device wafer. The surface is polished (more specifically, planarized) by combining a physical process such as polishing with a chemical process such as oxidation or chelation. In its most basic form, CMP involves applying a slurry, e.g., a dispersion of an abrasive and an active chemical, to a polishing pad that buffs the surface of the microelectronic device wafer to achieve a removal, planarization, and polishing process. The removal or polishing process is not desirably composed of purely physical or purely chemical actions, but rather it is the synergistic combination of both that achieves high-speed and uniform removal.

[0004] After CMP processing, particles, residues, and other contaminants may be present on the surface of the microelectronic device. For that purpose, post-CMP removal compositions for removing post-CMP residues, particles, and contaminants have been developed, which may interfere with subsequent device processing steps. However, in many cases, these post-CMP removal compositions unintentionally at least partially remove other materials that should be left on the device surface.

[0005] For example, as the high integration and miniaturization of semiconductor devices further progress, molybdenum films are attracting attention as new metal electrodes for next-generation semiconductor devices. However, during a typical post-CMP removal process, the removal composition often also removes unacceptable levels of molybdenum from the surface, which can lead to the occurrence of failures and pattern defects. This becomes a greater problem as the pH of the removal composition is higher.

[0006] In this regard, new additives (low etching rate and low roughness) are needed to suppress Mo corrosion while simultaneously and sufficiently cleaning the post-CMP cleaning of dielectric substrates (such as PTEOS, SiO2, thermal oxide, silicon nitride, silicon, etc.).

[0007] Therefore, there is still a need in the art for a high-pH aqueous removal composition that can effectively remove post-CMP residues from the surface of a microelectronic device while suppressing the removal of molybdenum from the device. SUMMARY OF THE INVENTION

[0008] In one embodiment, the present disclosure relates to a removal composition for removing post-CMP residues from the surface of a microelectronic device. The removal composition includes an aqueous base composition having a pH greater than 10, comprising water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster. The removal composition further includes a) a quaternary ammonium compound of formula A: Ar-R-N + (R 1 )(R2 )(R 3 )X - (A) [wherein, Ar is a substituted or unsubstituted aryl group, and X - is a hydroxy ion, a halide ion, a sulfate ion or a methanesulfonate ion, and 1) R is a methylene group or an ethylene group, and R 1 , R 2 , and R 3 are linear or branched alkyl groups, and at least one of R 1 , R 2 , and R 3 is a C4-C 20 alkyl group, 2) R is a C3-C 20 alkylene group, and R 1 , R 2 , and R 3 are a methyl group or an ethyl group, or 3) R is a C1-C 20 alkylene group, and R 1 , R 2 , and R 3 are linear or branched alkyl groups, and at least one of R 1 , R 2 , and R 3 contains a glycol group], b) Quaternary ammonium compound of formula B: (R 4 )(R 5 )(R 6 )(R 7 )N + X - (B) [wherein, R 4 , R 5 , R 6 and R 7 are linear or branched alkyl groups, and at least two of R 4 , R 5 , R 6 and R 7 are C6-C 20 alkyl groups] c) A pyridinium compound of formula C or a bipyridinium compound of formula D: R 9 -(C5H5N + )-R 8 X - (C), R 8 -( + NC5H5)-(C5H5N + )-R 8 X - (D) [Wherein, R 8 is an alkyl group, and R 9 is a substituted or unsubstituted linear or branched alkyl group or alkylene group], and d) A radical scavenger selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid comprises at least one molybdenum etching inhibitor selected from the group consisting of The removal composition removes molybdenum in a small amount from the surface of a microelectronic device containing molybdenum, as compared to an aqueous base composition.

[0009] In another embodiment, the present disclosure relates to a method for removing post-CMP residues from the surface of a microelectronic device containing a molybdenum material. This method includes contacting the surface of the microelectronic device with a removal composition and at least partially removing post-CMP residues from the surface of the microelectronic device. The removal composition includes an aqueous base composition having a pH greater than 10, which includes water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster. The removal composition further a) A quaternary ammonium compound of formula A: Ar-R-N + (R 1 )(R 2 )(R 3 )X - (A) [Wherein, Ar is a substituted or unsubstituted aryl group, and X -is a hydroxy ion, a halide ion, a sulfate ion or a methanesulfonic acid ion, and 1) R is a methylene group or an ethylene group, and R 1 , R 2 and R 3 are linear or branched alkyl groups, and R 1 , R 2 and R 3 at least one of which is a C4 - C 20 alkyl group, 2) R is a C3 - C 20 alkylene group, and R 1 , R 2 and R 3 are methyl groups or ethyl groups, or 3) R is a C1 - C 20 alkylene group, and R 1 , R 2 and R 3 are linear or branched alkyl groups, and R 1 , R 2 and R 3 at least one of which contains a glycol group], b) Quaternary ammonium compound of formula B: (R 4 )(R 5 )(R 6 )(R 7 )N + X - (B) [wherein, R 4 , R 5 , R 6 and R 7 are linear or branched alkyl groups, and R 4 , R 5 , R 6 and R 7 at least two of which are C6 - C 20 alkyl groups] c) Pyridinium compound of formula C or bipyridinium compound of formula D: R 9 -(C5H5N + )-R 8 X - (C), R8 -( + NC5H5)-(C5H5N + )-R 8 X - (D) [wherein, R 8 is an alkyl group, and R 9 is a substituted or unsubstituted linear or branched alkyl group or alkylene group], and d) a radical scavenger selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid and includes at least one molybdenum etching inhibitor selected from the group consisting of. The removal composition removes a smaller amount of molybdenum material from the surface of the microelectronic device than the aqueous base composition.

[0010] The present disclosure further relates to a method for suppressing the etching of molybdenum material from the surface of a microelectronic device. The method includes i) providing an aqueous base composition having a pH greater than 10, comprising water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster; ii) forming a removal composition by combining the aqueous base composition with at least one molybdenum etching inhibitor, wherein the molybdenum etching inhibitor is a) a quaternary ammonium compound of formula A: Ar-R-N + (R 1 )(R 2 )(R 3 )X - (A) [wherein, Ar is a substituted or unsubstituted aryl group, X - is a hydroxide ion, a halide ion, a sulfate ion or a methanesulfonate ion, and 1) R is a methylene group or an ethylene group, and R 1 , R 2 and R 3 are linear or branched alkyl groups, and R1 and R 2 and R 3 at least one of which is a C4-C 20 alkyl group, 2) R is a C3-C 20 alkylene group, and R 1 , R 2 and R 3 are a methyl group or an ethyl group, or 3) R is a C1-C 20 alkylene group, and R 1 , R 2 and R 3 are a linear or branched alkyl group, and R 1 , R 2 and R 3 at least one of which contains a glycol group], b) Quaternary ammonium compound of formula B: (R 4 )(R 5 )(R 6 )(R 7 )N + X - (B) [wherein R 4 , R 5 , R 6 and R 7 are a linear or branched alkyl group, and R 4 , R 5 , R 6 and R 7 at least two of which are C6-C 20 alkyl group] c) Pyridinium compound of formula C or bipyridinium compound of formula D: R 9 -(C5H5N + )-R 8 X - (C), R 8 -( + NC5H5)-(C5H5N + )-R 8 X - (D) [wherein R 8 is an alkyl group, and R 9is a substituted or unsubstituted linear or branched alkyl group or alkylene group, and d) a radical scavenger selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid selected from the group consisting of, forming, and iii) contacting the surface of the microelectronic device comprising the molybdenum material with the removal composition. The removal composition removes molybdenum from the surface of the microelectronic device in a lesser amount than an aqueous base composition.

DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure generally relates to an aqueous removal composition for removing post-CMP residues from the surface of a microelectronic device. The removal composition has a high pH and contains various specific molybdenum etching inhibitors, which surprisingly reduce the amount of molybdenum etching from the device surface even at a pH of 10 or higher compared to the same composition without a molybdenum etching composition.

[0012] As used herein, the term "post-CMP residue" corresponds to contaminants resulting from the use of a CMP slurry, such as particles containing abrasives and chemicals present in the slurry, reaction by-products of the polishing slurry, polishing pad particles, brush-off particles, structural particles of the equipment material, metals, organic residues, and any other material that is a by-product of the CMP process. Further, when various metal layers are removed during the CMP process, the post-CMP residue may further contain metal-containing particles.

[0013] Regarding the compositions of the present disclosure, when specific components of a composition are discussed in terms of weight percent ranges that include a zero lower limit, such components may or may not be present in various specific embodiments of the composition, and if such components are present, it will be understood that they may be present at low concentrations as low as 0.001 weight percent based on the total weight of the composition in which such components are used.

[0014] As used herein, the term "substantially absent" is defined as less than 2 weight percent, preferably less than 1 weight percent, more preferably less than 0.5 weight percent, and most preferably less than 0.1 weight percent. "Absent" is intended to correspond to less than 0.001 weight percent in view of environmental contamination. Thus, "absent" can refer to "not containing" a particular component. Further, as used herein, "about" is intended to correspond to ±5% of the stated value, for example ±2% or ±1% of that value.

[0015] As used herein, the term "microelectronic device" is not meant to be limiting in any way and includes any substrate that will ultimately become a microelectronic device or microelectronic assembly. For example, "microelectronic device" includes semiconductor substrates, flat panel displays, phase change memory devices, solar panels, and other products including solar cell devices, optoelectronics, and microelectromechanical systems (MEMS) manufactured for use in microelectronic integration, energy integration, or computer chip applications. A particularly preferred example of a microelectronic device is a 3D-NAND device. The device substrates from which CMP post-residues can be removed by the compositions described herein can be any of those known in the art, including substrates containing, for example, PETEOS, SiO2, thermal oxides, silicon nitride, silicon, and the like.

[0016] The device substrate may be polished with a CMP slurry containing abrasive particles such as silica and ceria, organic reagents, solvents, and other known components. Due to the strong interaction between the abrasive particles and the device surface, particularly due to hydrogen bonding and van der Waals forces at low or medium pH, and particle aggregation and reprecipitation at high pH, it has become increasingly difficult to clean the polished substrate to the required extent. Residues that are not removed often result in device defects.

[0017] Accordingly, the present disclosure relates to removal compositions and methods for removing post-CMP residues from the surface of microelectronic devices. The removal composition includes an aqueous base composition having a pH greater than 10, comprising water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster. The removal composition further includes at least one specific molybdenum etching inhibitor.

[0018] Accordingly, the removal composition described herein is a high-pH aqueous removal composition having a pH greater than 10. Preferably, the pH of the removal composition is from about 10 to about 14, such as from about 12 to about 14 (including a pH of 13 - 14). This aqueous composition having a high pH is generally expected to remove many types of post-CMP residues, but is also expected to remove various conductive metal layers such as molybdenum layers. It is known to be very difficult to achieve proper removal of post-CMP residues while suppressing molybdenum etching at high pH.

[0019] However, after extensive experimental investigations, the inventors have identified various classes of molybdenum etching inhibitors, and when these are combined with other additional components, surprisingly, it has been found that they reduce the etching of molybdenum but result in a high pH aqueous removal composition with a high post-CMP removal rate. The removal composition includes an aqueous (i.e., containing more than 50% water) base composition having a pH greater than 10, as described above. The aqueous base composition further includes at least one of an organic additive, at least one cleaning additive, at least one water-miscible organic solvent, and at least one pH adjuster. For example, the aqueous base composition can include one, two, three, or all four of these additional components. Preferably, the aqueous base composition includes each of these components. In addition to the aqueous base composition, the removal composition further includes at least one specific type of molybdenum etching inhibitor. Surprisingly, by including these specific classes of etching inhibitors, it has been found that the high pH removal composition has reduced molybdenum etching compared to an aqueous base composition of the same composition but without these inhibitors.

[0020] Accordingly, the removal composition of the present disclosure includes an aqueous base composition having a pH greater than 10. Preferably, the pH of the aqueous base composition is from about 10 to about 14, such as from about 12 to about 14 (including a pH of 13 - 14). The pH of the composition can be adjusted to achieve the desired pH by adding the desired amount of pH adjuster. The base composition is an aqueous composition containing more than 50% by weight (including more than 60% by weight or more than 70% by weight) water.

[0021] In one embodiment, the aqueous removal composition comprises at least one pH adjuster. Examples of suitable pH adjusters include bases such as alkali metal hydroxides, alkaline earth metal hydroxides, tetraalkylammonium hydroxides (such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide (TBAH)), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, tetraalkylphosphonium hydroxides (such as tetrabutylphosphonium (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrapropylphosphonium hydroxide), benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, N-propyltriphenylphosphonium hydroxide, and combinations thereof, but are not limited thereto. Preferably, the pH adjuster comprises choline hydroxide.

[0022] The compositions described herein can be ammonia or ammonium hydroxide and preferably are substantially free thereof. More preferably, the aqueous base composition is free of ammonia and ammonium hydroxide. These bases are effective in raising the pH to the desired level but present substantial health and environmental concerns and significantly increase the costs for handling and mitigation of these issues.

[0023] The pH adjuster may be present in any amount effective to provide and / or maintain a pH above 10. In particular, the aqueous base composition can comprise from about 0.1 wt% to about 40 wt% of the pH adjuster. Preferably, the amount of the pH adjuster is from about 1.0 wt% to about 30 wt%, more preferably from about 3 wt% to about 20 wt% (including from about 5 wt% to about 10 wt%).

[0024] The aqueous base composition may further contain at least one organic additive. As used herein, an organic additive can be any compound that can form a composite structure with individual atoms / molecules / materials. Suitable organic additives include complexing agents such as aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine (MEA), triethanolamine (TEA), 1-amino-2-propanol, 2-amino-1-butanol, isobutanolamine, triethylenediamine, 4-(2-hydroxyethyl)morpholine (HEM), ethylenediaminetetraacetic acid (EDTA), m-xylenediamine (MXDA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, alanine, arginine, asparagine, aspartic acid, cysteine, glutamic acid, glutamine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine, 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), aminotris(methylenephosphonic acid), bis(hexamethylene)triaminepentamethylenephosphonic acid, 1,4,7-triazacyclononane-N,N’,N’’-tris(methylenephosphonic acid (NOTP), hydroxyethyldiphosphonate, nitrilotris(methylene)phosphonic acid, 2-phosphono-butane-1,2,3,4-Tetracarboxylic acid, carboxyethylphosphonic acid, aminoethylphosphonic acid, glyphosate, ethylenediaminetetra(methylenephosphonic acid)phenylphosphonic acid, oxalic acid, succinic acid, maleic acid, malic acid, malonic acid, adipic acid, phthalic acid, lactic acid, citric acid, sodium citrate, potassium citrate, ammonium citrate, tricarballylic acid, trimethylolpropionic acid, tartaric acid, glucuronic acid, 2-carboxypyridine, disodium 4,5-dihydroxy-1,3-benzenedisulfonate, and combinations thereof, but not limited thereto. Preferably, the organic additive is selected from the group consisting of 1-amino-2-propanol and monoethanolamine.,

[0025] The organic additive may be present in any amount effective to improve the removal rate of the CMP post-residue. For example, when used, the aqueous base composition may contain from about 0.1 wt% to about 20 wt% of the organic additive. Preferably, the amount of the organic additive is from about 0.2 wt% to about 15 wt%, more preferably from about 0.3 wt% to about 10 wt% (including from 0.5 wt% to about 5 wt%).

[0026] The aqueous base composition may further comprise at least one cleaning additive that aids in removing post-CMP residues from the surface of the microelectronic device. Suitable examples of cleaning additives include, for example, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, dimethyl sulfoxide, sulfolane, poly(styrene sulfonic acid) or its salts, poly(vinyl pyrrolidone), poly(vinyl pyrrolidone) / vinyl acetate, poly(vinyl acetate), poly(vinyl alcohol), homopolymers, such as phosphonated polyethylene glycol oligomers, poly(acrylamide), poly(acrylic acid) (PAA) and its salts, such as poly(acrylic acid) ammonium salt, poly(methacrylic acid) and its salts, such as poly(methacrylic acid) ammonium salt, acrylic acid and methacrylic acid homopolymers and copolymers with, for example, acrylamidomethylpropanesulfonic acid and maleic acid, and their salts;Poly(2-acrylamido-2-methyl-1-propanesulfonic acid) and their copolymers, polydiallyldimethylammonium chloride, poly(dimethylaminoethyl methacrylate) and their copolymers, poly(trimethylaminoethyl methacrylate) salts and their copolymers, poly(hydroxyethyl) acrylate (and their copolymers), poly(hydroxyethyl) methacrylate (and their copolymers), maleic acid / vinyl ether copolymer, poly(ethylene glycol) (PEG), polypropylene glycol) (PPG), polyethylene glycol-co-polypropylene glycol, PPG-PEG-PPG block copolymer, PEG-PPG-PEG block copolymer, poly(styrenesulfonic acid), poly(vinylsulfonic acid), poly(vinylphosphonic acid), poly(vinylphosphoric acid), poly(ethyleneimine), poly(propyleneimine), polyallylamine, polyethylene oxide (PEO), hydroxyethyl cellulose, methylhydroxyethyl cellulose, hydroxypropyl cellulose, methylhydroxypropyl cellulose, xanthan gum, potassium alginate, pectin, carboxymethyl cellulose, glucosamine, poly(diallyldimethylammonium) chloride, PEGylated (i.e., polyethylene glycolated) methacrylate / acrylate copolymer, poly(2-methacryloxyethyltrimethylammonium chloride) and their copolymers, ethoxylated alcohol or phenol, ethoxylated fatty acid sugar, dodecylbenzenesulfonic acid, laurylsulfonic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, benzyldimethyldodecylammonium chloride, benzyldimethyldodecylammonium hydroxide, and trimethyldodecylammonium chloride, and combinations thereof. The above copolymers may be random copolymers or block copolymers. Preferably, the cleaning additive is selected from the group consisting of nonanoic acid, ethoxylated alcohol, poly(acrylic acid), diethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and dodecylbenzenesulfonic acid (DDBSA).;

[0027] When present, the amount of the cleaning additive in the aqueous base composition ranges from about 0.001% by weight to about 20% by weight based on the total weight of the aqueous base composition. For example, the cleaning additive may be present in an amount of from about 0.1% by weight to about 10% by weight (including an amount of from about 0.5% by weight to about 5% by weight) based on the total weight of the composition.

[0028] The aqueous base composition may further contain at least one water-miscible organic solvent. Suitable examples of water-miscible solvents include, for example, glycols, 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-1-propanol, 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, dimethyl sulfoxide, tetramethylene sulfone, diethyl ether, phenoxy-2-propanol, propiophenone, ethyl lactate, ethyl acetate, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol, 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, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, 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, glycerol carbonate, N - formylmorpholine, triethyl phosphate, glycerol, sorbitol, glycol ether, urea, dicyandiamide, and combinations thereof. Preferably, the water - miscible solvent is selected from the group consisting of glycerol and sorbitol.,

[0029] When present, the amount of the water - miscible solvent in the aqueous base composition is in the range of about 0.1 wt% to about 20 wt% based on the total weight of the aqueous base composition. For example, the cleaning additive may be present in an amount of about 0.2 wt% to about 15 wt% (including amounts of about 0.5 wt% to about 10 wt%, about 1.0 wt% to about 10 wt%, or about 5.0 wt% to about 10 wt%) based on the total weight of the composition.,

[0030] Accordingly, the aqueous base composition includes water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster, and has a pH greater than 10. This composition can be used as a base for forming a removal composition for removing post-CMP residues from the surface of a microelectronic device by including at least one molybdenum etching inhibitor. The etching inhibitor and the aqueous base composition can be combined by any method known in the art to form the removal composition. For example, the inhibitor may be combined with a pre-formed aqueous base composition or may be included when the aqueous base composition is being formed.

[0031] More specifically, the removal composition includes an aqueous base composition and at least one molybdenum etching inhibitor. The inhibitor is a quaternary ammonium compound having the formula Ar-R-N + (R 1 )(R 2 )(R 3 )X - (referred to herein as formula A), a quaternary ammonium compound having the formula (R 4 )(R 5 )(R 6 )(R 7 )N + X - (referred to herein as formula B), a pyridinium compound having the formula R 9 -(C5H5N + )-R 8 X - (referred to herein as formula C), or a compound having the formula R 8 -( + NC5H5)-(C5H5N + )-R 8 X -A bipyridinium compound having (referred to herein as formula D), and a radical scavenger selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid. By including at least one of these selected types of etching inhibitors, the removal composition surprisingly removes molybdenum in a smaller amount from the surface of a microelectronic device containing molybdenum than an aqueous base composition, without significantly affecting its ability to remove CMP residues from the device surface.

[0032] Therefore, the removal composition comprises a quaternary ammonium compound of formula A: Ar-R-N + (R 1 )(R 2 )(R 3 )X - (A) . In this formula, Ar is a substituted or unsubstituted aryl group, such as a phenyl group, and X - is a counter ion, such as a hydroxy ion, a halide ion, a sulfate ion, or a methanesulfonate ion. As a specific embodiment of the quaternary ammonium compound of formula A, R is a methylene group or an ethylene group, and R 1 , R 2 and R 3 are linear or branched alkyl groups, and at least one of R 1 , R 2 and R 3 is a C4-C 20 alkyl group. For example, R 1 , R 2 and R 3 may be C 10 -C 20 alkyl groups. As another specific embodiment of the quaternary ammonium compound of formula A, R is a C3-C 20 alkylene group, and R 1 , R 2 and R 3 are methyl groups or ethyl groups. For example, R is C4-C10 It may be an alkylene group. As yet another specific embodiment, R is C1-C 20 is an alkylene group. R 1 , R 2 and R 3 are linear or branched alkyl groups, and at least one of R 1 , R 2 and R 3 contains a glycol group. For example, the glycol group may be an ethylene glycol group. Suitable specific examples of the quaternary ammonium compound of formula A include benzyl dodecyl dimethyl ammonium salt, benzyl tetradecyl dimethyl ammonium salt, phenylpropyl triethyl ammonium salt, or benzethonium salt.

[0033] Furthermore, or alternatively, the removal composition comprises a quaternary ammonium compound of formula B: (R 4 )(R 5 )(R 6 )(R 7 )N + X - (B) . In this formula, R 4 , R 5 , R 6 and R 7 are linear or branched alkyl groups, and at least two of R 4 , R 5 , R 6 and R 7 are C6-C 20 alkyl groups. In a specific embodiment, at least three of R 4 , R 5 , R 6 and R 7 are C6-C 20 alkyl groups. Suitable specific examples of the quaternary ammonium compound of formula B include tetrapropyl ammonium salt, tetrabutyl ammonium salt, or methyltrioctyl ammonium salt.

[0034] Furthermore, or alternatively, the removal composition comprises a quaternary ammonium compound of formula C: R 9 -(C5H5N + )-R 8 X - (C) pyridinium compound of or formula D: R 8 -( + NC5H5)-(C5H5N + )-R 8 X - (D) bipyridinium compound of is included. In these formulas, R 8 is an alkyl group, and R 9 is a substituted or unsubstituted linear or branched alkyl group or alkylene group. Suitable specific examples of the pyridinium compound of formula C include N-ethyl-4-(3-phenylpropyl)pyridine, and suitable specific examples of the bipyridinium compound of formula D include ethyl viologen dihalide salt.

[0035] Furthermore, or alternatively, the removal composition includes a radical scavenger selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid. Suitable specific examples of the radical scavenger include 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-TEMPO, 4-phosphonoxy-TEMPO, 3-methyl-1-phenyl-2-pyrazolin-5-one, trans-4-hydroxycinnamic acid, guaiacol, t-butyl alcohol, or glucono-1,5-lactone.

[0036] When present, the amount of the molybdenum etching inhibitor in the removal composition is in the range of about 0.05 wt% to about 10 wt% based on the total weight of the removal composition. For example, the molybdenum etching inhibitor additive may be present in an amount of about 0.1 wt% to about 8.0 wt% (including an amount of about 0.2 wt% to about 5.0 wt%) based on the total weight of the composition.

Example

[0037] The aqueous removal composition of the present disclosure was prepared by combining various aqueous base compositions with a specific molybdenum etching inhibitor, as shown in Table 1 below. The removal compositions of the comparative examples were prepared in the same manner and included in this table. Specific information regarding the aqueous base compositions is shown in Tables 2A - 2C, and the inhibitors used are shown in Table 3. The molybdenum etching rate was determined by exposing a coupon having a molybdenum layer to a specific composition at a temperature of 30°C.

[0038] As the results show, for the compositions containing the inhibitor described in the present disclosure, a significant suppression of molybdenum etching was found without significantly reducing the removal of post - CMP residues. Compounds having a similar structure but not meeting the specific requirements outlined herein (i.e., comparative compounds) did not achieve suppression of molybdenum etching. TIFF2025518848000001.tif143170TIFF2025518848000002.tif39170TIFF2025518848000003.tif39170TIFF2025518848000004.tif48170TIFF2025518848000005.tif231170TIFF2025518848000006.tif243170TIFF2025518848000007.tif239170TIFF2025518848000008.tif81170

Claims

1. A removal composition for removing post-CMP residues from the surface of a microelectronic device, the removal composition comprising water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster, and comprising an aqueous base composition having a pH greater than 10, The removal composition further comprises, a) a quaternary ammonium compound of formula A: Ar-R-N ＋ (R １ )(R ２ )(R ３ )X － (A) [wherein Ar is a substituted or unsubstituted aryl group, X － is a hydroxy ion, a halide ion, a sulfate ion or a methanesulfonate ion, and 1) R is a methylene group or an ethylene group, and R １ , R ２ , and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ , and R ３ is a C ４ -C ２０ alkyl group, 2) R is a C ３ -C ２０ alkylene group, and R １ , R ２ , and R ３ are methyl groups or ethyl groups, or 3) R is a C １ -C ２０ alkylene group, and R １ , R ２ , and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ and R ３ contains a glycol group], b) a quaternary ammonium compound of formula B: (R ４ )(R ５ )(R ６ )(R ７ )N ＋ X － (B) [wherein, R ４ , R ５ , R ６ and R ７ are linear or branched alkyl groups, and at least two of R ４ , R ５ , R ６ and R ７ are C ６ -C ２０ alkyl groups] c) A pyridinium compound of formula C or a bipyridinium compound of formula D: R ９ -(C ５ H ５ N ＋ )-R ８ X － (C), R ８ -( ＋ NC ５ H ５ )-(C ５ H ５ N ＋ )-R ８ X － (D) [wherein, R ８ is an alkyl group, and R ９ is a substituted or unsubstituted linear or branched alkyl group or alkylene group], and d) At least one molybdenum etching inhibitor selected from the group consisting of radical scavengers selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid, The removal composition is a removal composition for removing the CMP post-residue from the surface of a microelectronic device, which removes molybdenum in a smaller amount from the surface of the microelectronic device containing molybdenum than the aqueous base composition.

2. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is a methylene group or an ethylene group, R １ , R ２ and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ , and R ３ is a C ４ -C ２０ alkyl group], the removal composition according to claim 1.

3. At least one of R １ , R ２ , and R ３ is a C １０ -C ２０ alkyl group, the removal composition according to claim 2.

4. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is a C ３ -C ２０ alkylene group, and R １ , R ２ and R ３ are methyl groups or ethyl groups], the removal composition according to claim 1.

5. R is a C ４ -C １０ alkylene group, the removal composition according to claim 4.

6. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is a C １ -C ２０ alkylene group, and R １ , R ２ and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ and R ３ contains a glycol group], the removal composition according to claim 1.

7. The glycol group is an ethylene glycol group, the removal composition according to claim 6.

8. The quaternary ammonium compound of formula A is a benzyl dodecyl dimethyl ammonium salt, benzyl tetradecyl dimethyl ammonium salt, phenylpropyl triethyl ammonium salt, or benzethonium salt, and the removal composition according to claim 1.

9. The molybdenum etching inhibitor is a quaternary ammonium compound of formula B, and the removal composition according to claim 1.

10. R ４ 、R ５ 、R ６ 、and R ７ Among them, at least three are C ６ ~C ２０ alkyl groups, and the removal composition according to claim 9.

11. The molybdenum etching inhibitor is a tetrapropyl ammonium salt, tetrabutyl ammonium salt, or methyltrioctyl ammonium salt, and the removal composition according to claim 9.

12. The molybdenum etching inhibitor is a pyridinium compound of formula C, and the removal composition according to claim 1.

13. The molybdenum etching inhibitor is N-ethyl-4-(3-phenylpropyl)pyridine, and the removal composition according to claim 12.

14. The molybdenum etching inhibitor is a bipyridinium compound of formula D, and the removal composition according to claim 1.

15. The molybdenum etching inhibitor is an ethyl viologen dihalide salt, and the removal composition according to claim 14.

16. The removal composition according to claim 1, wherein the molybdenum etching inhibitor is a radical scavenger selected from the group consisting of 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-TEMPO, 3-methyl-1-phenyl-2-pyrazolin-5-one, trans-4-hydroxycinnamic acid, guaiacol, t-butyl alcohol, or glucono-1,5-lactone.

17. The removal composition according to claim 1, wherein the removal composition has a pH of from about 10 to about 14.

18. The removal composition according to claim 1, wherein the removal composition has a pH of from about 11 to about 13.

5.

19. A method for removing post-CMP residues from the surface of a microelectronic device containing a molybdenum material, comprising: i) contacting the surface of the microelectronic device with a removal composition comprising water and an aqueous base composition having a pH greater than 10 and comprising at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster; The removal composition further comprises: a) a quaternary ammonium compound of formula A: Ar-R-N ＋ (R １ (R ２ (R ３ )X － (A) [wherein Ar is a substituted or unsubstituted aryl group, X － is a hydroxy ion, a halide ion, a sulfate ion or a methanesulfonate ion, and 1) R is a methylene group or an ethylene group, and R １ , R ２ , and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ , and R ３ is a C ４ -C ２０ alkyl group. 2) R is C ３ ~C ２０ is an alkylene group, and R １ , R ２ , and R ３ are a methyl group or an ethyl group, or 3) R is C １ ~C ２０ is an alkylene group, and R １ , R ２ , and R ３ are a linear or branched alkyl group, and R １ , R ２ , and R ３ of which at least one contains a glycol group], b) Quaternary ammonium compound of formula B: (R ４ )(R ５ )(R ６ )(R ７ )N ＋ X － (B) [In the formula, R ４ , R ５ , R ６ and R ７ are a linear or branched alkyl group, and R ４ , R ５ , R ６ and R ７ of which at least two are C ６ ~C ２０ alkyl group].[[]] c) Pyridinium compound of formula C or bipyridinium compound of formula D: R ９ -(C ５ H ５ N ＋ )-R ８ X － (C), R ８ -( ＋ NC ５ H ５ )-(C ５ H ５ N ＋ )-R ８ X － (D) [In the formula, R ８is an alkyl group, R ９ is a substituted or unsubstituted linear or branched alkyl group or alkylene group], and d) at least one molybdenum etching inhibitor selected from the group consisting of radical scavengers selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid including contacting; ii) at least partially removing the CMP residue from the surface of the microelectronic device and The removal composition removes a smaller amount of molybdenum material from the surface of the microelectronic device than the aqueous base composition.

20. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is a methylene group or an ethylene group, and R １ , R ２ and R ３ are linear or branched alkyl groups, and R １ , R ２ , and R ３ at least one of which is a C ４ to C ２０ alkyl group]. The method according to claim 19.

21. R １ , R ２ , and R ３ at least one of which is a C １０ to C ２０ alkyl group. The method according to claim 20.

22. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is a C ３ to C ２０ alkylene group, and R １ , R ２ , and R ３ are methyl groups or ethyl groups]. The method according to claim 19.

23. R is C ４ - C １０ an alkylene group, the method according to claim 22.

24. The molybdenum etching inhibitor is a quaternary ammonium compound of formula A [wherein R is C １ - C ２０ an alkylene group, R １ , R ２ , and R ３ are linear or branched alkyl groups, and at least one of R １ , R ２ , and R ３ contains a glycol group], the method according to claim 19.

25. The glycol group is an ethylene glycol group, the method according to claim 24.

26. The quaternary ammonium compound of formula A is benzyl dodecyl dimethyl ammonium salt, benzyl tetradecyl dimethyl ammonium salt, phenylpropyl triethyl ammonium salt, or benzethonium salt, the method according to claim 19.

27. The molybdenum etching inhibitor is a quaternary ammonium compound of formula B, the method according to claim 19.

28. R ４ , R ５ , R ６ , and R ７ Among them, at least three are C ６ - C ２０ an alkyl group, the method according to claim 27.

29. The molybdenum etching inhibitor is tetrapropyl ammonium salt, tetrabutyl ammonium salt, or methyltrioctyl ammonium salt, the method according to claim 27.

30. The molybdenum etching inhibitor is a pyridinium compound of formula C, the method according to claim 19.

31. The method according to claim 30, wherein the molybdenum etching inhibitor is N-ethyl-4-(3-phenylpropyl)pyridine.

32. The method according to claim 19, wherein the molybdenum etching inhibitor is a bipyridinium compound of formula D.

33. The method according to claim 32, wherein the molybdenum etching inhibitor is an ethyl viologen dihalide salt.

34. The method according to claim 19, wherein the molybdenum etching inhibitor is a radical scavenger selected from the group consisting of 2,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 4-hydroxy-TEMPO, 3-methyl-1-phenyl-2-pyrazolin-5-one, trans-4-hydroxycinnamic acid, guaiacol, t-butyl alcohol, or glucono-1,5-lactone.

35. The method according to claim 19, wherein the removal composition has a pH of from about 10 to about 14.

36. The method according to claim 19, wherein the removal composition has a pH of from about 11 to about 13.

5.

37. A method for suppressing the etching of a molybdenum material from the surface of a microelectronic device, comprising: i) providing an aqueous base composition having a pH greater than 10, comprising water and at least one of an organic additive, a cleaning additive, a water-miscible organic solvent, and a pH adjuster; ii) combining the aqueous base composition with at least one molybdenum etching inhibitor to form a removal composition, wherein the molybdenum etching inhibitor is: a) a quaternary ammonium compound of formula A: Ar - R - N ＋ (R １ )(R ２ )(R ３ )X － (A) [wherein, Ar is a substituted or unsubstituted aryl group, and X － is a hydroxy ion, a halide ion, a sulfate ion or a methanesulfonate ion, and 1) R is a methylene group or an ethylene group, and R １ , R ２ , and R ３ are linear or branched alkyl groups, and R １ , R ２ , and R ３ at least one of which is a C ４ - C ２０ alkyl group], 2) R is a C ３ - C ２０ alkylene group, and R １ , R ２ and R ３ are methyl groups or ethyl groups, or 3) R is a C １ - C ２０ alkylene group, and R １ , R ２ , and R ３ are linear or branched alkyl groups, and R １ , R ２ , and R ３ at least one of which contains a glycol group], b) a quaternary ammonium compound of formula B: (R ４ )(R ５ )(R ６ )(R ７ )N ＋ X － (B) [wherein, R ４ , R ５ , R ６ and R ７ are linear or branched alkyl groups, and R ４ , R ５ , R ６ , and R ７ at least two of which are C ６ - C ２０ alkyl groups]], c) A pyridinium compound of formula C or a bipyridinium compound of formula D: R ９ -(C ５ H ５ N ＋ )-R ８ X － (C), R ８ -( ＋ NC ５ H ５ )(C ５ H ５ N ＋ )-R ８ X － (D) [wherein, R ８ is an alkyl group, and R ９ is a substituted or unsubstituted linear or branched alkyl group or alkylene group], and d) Forming, selected from the group consisting of radical scavengers selected from the group consisting of hydroxybenzene, pyrazolinone, a compound having an aminoxyl radical, gluconolactone, a tertiary alkyl alcohol, and ascorbic acid, and iii) Contacting the surface of a microelectronic device containing a molybdenum material with a removal composition, wherein the removal composition removes less molybdenum from the surface of the microelectronic device than an aqueous base composition, contacting A method comprising.

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