Chemical mechanical grinding formulations and usage methods

Abstract

This application relates to post-chemical mechanical polishing (CMP) formulations and methods of use. The present invention provides a cleaning composition and method for cleaning CMP residues and contaminants from microelectronic devices having such residues and contaminants thereon. The composition achieves efficient cleaning of CMP residues and contaminants from the surface of the microelectronic device without damaging low-k dielectric materials or copper interconnect materials. Furthermore, the cleaning composition is compatible with ruthenium-containing materials.

Description

[0001] This application is a divisional application of the invention patent application filed on April 11, 2018, with application number 201880024133.9 and invention title "Chemical Mechanical Grinding Formulation and Method of Use". Technical Field

[0002] The present invention generally relates to a composition for cleaning residues and / or contaminants from microelectronic devices having residues and / or contaminants thereon, and specifically includes residues and / or contaminants from at least one of copper-containing materials, tantalum-containing materials, cobalt-containing materials and ruthenium-containing materials. Background Technology

[0003] Microelectronic device wafers are used to form integrated circuits. Microelectronic device wafers contain a substrate, such as silicon, in which regions are patterned for depositing different materials with insulating, conductive, or semiconductive properties.

[0004] To achieve proper patterning, excess material used to form layers on the substrate must be removed. Furthermore, to fabricate functional and reliable circuits, it is important to prepare a flat or planar surface for the microelectronic wafer before subsequent processing. Therefore, it is necessary to planarize and / or grind certain surfaces of the microelectronic device wafer.

[0005] Chemical mechanical polishing or planarization (“CMP”) is a process for removing material from the surface of a microelectronic device wafer, and planarizing and polishing the surface by coupling physical processes, such as abrasion, with chemical processes, such as oxidation or chelation. In its most basic form, CMP involves applying a slurry (e.g., a solution of abrasives and active chemicals) to an abrasive pad on the surface of a microelectronic device wafer to achieve a removal, planarization, and polishing process. Typically, removal or polishing processes consisting of purely physical or purely chemical actions are not required; rather, both are combined synergistically to achieve rapid and uniform removal. In the fabrication of integrated circuits, CMP slurries should also be able to preferentially remove films comprising composite layers of metals and other materials, thereby producing highly planar surfaces for subsequent photolithography or patterning, etching, and thin-film processing.

[0006] In copper damascene processes, commonly used for metallizing circuits in microelectronic device fabrication, layers that must be removed and planarized include a copper layer approximately 1–1.5 μm thick and a copper seed layer approximately 0.05–0.15 μm thick. These copper layers are separated from the dielectric surface by a barrier material layer, typically approximately 50–300 Å thick, which prevents copper from diffusing into the oxide dielectric. A key to achieving good uniformity on the wafer surface after polishing is the use of a CMP slurry with the correct removal selectivity for each material.

[0007] Tantalum and tantalum nitride are currently used as barrier layer materials to prevent device contamination caused by copper diffusion through the dielectric layer. However, due to tantalum's high resistivity, especially in high aspect ratio features, it is difficult to effectively deposit copper onto the barrier layer. Therefore, a copper seed layer must be initially deposited on the barrier layer. As circuit feature sizes decrease to 65 nm, 45 nm, and 32 nm scales, controlling the precise thickness of the seed layer to prevent trench top protrusions and void formation becomes extremely difficult, especially for 32 nm technology nodes and beyond.

[0008] The aforementioned process operations involving wafer substrate surface preparation, deposition, electroplating, etching, and chemical mechanical polishing all require cleaning operations to ensure that the microelectronic device product is free of residues and contaminants that would otherwise adversely affect the product's functionality or even render it unusable for its intended function. Typically, these contaminant particles are smaller than 0.3 μm. Following CMP processes, these residues and contaminants include CMP slurry components, particles from the removed layers, and corrosion inhibitor compounds such as benzotriazole (BTA). If not removed, these residues can lead to damage to copper wires or severe roughening of copper metallides, resulting in poor adhesion of post-CMP layers to the device substrate. Severe roughening of copper metallides is particularly difficult to address because excessively rough copper can lead to poor electrical performance of the microelectronic device.

[0009] There is a continuing need in the field for compositions and methods for effectively removing residues and contaminants from substrates, including substrates containing barrier materials other than tantalum and tantalum nitride. The compositions and methods should eliminate particles and other defects on copper without corroding or otherwise damaging the copper. Summary of the Invention

[0010] This invention generally relates to a composition and method for cleaning residues and / or contaminants from microelectronic devices having residues and contaminants thereon. The residues may include post-CMP, post-etching, and / or post-ashing residues. The composition and method are particularly advantageous for cleaning microelectronic surfaces comprising copper, low-k dielectric materials, and barrier materials comprising at least one of tantalum-containing, cobalt-containing, and ruthenium-containing materials.

[0011] In one aspect, a cleaning composition is described, the cleaning composition comprising at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor.

[0012] In another aspect, a method for removing residues and contaminants from a microelectronic device having residues and contaminants thereon, the method comprising contacting the microelectronic device with a cleaning composition for a sufficient time to at least partially clean the residues and contaminants from the microelectronic device, wherein the cleaning composition is compatible with copper, low-k dielectric materials and barrier materials, wherein the barrier material includes at least one of tantalum-containing materials, cobalt-containing materials and ruthenium-containing materials, and wherein the cleaning composition includes at least one organic amine, water, at least one pH adjuster, at least one organic additive and at least one metal corrosion inhibitor.

[0013] Other aspects, features and advantages will become more fully apparent from the following disclosure and the appended claims. Detailed Implementation

[0014] This invention generally relates to compositions suitable for removing materials from microelectronic devices having residues and contaminants thereon. The compositions are particularly suitable for removing residues after CMP, etching, or ashing.

[0015] For ease of reference, "microelectronic device" refers to semiconductor substrates, flat panel displays, phase-change memory devices, solar panels, and other products, including solar substrates, photovoltaic devices, and microelectromechanical systems (MEMS), manufactured for use in microelectronic, integrated circuit, or computer chip applications. Solar substrates include (but are not limited to) silicon, amorphous silicon, polycrystalline silicon, monocrystalline silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. It should be understood that the term "microelectronic device" is not intended to limit or include in any way the substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0016] As used herein, “residue” refers to particles generated during the fabrication of microelectronic devices that include (but are not limited to) plasma etching, ashing, chemical mechanical polishing, wet etching, and combinations thereof.

[0017] As used herein, “contaminant” refers to chemicals present in CMP slurries, reaction byproduct residues in grinding slurries, chemicals present in wet etching compositions, reaction byproducts of wet etching compositions, and any other material that is a byproduct of CMP processes, wet etching, plasma etching, or plasma ashing processes. Common contaminants include benzotriazole, which is typically present in CMP slurries.

[0018] As used herein, “CMP post-residue” refers to particles from the grinding slurry (e.g., silica-containing particles), chemicals present in the slurry, reaction byproducts of the grinding slurry, carbon-rich particles, grinding pad particles, brush-removed particles, equipment materials used to build particles, metals, metal oxides, organic residues, barrier layer residues, and any other materials that are byproducts of the CMP process. As defined herein, “metals” typically ground include copper, aluminum, and tungsten.

[0019] As defined herein, “low-k dielectric material” refers to any material used as a dielectric material in a layered microelectronic device, wherein the dielectric constant of the material is less than about 3.5. Preferably, low-k dielectric materials comprise low-polarity materials, such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicon glasses (OSG), TEOS, fluorinated silicate glasses (FSG), silicon dioxide, and carbon-doped oxide (CDO) glasses. It should be understood that low-k dielectric materials can have different densities and different porosities.

[0020] As defined herein, "complexing agent" includes those compounds that are understood by those skilled in the art to be complexing agents, chelating agents, and / or sequestering agents. A complexing agent chemically binds or physically clamps said metal atoms and / or metal ions to be removed using the composition described herein.

[0021] As defined herein, the term "barrier material" refers to any material used in the art to seal metal wires (e.g., copper interconnects) to minimize the diffusion of said metal (e.g., copper) into the dielectric material. Preferred barrier layer materials include tantalum, titanium, ruthenium, hafnium, tungsten, cobalt, and nitrides and silicides of any of the aforementioned metals.

[0022] As defined herein, “post-etching residue” refers to the material retained after a vapor phase plasma etching process (e.g., BEOL bimetallic damascene process) or a wet etching process. Post-etching residue can be organic, organometallic, organosilicon, or essentially inorganic, such as silica-containing materials, carbon-based organic materials, and etching gas residues such as oxygen and fluorine.

[0023] As defined herein, “ash residue” as used herein refers to the material retained after oxidative or reduction plasma ashing used to remove hardened photoresist and / or bottom antireflective coating (BARC) material. Ash residue may be organic, organometallic, organosilicon, or essentially inorganic.

[0024] "Substantially free of" is defined herein as less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and most preferably less than 0.1 wt.%. In one embodiment, "substantially free of" corresponds to zero percent.

[0025] As defined herein, “ruthenium-containing materials” and “ruthenium species” include (but are not limited to) pure ruthenium, ruthenium nitrides (including ruthenium nitrides which include additional elements such as Si, Ta, or Li), ruthenium oxides (including ruthenium oxides which include hydroxides), and ruthenium alloys. Those skilled in the art will understand that the chemical formulas of various ruthenium oxides and ruthenium nitrides can vary based on the oxidation state of the ruthenium ion, with common oxidation states of ruthenium being 0, +2, +3, +4, +6, +7, +8, or -2.

[0026] As defined herein, “tantalum-containing materials” and “tantalum species” include (but are not limited to) pure tantalum, tantalum nitrides (including tantalum nitrides which include additional elements such as Si), tantalum oxides (including tantalum oxides which include hydroxides), tantalum aluminum compounds, and tantalum alloys. Those skilled in the art will understand that the chemical formulas of various tantalum oxides and tantalum nitrides can vary based on the oxidation state of the tantalum ion, with common oxidation states of tantalum being -1, -3, +1, +2, +3, +4, and +5.

[0027] As defined herein, “cobalt-containing materials” and “cobalt species” include (but are not limited to) pure cobalt, cobalt oxides, cobalt hydroxides, cobalt nitrides (including cobalt nitrides which may include additional elements such as Ta or Ti), CoW, CoP, CoSi, and cobalt silicide. Those skilled in the art will understand that the chemical formulas of various cobalt oxides and cobalt nitrides can vary based on the oxidation state of the cobalt ion, with common oxidation states of cobalt being -3, -1, +1, +2, +3, +4, and +5.

[0028] As defined herein, “ruthenium-containing materials” and “ruthenium species” include (but are not limited to) pure ruthenium, ruthenium nitrides (including ruthenium nitrides which include additional elements such as Si, Ta, or Li), ruthenium oxides (including ruthenium oxides which include hydroxides), and ruthenium alloys. Those skilled in the art will understand that the chemical formulas of various ruthenium oxides and ruthenium nitrides can vary based on the oxidation state of the ruthenium ion, with common oxidation states of ruthenium being 0, +2, +3, +4, +6, +7, +8, or -2.

[0029] As used in this article, “about” is intended to correspond to ±5% of the stated value.

[0030] As defined herein, “reaction products or degradation products” include (but are not limited to) products or byproducts that form as products of surface catalysis, oxidation, reduction, reaction with constitutive components, or otherwise polymerization; products or byproducts that form as products of changes or transformations in which a substance or material (e.g., a molecule, compound, etc.) is combined with other substances or materials, interchanges components with other substances or materials, decomposes, rearranges, or otherwise chemically and / or physically alters; and intermediates or byproducts of any of the foregoing, or any combination of the foregoing reactions, changes, and / or transformations. It should be understood that reactants or degradation products may have a larger or smaller molar mass than the original reactants.

[0031] "Oxidizing agent" is well known in the chemical field as a species that can oxidize another species while being reduced itself. For the purposes of this application, oxidizing agents may include (but are not limited to) ozone, nitric acid, bubbled air, cyclohexanesulfonic acid, hydrogen peroxide, FeCl3, potassium persulfate, perborate, perchlorate, periodate, persulfate, permanganate, chlorite, chlorate, iodate, hypochlorite, nitrate, peroxymonosulfate, peroxymonosulfate, ferric nitrate, amine-N-oxide, urea peroxide, peracetic acid, periodic acid, potassium dichromate, 2-nitrophenol, 1,4-benzoquinone, peroxybenzoic acid, peroxyphthalate, vanadium oxide, ammonium metavanadate, ammonium tungstate, sulfuric acid, and combinations thereof.

[0032] "Zetzolium-containing corrosion inhibitors" or "azole-containing passivators" include triazoles and their derivatives, benzotriazoles and their derivatives, toluenetriazoles, thiazoles and their derivatives, tetrazoliums and their derivatives, imidazoles and their derivatives, and azines and their derivatives.

[0033] As used herein, "fluorine-containing compound" refers to a compound containing a fluoride ion (F) bonded to another atomic ion. - ) salts or acid compounds.

[0034] As used herein, the “suitability” of cleaning residues and contaminants from microelectronic devices having such residues and contaminants corresponds to at least partial removal of the residues / contaminants from the microelectronic device. The effectiveness of cleaning is assessed by the reduction of the target on the microelectronic device. For example, atomic force microscopy can be used for pre-cleaning and post-cleaning analyses. Particles on the sample can be registered as pixel ranges. Histograms (e.g., Sigma Scan Pro) can be applied to filter pixels of a certain intensity (e.g., 231-235) and the number of counted particles. Particle reduction can be calculated using the following formula:

[0035]

[0036] It is worth noting that the method for determining cleaning effectiveness is provided for illustrative purposes only and is not intended to limit the scope thereof. Alternatively, cleaning effectiveness can be considered as the percentage of the total surface area covered by particulate material. For example, AFM can be programmed to perform a z-plane scan to identify areas of surface morphology of interest above a certain height threshold, and then calculate the total surface area covered by said areas of interest. Those skilled in the art will readily understand that the smaller the area covered by said areas of interest after cleaning, the more effective the removal composition. Preferably, using the compositions described herein, at least 75% of residues / contaminants are removed from the microelectronic device, more preferably at least 90%, even more preferably at least 95%, and most preferably at least 99%.

[0037] As described more fully below, the compositions described herein can be implemented in a wide variety of specific formulations.

[0038] In all these compositions, the reference weight percentage range (including the lower limit of zero) refers to a particular component of the composition. It should be understood that these components may or may not be present in various specific embodiments of the composition, and in examples where these components are present, they may be present at a concentration as low as 0.001 weight percentage based on the total weight of the composition in which these components are used.

[0039] In one aspect, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor. In one embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least two pH adjusters, at least one organic additive, and at least one metal corrosion inhibitor. In another embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least one pH adjuster, at least two organic additives, and at least one metal corrosion inhibitor. In yet another embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least two pH adjusters, at least two organic additives, and at least one metal corrosion inhibitor. In yet another embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least two pH adjusters, at least one organic additive, and at least two metal corrosion inhibitors. In yet another embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least one pH adjuster, at least two organic additives, and at least two metal corrosion inhibitors. In yet another embodiment, the cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least two pH adjusters, at least two organic additives, and at least two metal corrosion inhibitors. Any of the embodiments may additionally contain at least one reducing agent, at least one buffer, or both at least one reducing agent and at least one buffer. Furthermore, any of the embodiments disclosed herein may additionally contain at least one surfactant. Advantageously, the cleaning composition enhances the removal of contaminants such as benzotriazole while simultaneously reducing the corrosion rate of exposed copper and the amount of residues retained on the exposed copper (e.g., post-CMP residues, including post-CMP residues comprising a barrier layer material comprising at least one of tantalum, cobalt, and ruthenium species).

[0040] Before removing residual material from the microelectronic device, the cleaning composition of the first aspect may be substantially free of or contain no at least one oxidant; fluorine source; abrasive; tetramethylammonium hydroxide; azole corrosion inhibitor; gallic acid; sulfonium compound; aminooxime compound; and combinations thereof. Furthermore, the cleaning composition should not cure to form a polymeric solid, such as photoresist. Although it is contemplated that the formulation may contain at least one surfactant, it is also contemplated that the formulation is substantially free of surfactants, as will be readily understood by those skilled in the art. Furthermore, by total weight of the composition, at least one organic additive is present in the cleaning composition in an amount of less than 20 wt%, preferably less than 10 wt%, and more preferably less than 5 wt%, and at least one pH adjuster preferably comprises an alkali metal hydroxide, such as KOH.

[0041] In a preferred embodiment, the cleaning composition of the first aspect comprises, consists of, or is primarily composed of: at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably about 5 to about 50, more preferably about 10 to about 25, and most preferably about 12 to about 20; a pH adjuster / metal corrosion inhibitor ranging from about 0.1 to about 50, preferably about 1 to about 30, more preferably about 2 to about 20, and most preferably about 4 to about 10; and an organic additive / metal corrosion inhibitor ranging from about 0.01 to about 50, preferably about 0.1 to about 25, more preferably about 1 to about 15, and most preferably about 2 to about 10. As disclosed herein and as understood by those skilled in the art, the amount of pH adjuster added depends on the desired pH. The amount of water in the cleaning composition is at least 80 wt%, preferably at least 85 wt%, and more preferably at least 90 wt%, based on the total weight of the composition. The cleaning composition may additionally include at least one reducing agent, at least one buffer, or both at least one reducing agent and at least one buffer.

[0042] Illustrative organic amines applicable to specific compositions include those having the general formula NR. 1 R 2 R 3 Species, of which R 1 R 2 and R 3 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), straight-chain or branched C1-C6 alcohols (e.g., methanol, ethanol, propanol, butanol, pentanol, and hexanol), and having the formula R. 4 -OR 5 Straight-chain or branched-chain ethers, wherein R 4and R 5 These can be the same as or different from each other and are selected from the group consisting of C1-C6 alkyl groups as defined above. When an amine contains an ether component, it can be considered an alkoxyamine. Other organic amines are conceived to include dicyandiamide (C2N3). - ), and its salts and analogues. Most preferably, R 1 R 2 and R 3 At least one of them is a straight-chain or branched-chain C1-C6 alcohol. Examples include (but are not limited to): alkanolamines, such as aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, aminoethoxyethoxyethanol, butoxypropylamine, methoxypropylamine, butoxyisopropylamine, 2-ethylhexylisopropoxyamine, ethanolpropylamine, ethylethanolamine, N-hydroxyethylmorpholine, aminopropyl diethanolamine, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, diisopropylamine, aminomethylpropylene glycol, N,N-dimethylaminomethylpropylene glycol, aminoethylpropylene glycol, N,N-dimethylaminoethylpropylene glycol, isopropylamine 2-Amino-1-butanol, aminomethylpropanol, aminodimethylpropanol, N,N-dimethylaminomethylpropanol, isobutanolamine, diisopropanolamine, 3-amino, 4-hydroxyoctane, 2-aminobutanol, tris(hydroxymethyl)aminomethane (TRIS), N,N-dimethyltris(hydroxymethyl)aminomethane, hydroxypropylamine, benzylamine, hydroxyethylamine, tris(hydroxyethyl)aminomethane, other C1-C8 alkanolamines and combinations thereof; amines, such as triethylenediamine, ethylenediamine, hexamethylenediamine, tetraethylenepentamine (TEPA), triethylenetetramine, diethylenetriamine, triethylamine, trimethylamine and combinations thereof; diethylene glycolamine; morpholine; and combinations of amines and alkanolamines. Preferably, organic amines include monoethanolamines.

[0043] pH adjusters include alkali metal hydroxides (e.g., LiOH, KOH, RbOH, CsOH), alkaline earth metal hydroxides (e.g., Be(OH)2, Mg(OH)2, Ca(OH)2, Sr(OH)2, Ba(OH)2), and those having the formula NR. 1 R 2 R 3 R 4 Compounds of OH, in which R 1 R 2 R 3 and R 4 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C2-C6 alkyl groups (e.g., ethyl, propyl, butyl, pentyl, and hexyl), C1-C6 alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy), and substituted or unsubstituted C6-C groups. 10aryl (e.g., benzyl), where R 1 R 2 R 3 and R 4 Not all are methyl. Commercially available tetraalkylammonium hydroxides may be used, including tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide, ethyltrimethylammonium hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide, diethyldimethylammonium hydroxide, triethylmethylammonium hydroxide, trihydroxyethylmethylammonium hydroxide, and combinations thereof. Alternatively or additionally, at least one quaternary base may be of the formula (PR... 1 R 2 R 3 R 4 Compounds of OH, wherein R 1 R 2 R 3 and R 4 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain C1-C6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl), branched-chain C1-C6 alkyl, C1-C6 alkoxy (e.g., methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy), substituted C6-C 10 Aryl, unsubstituted C6-C 10 The pH adjuster comprises an aryl group (e.g., benzyl) and any combination thereof, such as tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium hydroxide, methyltriphenylphosphonium hydroxide, ethyltriphenylphosphonium hydroxide, and n-propyltriphenylphosphonium hydroxide. In one embodiment, the pH adjuster comprises KOH. In another embodiment, the pH adjuster comprises choline hydroxide. In yet another embodiment, the pH adjuster comprises at least one alkali metal hydroxide and at least one additional hydroxide listed herein. In yet another embodiment, the pH adjuster comprises KOH and at least one additional hydroxide listed herein. In still another embodiment, the pH adjuster comprises KOH and choline hydroxide.

[0044] The metal corrosion inhibitors envisioned in this article include (but are not limited to): acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, isocynic acid, lactic acid, leucine, lysine, and cis-butene. Diosmic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, pyrocatechol, benzoic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, benzoic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, pyridinecarboxylic acid, 1,3-cyclopentanedione, catechol, pyrogallol, m-phenylene Bisphenol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, phenyl isohydroxyxamic acid, 2,5-dicarboxypyridine, 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), N-(hydroxyethyl)-ethylenediaminetetraacetic acid (EDTA) HEdTA), iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), azirmonotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperidine, N-(2-aminoethyl)piperidine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyxamic acid, 5-sulfosalicylic acid, and combinations thereof. In a preferred embodiment, preferably, the metal corrosion inhibitor comprises at least one of cysteine, oxalic acid, and histidine, or any combination thereof. In another preferred embodiment, the metal corrosion inhibitor comprises cysteine ​​and oxalic acid. In yet another preferred embodiment, the metal corrosion inhibitor comprises cysteine, oxalic acid, and at least one additional metal corrosion inhibitor.

[0045] The envisioned organic additives include (but are not limited to): 2-pyrrolidone, 1-(2-hydroxyethyl)-2-pyrrolidone (HEP), glycerol, 1,4-butanediol, tetramethylene sulfone (sulfolane), dimethyl sulfone, ethylene glycol, propylene glycol, dipropylene glycol, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, glycol ethers (e.g., 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 (DEGBE), triethylene glycol monobutyl ether (TEGBE), ethylene glycol monohexyl ether (EGHE), diethylene glycol monohexyl ether (DEGHE), ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether (DPGME), tripropylene glycol methyl ether (TPGME), dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether (DPGPE), tripropylene glycol n-propyl ether, propylene glycol n-butyl ether (DOWANOL PnB), dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether (DOWANOL PPh), and combinations thereof. Alternatively or additionally, the organic additive may contain: phosphonic acids and their derivatives, such as 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"'-tetra(methylenephosphonic acid) (DOTP), azoxytris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DETAP), aminotris(methylenephosphonic acid), bis(hexamethylene)triaminephosphonic acid, 1,4,7-triazacyclononane-N,N',N"-tris(methylenephosphonic acid) (NOTP), their salts, and their derivatives. Alternatively or additionally, the organic additive may contain hydroxypropyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose. Sodium carboxymethyl cellulose (Na CMC), polyvinylpyrrolidone (PVP), any polymer synthesized using N-vinylpyrrolidone monomer, polyacrylates and polyacrylate analogs, polyamino acids (e.g., polyalanine, polyleucine, polyglycine), polyamide hydroxyurea, polylactone, polyacrylamide, succinate, polyglucosamine, polyethylene oxide, polyvinyl alcohol (PVA), polyvinyl acetate, polyacrylic acid, polyethylene imine (PEI), sugar alcohols (e.g., sorbitol and xylitol), esters of dehydrated sorbitol, secondary alcohol ethoxylates (e.g., TERGITOL), and combinations thereof. In a preferred embodiment, at least one organic additive comprises HEDP. In another preferred embodiment, at least one organic additive comprises at least one glycol ether, said glycol ether comprising triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether. In yet another preferred embodiment, at least one organic additive comprises HEDP and at least one glycol ether comprising triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether.In another preferred embodiment, at least one organic additive includes HEC or a combination of HEDP and HEC, or a combination of HEC, HEDP and at least one glycol ether including triethylene glycol monobutyl ether, propylene glycol n-butyl ether or propylene glycol phenyl ether, or a combination of HEC and at least one glycol ether including triethylene glycol monobutyl ether, propylene glycol n-butyl ether or propylene glycol phenyl ether.

[0046] The reducing agent (if present) comprises (but is not limited to): ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, gallic acid, methanose sulfinic acid, uric acid, tartaric acid, cysteine, potassium D-gluconate, hydroxylamine, potassium nitrite, guanidine carbonate, 8-hydroxy-5-quinoline sulfonic acid hydrate, and any combination thereof. Preferably, the reducing agent comprises ascorbic acid, tartaric acid, or a combination thereof. If present, at least one reducing agent is present in the cleaning composition of the first aspect in an amount of about 0.0001 wt% to about 1 wt%, preferably about 0.0001 wt% to about 0.2 wt%, based on the total weight of the composition.

[0047] Surfactants (if present) include (but are not limited to) anionic, nonionic, cationic, and / or amphoteric surfactants, such as: alginate and its salts; carboxymethyl cellulose; dextran sulfate and its salts; poly(galacturonic acid) and its salts; homopolymers of (meth)acrylic acid and its salts, maleic acid, maleic anhydride, styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, acrylamidopropyl sulfonic acid and its salts; (meth)acrylic acid and its salts, maleic acid, maleic anhydride, Copolymers of styrene sulfonic acid and its salts, vinyl sulfonic acid and its salts, allyl sulfonic acid and its salts, and acrylamidopropyl sulfonic acid and its salts; polyglucosamine; cationic starch; polylysine and its salts; diallyl dimethyl ammonium chloride (DADMAC), diallyl dimethyl ammonium bromide, diallyl dimethyl ammonium sulfate, diallyl dimethyl ammonium phosphate, dimethylallyl dimethyl ammonium chloride, diethylallyl dimethyl ammonium chloride, diallyl di(β-hydroxyethyl) ammonium chloride, diallyl di(β-ethoxyethyl) ammonium chloride, Addition salts and quaternary salts of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 7-amino-3,7-dimethyloctyl methacrylate, N,N'-dimethylaminopropylacrylamide, allylamine, diallylamine, ethyleneamine, and vinylpyridine homopolymers; and diallyl dimethylammonium chloride (DADMAC), diallyl dimethylammonium bromide, and diallyl dimethylammonium sulfate. Diallyl dimethylammonium phosphate, dimethylallyl dimethylammonium chloride, diethylallyl dimethylammonium chloride, diallyl di(β-hydroxyethyl)ammonium chloride, diallyl di(β-ethoxyethyl)ammonium chloride, addition salts and quaternary salts of (meth)acrylate dimethylaminoethyl ester, addition salts and quaternary salts of (meth)acrylate diethylaminoethyl ester, addition salts and quaternary salts of (meth)acrylate 7-amino-3,7-dimethyloctyl ester, addition salts and quaternary salts of N,N'-dimethylaminopropylacrylamide acid addition salts Copolymers of salts and quaternary salts, allylamine, diallylamine, ethyleneamine, and vinylpyridine; cocoyl dimethyl carboxymethyl betaine; lauryl dimethyl carboxymethyl betaine; lauryl dimethyl-α-carboxyethyl betaine; hexadecyl dimethyl carboxymethyl betaine; lauryl-bis-(2-hydroxyethyl)carboxymethyl betaine; octadecyl-bis-(2-hydroxypropyl)carboxymethyl betaine; oleyl dimethyl-γ-carboxypropyl betaine; lauryl-bis-(2-hydroxypropyl)α-carboxyethyl betaine ; Coco-dimethyl-sulfopropyl-betaine; Stearyl-dimethyl-sulfopropyl-betaine; Lauryl-bis-(2-hydroxyethyl)sulfopropyl-betaine; Sodium dodecyl sulfate; Sodium dioctyl sulfosuccinate; Sodium lauryl ether sulfate; Polyethylene glycol branched nonylphenyl ether ammonium sulfate; Disodium 2-dodecyl-3-(2-sulfonate phenoxy); PEG25-PABA; Polyethylene glycol mono-C10-16-alkyl ether sodium sulfate; (2-N-butoxyethoxy)acetic acid;Hexadecylbenzenesulfonic acid; hexadecyltrimethylammonium hydroxide; dodecyltrimethylammonium hydroxide; dodecyltrimethylammonium chloride; hexadecyltrimethylammonium chloride; N-alkyl-N-benzyl-N,N-dimethylammonium chloride; dodecylamine; polyethylene oxide lauryl ether; dodecenyl succinic acid monodiethanolamide; ethylenediaminetetra(ethoxylate-block-propoxylate); and combinations thereof. If present, at least one surfactant is present in the cleaning composition of the first aspect in an amount of about 0.00001 wt% to about 1 wt%, preferably about 0.00001 wt% to about 0.2 wt%, based on the total weight of the composition.

[0048] If present, a buffer is added during dilution and manufacturing to stabilize the washing composition and achieve a suitable compositional pH, as readily determined by those skilled in the art. Contemplated buffers include (but are not limited to): phosphoric acid, dipotassium phosphate, potassium carbonate, boric acid, lysine, proline, β-alanine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), dimethylglyoxime, diphosphates (e.g., (NH4)2HPO4, K2HPO4), triphosphates (e.g., (NH4)3PO4, K3PO4), mixtures of diphosphates and triphosphates (e.g., K2HPO4 / K3PO4), mixtures of dicarbonates and tricarbonates (e.g., K2CO3 / KHCO3), hydroxyethylidene diphosphonic acid (HEDP), and combinations thereof. Preferred buffers (if present) include phosphoric acid, potassium carbonate, and combinations thereof. If present, at least one buffer is present in the cleaning composition of the first aspect in an amount of about 0.0001 wt% to about 20 wt%, preferably about 1 wt% to about 20 wt%, or about 1 wt% to about 10 wt%, or about 0.1 wt% to about 5 wt%, based on the total weight of the composition.

[0049] In a particularly preferred embodiment, the cleaning composition of the first aspect comprises, consists of, or mainly comprises: at least one organic amine, water, at least one organic additive, at least one metal corrosion inhibitor, and at least one of choline hydroxide and alkali metal hydroxide, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably from about 5 to about 50, more preferably from about 10 to about 25, and most preferably from about 12 to about 20; the organic amine / metal corrosion inhibitor ranging from about The composition comprises: 0.01 to about 25, preferably about 0.1 to about 15, more preferably about 1 to about 10, and most preferably about 1 to about 6, of choline hydroxide / metal corrosion inhibitors; 0.01 to about 30, preferably about 0.5 to about 20, more preferably about 2 to about 10, and most preferably about 2 to about 6, of alkali metal hydroxides / metal corrosion inhibitors; and 0.01 to about 50, preferably about 0.1 to about 25, more preferably about 1 to about 15, and most preferably about 2 to about 10, of organic additives / metal corrosion inhibitors. The amount of water in the cleaning composition is at least 80 wt%, preferably at least 85 wt%, and more preferably at least 90 wt%, based on the total weight of the composition. Preferably, both choline hydroxide and alkali metal hydroxides are present, and at least one alkali metal hydroxide includes KOH. Surprisingly, the most preferred product, by total weight of the composition, comprises the following combination: (a) oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1 to about 3:1; or (b) histidine, oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1:1 to about 2:3:1.

[0050] In another preferred embodiment, the cleaning composition of the first aspect comprises, consists of, or mainly comprises: at least one organic amine, water, at least one pH adjuster, phosphonic acid or a derivative thereof, at least one glycol ether, and at least one metal corrosion inhibitor, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably from about 5 to about 50, more preferably from about 10 to about 25, and most preferably from about 12 to about 20; and an organic amine / metal corrosion inhibitor ranging from about 0.1%. The composition comprises: a pH adjuster / metal corrosion inhibitor ranging from about 50, preferably from about 1 to about 30, more preferably from about 2 to about 20, and most preferably from about 4 to about 10; a phosphonic acid or its derivative / metal corrosion inhibitor ranging from about 0.01 to about 25, preferably from about 0.1 to about 15, more preferably from about 0.5 to about 10, and most preferably from about 0.5 to about 4; and a glycol ether / metal corrosion inhibitor ranging from about 0.01 to about 25, preferably from about 0.1 to about 20, more preferably from about 0.5 to about 10, and most preferably from about 1 to about 6. The amount of water in the cleaning composition is at least 80 wt%, preferably at least 85 wt%, and more preferably at least 90 wt%, based on the total weight of the composition. Preferably, the phosphonic acid or its derivative includes HEDP, and at least one glycol ether includes triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether. Surprisingly, the most preferred product, by total weight of the composition, comprises the following combination: (a) oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1 to about 3:1; or (b) histidine, oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1:1 to about 2:3:1.

[0051] In yet another embodiment, the cleaning composition of the first aspect comprises, consists of, or mainly comprises: at least one organic amine, water, phosphonic acid or a derivative thereof, at least one glycol ether, at least one metal corrosion inhibitor, and at least one of choline hydroxide and an alkali metal hydroxide, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably from about 5 to about 50, more preferably from about 10 to about 25, and most preferably from about 12 to about 20; and an organic amine / metal corrosion inhibitor ranging from about 0.01 to about 25, preferably from about 0.1 to about 15, more preferably from about 1 to about 10. The preferred components are choline hydroxide / metal corrosion inhibitors ranging from about 1 to about 6; alkali metal hydroxides / metal corrosion inhibitors ranging from about 0.01 to about 30, preferably about 0.5 to about 20, more preferably about 2 to about 10, and most preferably about 2 to about 6; phosphonic acids or their derivatives / metal corrosion inhibitors ranging from about 0.01 to about 25, preferably about 0.1 to about 15, more preferably about 0.5 to about 10, and most preferably about 0.5 to about 4; and glycol ethers / metal corrosion inhibitors ranging from about 0.01 to about 25, preferably about 0.1 to about 20, more preferably about 0.5 to about 10, and most preferably about 1 to about 6. The amount of water in the cleaning composition is at least 80 wt%, preferably at least 85 wt%, and more preferably at least 90 wt%, based on the total weight of the composition. Preferably, the composition contains both choline hydroxide and an alkali metal hydroxide, with at least one alkali metal hydroxide including KOH, a phosphonic acid or a derivative thereof including HEDP, and at least one glycol ether including triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether. Surprisingly, the most preferred product, by total weight of the composition, comprises the following combination: (a) oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1 to about 3:1; or (b) histidine, oxalic acid, and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1:1 to about 2:3:1.

[0052] In yet another embodiment, the cleaning composition of the first aspect comprises, consists of, or mainly comprises: at least one organic amine, water, at least one glycol ether, at least one buffer, at least one metal corrosion inhibitor, and at least one of choline hydroxide and an alkali metal hydroxide, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably from about 5 to about 50, more preferably from about 10 to about 25, and most preferably from about 12 to about 20; and an organic amine / metal corrosion inhibitor ranging from about 0.01 to about 25, preferably from about 0.1 to about 15, more preferably from about 1 to about 1. The composition comprises: 0.01 to about 50.01.05 to about 30.05 ... Preferably, the composition contains both choline hydroxide and an alkali metal hydroxide, with at least one alkali metal hydroxide including KOH, at least one glycol ether including triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether, and at least one buffer including phosphoric acid or potassium carbonate. Surprisingly, the most preferred product, by total weight of the composition, comprises the following combination: (a) oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1 to about 3:1; or (b) histidine, oxalic acid, and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1:1 to about 2:3:1.

[0053] In yet another embodiment, the cleaning composition of the first aspect comprises, consists of, or mainly comprises: at least one organic amine, water, phosphonic acid or a derivative thereof, at least one glycol ether, at least one buffer, at least one metal corrosion inhibitor, and at least one of choline hydroxide and an alkali metal hydroxide, wherein the cleaning composition is formulated in the following weight percentage ratios: an organic amine / metal corrosion inhibitor ranging from about 1 to about 100, preferably from about 5 to about 50, more preferably from about 10 to about 25, and most preferably from about 12 to about 20; and a choline hydroxide / metal corrosion inhibitor ranging from about 0.01 to about 25, preferably from about 0.1 to about 15, more preferably from about 1 to about 10, and most preferably from about 1 to about 6. The composition comprises: alkali metal hydroxides / metal corrosion inhibitors ranging from about 0.01 to about 30, preferably about 0.5 to about 20, more preferably about 2 to about 10, and most preferably about 2 to about 6; phosphonic acids or their derivatives / metal corrosion inhibitors ranging from about 0.01 to about 25, preferably about 0.05 to about 15, more preferably about 0.1 to about 10, and most preferably about 0.1 to about 4; glycol ethers / metal corrosion inhibitors ranging from about 0.01 to about 25, preferably about 0.1 to about 20, more preferably about 0.5 to about 10, and most preferably about 1 to about 6; and buffers / metal corrosion inhibitors ranging from about 1 to about 100, preferably about 5 to about 60, more preferably about 10 to about 50, and most preferably about 20 to about 40. The amount of water in the cleaning composition is at least 80 wt% of the total weight of the composition. Preferably, the composition contains both choline hydroxide and an alkali metal hydroxide, with at least one alkali metal hydroxide including KOH, a phosphonic acid or a derivative thereof including HEDP, at least one buffer including phosphoric acid or potassium carbonate, and at least one glycol ether including triethylene glycol monobutyl ether, propylene glycol n-butyl ether, or propylene glycol phenyl ether. Surprisingly, the most preferred product, by total weight of the composition, comprises the following combination: (a) oxalic acid and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1 to about 3:1; or (b) histidine, oxalic acid, and cysteine ​​as metal corrosion inhibitors in a weight percentage ratio of about 1:1:1 to about 2:3:1.

[0054] The range of weight percentage ratios of the components will cover all possible concentrated or diluted embodiments of the composition of the first aspect. For this purpose, in one embodiment, a concentrated cleaning composition that can be diluted for use as a cleaning solution is provided. The concentrated cleaning composition or “concentrate” is preferably allowed to be diluted to a desired strength and pH by a user (e.g., a CMP process engineer) during use. The dilution ratio of the concentrated cleaning composition may range from about 1:1 to about 2500:1, preferably from about 10:1 to about 200:1, and most preferably from about 30:1 to about 150:1, wherein the cleaning composition is diluted when or just before using a solvent (e.g., deionized water). Those skilled in the art will understand that the range of weight percentage ratios of the components disclosed herein should remain unchanged after dilution.

[0055] The concentration of the cleaning composition of the first aspect has a pH greater than 7, preferably in the range of about 10 to greater than 14, more preferably in the range of about 12 to about 14, and most preferably in the range of about 13 to 14. Those skilled in the art will understand that, upon dilution, the pH of the cleaning composition will decrease to the range of about 10 to about 12.

[0056] The compositions of the first aspect can be used in applications including (but not limited to) the following: post-etching residue removal, post-ashing residue removal, surface preparation, post-electroplating cleaning, and post-CMP residue removal. Additionally, it is envisioned that the cleaning compositions can be used to clean and protect other metal (e.g., copper-containing) products including (but not limited to): decorative metals, wire bonding, printed circuit boards, and other electronic packages using metals or metal alloys.

[0057] In yet another preferred embodiment, the cleaning composition of the first aspect further comprises residues and / or contaminants. The residues and contaminants are soluble in the composition. Alternatively, the residues and contaminants may be suspended in the composition. Preferably, the residues comprise post-CMP residues, post-etching residues, post-ashing residues, contaminants, or combinations thereof.

[0058] The cleaning compositions described herein can be readily formulated by adding only the individual components and mixing them into a homogeneous state. Furthermore, the compositions can be readily formulated as single-component formulations or as multi-component formulations mixed at or before use; for example, individual portions of a multi-component formulation may be mixed at the tool or in a reservoir upstream of the tool. The concentrations of the individual components can vary widely across specific multiples of the composition, i.e., becoming more dilute or more concentrated, and it should be understood that the compositions described herein may differently and alternatively comprise any combination of components consistent with the disclosure herein, consist of any combination of components, or consist primarily of any combination of components.

[0059] Therefore, another aspect relates to a kit containing one or more components adapted to form the cleaning composition described herein in one or more containers. The kit may contain at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor in one or more containers for combination with additional water during manufacturing or use. In another embodiment, the kit may contain at least one organic amine, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor in one or more containers for combination with water during manufacturing or use. The container of the kit must be suitable for storing and shipping the cleaning composition, such as a NOWPak® container (Entegris, Inc., Billerica, Mass., USA).

[0060] When applied to microelectronics manufacturing operations, the cleaning compositions described herein are effectively used to remove post-CMP residues and / or contaminants, or post-etching residues or post-ashing residues from the surfaces of microelectronic devices. The cleaning compositions do not substantially impair low-k dielectric materials, barrier layer materials (e.g., at least one of ruthenium-containing, tantalum-containing, and cobalt-containing materials), or corrode metal interconnects (e.g., copper) on the device surface. Preferably, the cleaning compositions remove at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99% of the residues present on the device before residue removal.

[0061] In post-CMP residue and contaminant cleaning applications, the cleaning compositions described herein can be used with a wide variety of conventional cleaning tools, including (but not limited to): Verteq single-wafer mega-sonic Goldfinger, OnTrak System DDS (double-sided scrubber), SEZ or other single-wafer spray rinsing, Applied Materials Mirra-Mesa™ / Reflexion™ / Reflexion LK™, and mega-sonic batch wet cleaning station systems.

[0062] When using the composition to clean CMP residues, post-etching residues, post-ashing residues, and / or contaminants from microelectronic devices having CMP residues, post-etching residues, post-ashing residues, and / or contaminants thereon, the cleaning composition is typically in contact with the device for about 5 seconds to about 10 minutes, preferably about 1 second to 20 minutes, and more preferably about 15 seconds to about 5 minutes, at a temperature ranging from about 20°C to about 90°C, preferably about 20°C to about 50°C. These contact times and temperatures are illustrative, and any other suitable time and temperature conditions effective for at least partially cleaning CMP residues / contaminants from the device may be used in extensive practice of the method. Both "at least partially cleaning" and "substantially removing" correspond to removing at least 90%, more preferably at least 95%, even more preferably at least 98%, and most preferably at least 99% of the residues present on the device before residue removal.

[0063] After the desired cleaning action is achieved, the cleaning composition can be easily removed from the device previously applied thereto, which is desirable and effective for the given end-use application of the composition described herein. Preferably, the rinsing solution contains deionized water. Subsequently, the device can be dried using nitrogen or a rotary drying cycle.

[0064] Another aspect of the present invention relates to improved microelectronic devices manufactured according to the methods described herein and to products containing such microelectronic devices.

[0065] On the other hand, it relates to a recirculating cleaning composition, wherein, as readily determined by those skilled in the art, the cleaning composition can be circulated until the load of residues and / or contaminants reaches the maximum amount that the cleaning composition can accommodate.

[0066] Another aspect relates to a method of manufacturing an article comprising a microelectronic device, the method comprising using a cleaning composition comprising, consisting of, or primarily consisting of: at least one organic amine, water, at least one pH adjuster, at least one organic additive, at least one metal corrosion inhibitor, optionally at least one buffer, and optionally at least one reducing agent, contacting the microelectronic device with the cleaning composition for a sufficient time to clean the residues and contaminants from the microelectronic device having CMP residues and contaminants thereon, and incorporating the microelectronic device into the article.

[0067] In another aspect, a method for removing CMP residues and contaminants from a microelectronic device having CMP residues and contaminants thereon is described, the method comprising:

[0068] - Grinding microelectronic devices with CMP slurry;

[0069] - Contact the microelectronic device with the cleaning composition described herein for a sufficient time to remove post-CMP residues and contaminants from the microelectronic device, to form a composition containing post-CMP residues; and

[0070] - Ensure that the microelectronic device is in continuous contact with the cleaning composition for a sufficient amount of time to achieve substantial cleaning of the microelectronic device.

[0071] The cleaning composition comprises, consists of, or is primarily composed of: at least one organic amine, water, at least one pH adjuster, at least one organic additive, at least one metal corrosion inhibitor, optionally at least one buffer, and optionally at least one reducing agent.

[0072] On the other hand, it relates to an article comprising a cleaning composition, a microelectronic device, and a material selected from the group consisting of residues, contaminants, and combinations thereof, wherein the cleaning composition comprises at least one organic amine, water, at least one pH adjuster, at least one organic additive, at least one metal corrosion inhibitor, optionally at least one buffer, and optionally at least one reducing agent, and the residues comprise at least one of CMP residues, etching residues, and ashing residues. In a preferred embodiment, the microelectronic device comprises copper, a low-k dielectric material, and a barrier material, said barrier material comprising at least one of ruthenium-containing materials, tantalum-containing materials, and cobalt-containing materials.

[0073] The features and advantages of the invention are further illustrated by the following non-limiting examples, wherein all parts and percentages are by weight unless otherwise expressly stated.

[0074] Example 1

[0075] Prior to the experiments, the solutions shown in Table 1 were prepared and diluted with deionized water to a ratio of 60:1. Formulation A contained 0.05 wt% cysteine, 0.16 wt% choline hydroxide, 4.5 wt% MEA, and equilibrium water. Formulation BL contained 0.2 wt% oxalic acid, 0.1 wt% cysteine, 4.950 wt% MEA, a mixture of choline hydroxide and KOH to produce a pH of 13.2 in the formulations, and the remaining components are listed in Table 1. The solutions were tested to determine the BTA removal efficiency (in percentage) and copper etching rate (in Å / min), the results of which are also provided in Table 1. The BTA removal efficiency experiment was performed using a copper substrate on which a BTA layer was grown. The substrate with BTA was immersed in the solutions in Table 1 at room temperature. An ellipsometry was used to determine the BTA film thickness before and after contact with the solution. The copper etching rate experiment was also performed using a copper substrate at room temperature.

[0076] Example 2

[0077] Prior to the experiments, the solutions shown in Table 2 were prepared and diluted with deionized water to a ratio of 60:1. Formulation AA-KK contained 0.2 wt% oxalic acid, 0.075 wt% cysteine, 4.95 wt% MEA, and a mixture of choline hydroxide and KOH to produce a pH of 13.2 in the formulations (except for formulation CC), with the remaining components listed in Table 2. Notably, formulation CC contained a mixture of choline hydroxide and KOH to produce a pH of approximately 13.7. The solutions were tested to determine BTA removal efficiency (in percentage), copper etching rate (in Å / min), and low-k dielectric etching rate (in Å / min), the results of which are also shown in Table 2. The BTA removal efficiency experiments were performed using a copper substrate on which a BTA layer was grown. The substrate with BTA was immersed in the solutions in Table 2 at room temperature. An ellipsometer was used to determine the BTA film thickness before and after contact with the solution. Copper etching rate and low-k dielectric etching rate experiments were also performed at room temperature using low-k dielectric and copper substrates, respectively.

[0078] The results showed that formulations CC, DD, and HH exhibited the highest BTA removal and were comparable to other formulations in terms of copper etching rate and low-k dielectric etching rate. Notably, formulation HH was most effective in removing the specialized slurry from the copper surface of microelectronic substrates. Notably, formulation CC, being a higher pH form of BB, showed good slurry removal and a lower copper etching rate.

[0079] Clearly, the choice of organic additives and pH is important regarding BTA removal and slurry removal.

[0080] Table 1: Al formulations containing copper etching rate and BTA removal efficiency.

[0081]

[0082] Table 2: Formulas AA-KK including copper etching rate, low-k dielectric etching rate (ER), and BTA removal efficiency.

[0083]

[0084] Example 3

[0085] Prior to the experiments, the solutions shown in Table 3 were prepared and diluted with deionized water to a ratio of 60:1. Formulation LL-OO contained 0.2 wt% oxalic acid, 0.1 wt% cysteine, 4.95 wt% MEA, a mixture of choline hydroxide and KOH to produce a pH of 13.2 in the formulation, and the remaining components are listed in Table 3. The concentrate had a pH of approximately 13.2. The solutions were tested to determine BTA removal efficiency (in percentage) and copper etching rate (in Å / min), the results of which are also provided in Table 3. The BTA removal efficiency experiment was performed using a copper substrate on which a BTA layer was grown. The substrate with BTA was immersed in the solutions in Table 3 at room temperature. An ellipsometry was used to determine the BTA film thickness before and after contact with the solution. The copper etching rate experiment was also performed using a copper substrate at room temperature.

[0086] The results showed that formulations NN and OO exhibited the highest BTA removal rates and were comparable to other formulations in terms of copper etching rates. Notably, formulation OO was most effective in removing the specialized slurry from the surface of microelectronic substrates.

[0087] Table 3: Formulation LL-OO, copper etching rate, and BTA removal efficiency.

[0088]

[0089] Although the invention has been disclosed herein with reference to illustrative embodiments and features, it will be understood that the embodiments and features described above are not intended to limit the invention, and other variations, modifications, and other embodiments will be apparent to those skilled in the art based on the disclosure herein. Therefore, the invention will be generally explained as all the described variations, modifications, and alternative embodiments are covered within the spirit and scope of the claims set forth below.

Claims

1. A cleaning composition comprising at least one organic amine, water, at least one pH adjuster, at least one organic additive, and at least one metal corrosion inhibitor. The metal corrosion inhibitors mentioned herein include substances selected from the group consisting of: acetic acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine, asparagine, aspartic acid, betaine, dimethylglyoxime, formic acid, fumaric acid, gluconic acid, glutamic acid, glutamine, glutamate, glyceric acid, glycerol, glycolic acid, glyoxylic acid, histidine, iminodiacetic acid, isophthalic acid, itaconic acid, lactic acid, leucine, lysine. Amino acid, maleic acid, maleic anhydride, malic acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic acid, proline, propionic acid, catechol, benzopyrenic acid, quinic acid, serine, sorbitol, succinic acid, tartaric acid, terephthalic acid, trimellitic acid, benzopyrenic acid, tyrosine, valine, xylitol, oxalic acid, tannic acid, pyridinecarboxylic acid, 1,3-cyclopentanedione, catechol. Thiophene, resorcinol, hydroquinone, cyanuric acid, barbituric acid, 1,2-dimethylbarbituric acid, pyruvic acid, propanethiol, benzohydroxyxamic acid, 2,5-dicarboxypyridine, 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid (EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA), N-(hydroxyethyl)-ethylenediaminetriacetic acid (H) EdTA, iminodiacetic acid (IDA), 2-(hydroxyethyl)iminodiacetic acid (HIDA), azirmonotriacetic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine, cysteine, glutamic acid, isoleucine, methionine, piperidine, N-(2-aminoethyl)piperidine, pyrrolidine, threonine, tryptophan, salicylic acid, p-toluenesulfonic acid, salicylhydroxyxamic acid, 5-sulfosalicylic acid, and combinations thereof; and The weight percentage ratio of the organic amine to the corrosion inhibitor is in the range of 1 to 100, the weight percentage ratio of the pH adjuster to the corrosion inhibitor is in the range of 0.1 to 50, and the weight percentage ratio of the organic additive to the corrosion inhibitor is in the range of 0.01 to 50.

2. The cleaning composition according to claim 1, wherein the at least one organic amine comprises an organoamine having the general formula NR. 1 R 2 R 3 The substance in which R 1 R 2 and R 3 They can be the same or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C1-C6 alkyl, straight-chain or branched C1-C6 alcohol, and straight-chain or branched ether.

3. The cleaning composition according to claim 1, wherein the at least one organic amine comprises monoethanolamine.

4. The cleaning composition according to claim 1, wherein the at least one pH adjuster has the formula NR 1 R 2 R 3 R 4 OH or PR 1 R 2 R 3 R 4 OH, where R 1 R 2 R 3 and R 4 They may be the same as or different from each other and are selected from the group consisting of: hydrogen, straight-chain or branched C2-C6 alkyl, C1-C6 alkoxy, and substituted or unsubstituted C6-C 10 Aryl.

5. The cleaning composition according to claim 1, wherein the at least one pH adjuster comprises choline hydroxide.

6. The cleaning composition according to claim 1, wherein the at least one metal corrosion inhibitor comprises cysteine, oxalic acid, histidine, or any combination thereof.

7. The cleaning composition according to claim 1, wherein the organic additive comprises triethylene glycol monobutyl ether, propylene glycol n-butyl ether, propylene glycol phenyl ether, HEDP, HEC, or any combination thereof.

8. The cleaning composition according to claim 1, wherein the cleaning composition further comprises at least one reducing agent, the reducing agent comprising a substance selected from the group consisting of: ascorbic acid, L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives, gallic acid, formamidinium sulfinic acid, uric acid, tartaric acid, cysteine, potassium D-gluconate, hydroxylamine, potassium nitrite, guanidine carbonate, 8-hydroxy-5-quinoline sulfonic acid hydrate, and any combination thereof.

9. The cleaning composition of claim 1, wherein the cleaning composition further comprises at least one buffer, the buffer comprising a substance selected from the group consisting of: phosphoric acid, dipotassium phosphate, potassium carbonate, boric acid, lysine, proline, β-alanine, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), dimethylglyoxime, (NH4)2HPO4, K2HPO4, (NH4)3PO4, K3PO4, K2HPO4 / K3PO4, K2CO3 / KHCO3, hydroxyethylidene diphosphonic acid (HEDP), and combinations thereof.

10. The cleaning composition of claim 1, wherein the cleaning composition is free from at least one oxidant; a fluorine source; an abrasive; tetramethylammonium hydroxide; an azole corrosion inhibitor; gallic acid; sulfonium compounds; aminooxime compounds; and combinations thereof.

11. The cleaning composition of claim 1, wherein the weight percentage ratio of the organic amine to the corrosion inhibitor is in the range of 5 to 50, the weight percentage ratio of the pH adjuster to the corrosion inhibitor is in the range of 1 to 30, and the weight percentage ratio of the organic additive to the corrosion inhibitor is in the range of 0.1 to 25.

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