Cleaning composition for semiconductor substrates

Abstract

To provide a composition useful for removing residue and photoresist from a semiconductor substrate with minimum etch of aluminum-copper alloys, aluminum nitride, and tungsten.SOLUTION: There is provided compositions and methods useful for removing residue and photoresist from a semiconductor substrate comprising: from about 5 to about 60 wt.% of water; from about 10 to about 90 wt.% of a water-miscible organic solvent; from about 5 to about 90 wt.% of at least one alkanolamine; from about 0.05 to about 20 wt.% of at least one polyfunctional organic acid; and from about 0.1 to about 10 wt.% of at least one phenol-type corrosion inhibitor, wherein the composition is substantially free of hydroxylamine.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention provides cleaning compositions that can be used for a variety of applications, including, for example, removing unwanted resist films, post-etching and post-ashing residues on semiconductor substrates. Specifically, the present invention provides cleaning compositions that are particularly useful for removing photoresist, etch residues and antireflective coatings (ARCs), that are hydroxylamine-free and exhibit excellent compatibility with materials, such as aluminum copper alloys, aluminum nitride, tungsten, aluminum oxide and / or other materials, such as Al, Ti, TiN, Ta, TaN or silicides, such as tungsten silicides, or dielectrics. [Background technology]

[0002] The background of the present invention is described in relation to its use in cleaning applications involving the manufacture of integrated circuits, however, the use of the present invention has broader application as will be explained below.

[0003] In the manufacture of integrated circuits, it is sometimes necessary to etch openings or other features in thin films deposited or grown on silicon, gallium arsenide, glass or other substrates located on an integrated circuit wafer in process. Current methods for etching such films require that the film be exposed to a chemical etchant to remove a portion of the film. The specific etchant used to remove a portion of the film depends on the nature of the film. For example, for oxide films, the etchant may be hydrofluoric acid. For polysilicon films, the etchant is typically a mixture of hydrofluoric acid, nitric acid and acetic acid for isotropic silicon etching.

[0004] To ensure that only the desired portions of the film are removed, a photolithography process is used whereby a computer-designed photomask pattern is transferred onto the surface of the film. The mask serves to identify the areas of the film that are to be selectively treated. This pattern is formed of a photoresist material, which is a light-sensitive material that is spun onto the in-process integrated circuit wafer in a thin film and exposed to high-intensity radiation through the photomask. Depending on its composition, the exposed or unexposed photoresist material is typically dissolved by a developer, leaving behind a pattern that allows etching to occur in selected areas while preventing etching in other areas. For example, positive-tone resists are widely used as masking materials to delineate patterns on substrates that, when etched, become vias, trenches, contact holes, etc.

[0005] Dry etching processes, such as plasma etching, reactive ion etching or ion milling, are increasingly being used to attack photoresist-unprotected areas of a substrate to form vias, trenches, contact holes, etc. As a result of the plasma etching process, by-products of photoresist, etching gases and etched materials are deposited as residue around or on the sidewalls of the etched openings on the substrate.

[0006] Moreover, such dry etching processes typically make the photoresist extremely difficult to remove. For example, in complex semiconductor devices, such as advanced DRAM and logic devices with multiple layers of wiring steps of interconnect wiring, reactive ion etching (RIE) is used to create vias through interlayer dielectrics to provide contact between one level of silicon, silicide or metal wiring and the next level of wiring. Typically, these vias expose one or more of Al, AlCu, Cu, Ti, TiN, Ta, TaN, silicon or silicides, such as tungsten, titanium or cobalt silicides. The RIE process leaves behind residues on complex substrates that include a complex mixture that may include, for example, resputtered oxide materials, polymeric materials from the etching gases, and organic materials from the resist used to delineate the vias.

[0007] In addition, following completion of the etching process, the photoresist and etching residues must be removed from the protected areas of the wafer so that final finishing operations can be performed. This can be accomplished in a plasma "ashing" process by using a suitable plasma ashing gas. Typically, this is performed at high temperatures, for example above 200°C. Ashing converts many of the organic residues to volatile species, but leaves mainly inorganic residues on the substrate. Typically, such residues remain not only on the surface of the substrate, but also on the inner walls of any vias that may be present. As a result, ashed substrates are often treated with cleaning compositions, typically referred to as "liquid stripping compositions" or "cleaning compositions", to remove the strongly adherent residues from the substrate. It has also proven problematic to find a suitable cleaning composition for the removal of this residue without adversely affecting the metal circuitry, for example without corroding, dissolving or clouding the metal circuitry. The inability to completely remove or neutralize the residues can lead to discontinuities in the circuit wiring and undesirable increases in electrical resistance.

[0008] Dry ashing of the photoresist using a plasma, which is then applied to the etching plasma, results in the decomposition of the low-k material. Therefore, the ashing process is not suitable for cleaning the photoresist, either due to the compatibility of other layers, such as the metal layer AlCu, due to the integration scheme, or processes that do not require an ashing process. Alternative wet chemistries are used to remove the photoresist film, based on the decomposition of the photoresist in the composition. Wet stripping can achieve the removal of the photoresist layer without damaging other layers, either the metal layers, e.g. AlCu or AlN, or the dielectric layers.

[0009] Typically, cleaning compositions used to remove photoresist or other residues from semiconductor substrates contain hydroxylamine (HA) and / or quaternary ammonium hydroxide. The use of HA raises various environmental concerns due to its explosive nature, and therefore some end users impose strict restrictions on the use of HA. In the field, the problem with compositions that do not contain HA is that they typically exhibit reduced photoresist removal performance.

[0010] In addition to cleaning performance, the cleaning composition of the present invention must have high compatibility with new or additional materials present in structures on semiconductor substrates, such as aluminum nitride, aluminum copper alloys, and dielectric materials. High compatibility means that the cleaning composition does not cause or only causes limited etching damage to those materials, and therefore does not cause or only causes limited etching damage to structures made from those materials. As the structures on the substrate shrink, continuously improving the cleaning composition to improve cleaning performance while reducing etching of materials on the substrate is necessary to improve chip performance.

[0011] Therefore, there is a need in the art for a cleaning composition that has high compatibility requirements for aluminum copper alloys, aluminum nitride, tungsten, aluminum oxide and dielectrics, is hydroxylamine-free, non-toxic and environmentally friendly for various final cleaning operations including stripping photoresist and plasma ashing residues generated by, for example, plasma processes, without the above-mentioned drawbacks. Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention fulfills this need by providing a composition useful for removing residue and photoresist from semiconductor substrates with minimal etching of aluminum copper alloys, aluminum nitride and tungsten, the composition comprising, consisting essentially of, or consisting of: from about 5 to about 60 wt.% water; from about 10 to about 90 wt.% of at least one water-miscible organic solvent selected from pyrrolidones, sulfonyl-containing solvents, acetamides, glycol ethers, polyols, cyclic alcohols, and mixtures thereof; from about 5 to about 90 wt.% of at least one alkanolamine; from about 0.05 to about 20 wt.% of at least one polyfunctional organic acid; and from about 0.1 to about 10 wt.% of at least one phenol-type corrosion inhibitor, and is hydroxylamine-free.

[0013] In one embodiment, the composition comprises N-methylpyrrolidone (NMP), sulfolane, DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), tripropylene glycol methyl ether, propylene glycol propyl ether and diethylene glycol n-butyl ether, ethylene glycol, propylene glycol (PG), 1,4-butanediol, tetrahydrofurfuryl alcohol, venetium chloride, tetrahydrofuran ... at least one water-miscible organic solvent selected from the group consisting of, but not limited to, benzyl alcohol, and mixtures thereof; from about 5 to about 90 wt % of at least one alkanolamine; from about 0.1 to about 20 wt % of at least one polyfunctional organic acid; and from about 0.1 to about 10 wt % of at least one phenol-type corrosion inhibitor, such as, for example, selected from the group consisting of, but not limited to, catechol, 2,3-dihydroxybenzoic acid, and resorcinol, or at least one selected from gallic acid or t-butylcatechol, and is free of hydroxylamine. In another embodiment, the water miscible solvent can be selected from N-methylpyrrolidone (NMP), sulfolane, DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), ethylene glycol, propylene glycol (PG), 1,4-butanediol, tetrahydrofurfuryl alcohol, and benzyl alcohol.

[0014] In another aspect, the invention provides a method for removing photoresist or residue from a substrate comprising one or more of aluminum, aluminum copper alloy, tungsten, aluminum nitride, silicon oxide, and silicon, comprising: 1. A composition useful for removing residue and photoresist from a semiconductor substrate, comprising about 5 to about 60 wt % water; selected from or consisting of pyrrolidone, sulfonyl-containing solvents, acetamides, glycol ethers, polyols, cyclic alcohols, and mixtures thereof, N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), sulfolane, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether, ethylene glycol, propylene glycol (PG), 1,4-butanediol, tetrahydrofurfuryl alcohol, benzyl alcohol, and mixtures thereof. contacting the substrate with a hydroxylamine-free composition comprising, consisting essentially of, or consisting of: about 10 to about 90 wt % of a water-miscible organic solvent, which may be selected from a mixture of N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), dimethylacetamide (DMAC), m-dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof; about 5 to about 90 wt % of at least one alkanolamine; about 0.05 to about 20 wt % or about 0.1 to about 20 wt % of at least one multifunctional organic acid; and about 0.1 to about 10 wt % of at least one phenol-type inhibitor, which may be selected from, or may be selected from, the group consisting of gallic acid, t-butylcatechol, catechol, 2,3-dihydroxybenzoic acid, and resorcinol; rinsing the substrate with water; drying the substrate; The present invention provides a method comprising:

[0015] The compositions of the present invention have superior cleaning properties, are less toxic, and are more environmentally acceptable than compositions currently used in the semiconductor industry. Additionally, the compositions of the present invention exhibit compatibility with a variety of metals and dielectric materials commonly found on semiconductor substrates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] All references cited in this specification, including publications, patent applications, and patents, are hereby incorporated by reference to the same extent as if each reference was individually and specifically indicated to be incorporated by reference and to the same extent as if each reference was set forth in its entirety herein.

[0017] In the context of describing the present invention (especially in the context of the appended claims), the use of the terms "a," "an," and "the" and similar referents are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise indicated herein. The recitation of ranges of values ​​herein, unless otherwise indicated herein, is intended merely to serve as a shorthand method of referring individually to each individual value in the range, and each individual value is incorporated herein as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary words (e.g., "such as") provided herein is intended merely to better clarify the invention and does not limit the scope of the invention unless otherwise stated. No language in the specification should be construed as indicating any unrecited element as essential to the practice of the invention. Use of the term "comprising" in this specification and claims encompasses the narrower terms "consisting essentially of" and "consisting of."

[0018] Embodiments of the invention are described herein, including the best mode known to the inventors for carrying out the invention. Variations of those embodiments may become apparent to those skilled in the art upon reading the following description. The inventors expect those skilled in the art to employ such variations as appropriate, and the inventors intend the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations of the invention is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0019] For ease of reference, "microelectronic device" or "semiconductor substrate" corresponds to wafers, flat panel displays, phase change memory devices, solar panels and other products comprising solar substrates, photovoltaic cells, 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, single crystal silicon, CdTe, copper indium selenide, copper indium sulfide, and gallium arsenide on gallium. Solar substrates may be doped or undoped. The term "microelectronic device" is not meant to be limiting in any manner and is understood to include any substrate that will ultimately become a microelectronic device or microelectronic assembly.

[0020] As defined herein, "low-k dielectric material" or "dielectric" corresponds to any material having a dielectric constant less than about 3.5 that is used as a dielectric material in integrated microelectronic devices. Preferably, the low-k dielectric material includes low polarity materials such as silicon-containing organic polymers, silicon-containing hybrid organic / inorganic materials, organosilicate glass (OSG), TEOS, fluorinated silicate glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass. It is recognized that low-k dielectric materials can have various densities and various porosities.

[0021] As used herein, "substantially free" is defined as less than 0.001 wt%. "Substantially free" also includes 0.000 wt%. The term "free" means 0.000 wt%.

[0022] As used herein, the term "about" is intended to correspond to ±5% of the stated value.

[0023] In all such compositions where specific components of the composition are discussed in terms of a weight percent range including a lower limit of zero, it is understood that such components may be present or absent in various specific embodiments of the composition, for example, when such components are present, they may be present in concentrations as low as 0.001 weight percent based on the total weight of the composition in which they are used. The weight percentages specified are based on the total weight for the composition and total 100%.

[0024] The cleaning formulation is required for Al BEOL (interconnect process) cleaning of ashed or unashed substrates. It is well known to those skilled in the art that the key characteristic of an effective cleaning agent is the ability to attack and dissolve post-etch and post-ash residues without substantially attacking the underlying interconnect dielectric or metal; the choice of corrosion inhibitor may also be key to control the metal etch rate. The metals that may be present may be aluminum, aluminum copper alloys, aluminum nitride, aluminum oxide, etc., titanium-containing metals such as Ti, TiN, tantalum-containing metals such as Ta, TaN, tungsten-containing metals such as tungsten, or tungsten silicides; or other silicides. Additionally, a dielectric may be present thereon. Of particular interest are Al, AlNi, AlCu, W, TiN, and Ti.

[0025] In one broad aspect, the present invention provides a composition, the components of which are present in amounts that effectively remove residue or photoresist from a substrate, such as a semiconductor substrate. In applications involving semiconductor substrates, such residues include, for example, photoresist, photoresist residues, ashing residues, and etching residues, such as residues caused by reactive ion etching. In addition, the semiconductor substrate includes metals, silicon, silicates, and / or intermediate dielectric materials, such as deposited silicon oxides, that come into contact with the cleaning composition. Typical metals include titanium, titanium nitride, tantalum, tungsten, tantalum nitride, aluminum, aluminum alloys, and aluminum nitride. The cleaning compositions of the present invention are compatible with such materials because they exhibit low metal and / or dielectric etch rates.

[0026] The cleaning compositions of the present invention comprise from about 5 to about 60 wt % water; pyrrolidones, such as N-methylpyrrolidone (NMP); sulfonyl-containing solvents, such as dimethyl sulfoxide (DMSO) and sulfolane; acetamides, such as dimethylacetamide (DMAC); glycol ethers, such as dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), and 3-methoxymethylbutanol (MMB), tripropylene glycol methyl ether, propylene glycol propyl ether, and diethylene glycol n-butyl ether; polyols, such as ethylene glycol, propylene glycol (PG), 1,4-butanediol, and glycerol; cyclic alcohols, such as tetrahydrofuran, ... and mixtures thereof; from about 5 to about 90 wt % of at least one alkanolamine; from about 0.05 or 0.1 to about 20 wt % of at least one polyfunctional organic acid; from about 0.1 to about 10 wt % of at least one phenol-type corrosion inhibitor, which may be selected from the group consisting of gallic acid, t-butylcatechol, catechol, 2,3-dihydroxybenzoic acid, and resorcinol, and is substantially free or free of hydroxylamine and / or substantially free or free of quaternary ammonium hydroxide. The compositions disclosed herein are useful, inter alia, for removing residue and photoresist from semiconductor substrates during the manufacture of microelectronic devices.

[0027] water The cleaning composition of the present invention comprises water. In the present invention, water functions in various ways, such as to dissolve and / or lift off one or more solid components of the composition, as a carrier of components, as an aid to facilitate removal of residues, and as a diluent.Preferably, the water used in the cleaning composition is deionized (DI) water.

[0028] In many applications, water will comprise, for example, about 5 to about 60 wt% of the composition. Other preferred embodiments of the invention may include about 5 to about 40 wt% water. Still other preferred embodiments of the invention may include about 10 to about 30 wt%, 10 to about 25 wt%, about 5 to about 30 wt%, about 5 to about 15 wt%, or 12 to about 28 wt% water. In other embodiments, the amount of water may be any weight percent range bounded by any combination of the following: 5, 7, 10, 12, 15, 18, 20, 22, 25, 28, 30, 35, 40, 50, and 60 wt%.

[0029] Water-miscible organic solvents The compositions disclosed herein further comprise at least one water-miscible organic solvent. Examples of water-miscible organic solvents that can be used in the compositions of the present invention include any one or more of the following types of solvents: pyrrolidones, sulfonyl-containing solvents, acetamides, glycol ethers, polyols, cyclic alcohols, and mixtures thereof. Cyclic alcohols are alcohols with 5- or 6-membered carbon rings. The carbon rings may be aromatic or aliphatic, and may have only carbons forming the ring or one or more heteroatoms in the ring. An example of a pyrrolidone includes N-methylpyrrolidone (NMP). An example of a sulfonyl-containing solvent includes sulfolane and dimethyl sulfoxide (DMSO). An example of an acetamide includes dimethylacetamide (DMAC). Examples of glycol ethers include dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), tripropylene glycol methyl ether, propylene glycol propyl ether and diethylene glycol n-butyl ether (e.g., commercially available under the name Dowanol® DB). Examples of polyols include ethylene glycol, propylene glycol, 1,4-butanediol and glycerol. Examples of cyclic alcohols include tetrahydrofurfuryl alcohol and benzyl alcohol. Solvents can be used alone or in any mixture of solvent types or solvents. Preferred solvents include ethylene glycol, propylene glycol, benzyl alcohol, dimethyl sulfoxide, dimethylacetamide, dipropylene glycol monomethyl ether, n-methylpyrrolidone, tetrahydrofurfuryl alcohol and mixtures thereof. In some embodiments, the solvent can be selected from dimethylsulfoxide, dimethylacetamide, dipropylene glycol monomethyl ether, n-methylpyrrolidone (NMP), 3-methoxymethylbutanol (MMB), and diethylene glycol.

[0030] In another preferred embodiment, the water-miscible organic solvent is selected from or consisting of n-methylpyrrolidone (NMP), ethylene glycol, propylene glycol, benzyl alcohol, dimethyl sulfoxide, dipropylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, and mixtures thereof. N-methylpyrrolidone (NMP) and dimethyl sulfoxide are the most preferred water-miscible organic solvents.

[0031] In other embodiments, the water-miscible organic solvent is selected from the group consisting of N-methylpyrrolidone (NMP), DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof. Alternatively, some embodiments may be substantially free or free of any of the aforementioned classes or individual types of solvents, either alone or in any combination. For example, the cleaning compositions of the present invention may be substantially free or free of pyrrolidone, sulfonyl-containing solvents, acetamide, glycol ether, polyol, and / or cyclic alcohol, or the cleaning compositions of the present invention may be substantially free or free of, for example, ethylene glycol, propylene glycol, THFA, DGME, and / or MMB.

[0032] For many applications, the amount of water-miscible organic solvent in the composition can be a range having beginning and ending points selected from the following list: 10, 15, 17, 20, 22, 25, 27, 29, 30, 31, 33, 35, 37, 38, 40, 42, 45, 48, 50, 53, 55, 60, 70, 80, and 90 wt %. Examples of such ranges of solvent include about 10 wt% to about 90 wt%; about 10 wt% to about 60 wt%; about 20 wt% to about 60 wt%; about 10 wt% to about 50 wt%; about 10 wt% to about 40 wt%; about 10 wt% to about 30 wt%; about 5 wt% to about 30 wt%; 5 wt% to about 15 wt%; about 10 wt% to about 20 wt%; about 30 wt% to about 70 wt%; about 30 wt% to about 50 wt%; or about 20 wt% to about 50 wt% of the composition.

[0033] Alkanolamines The compositions disclosed herein include at least one alkanolamine. The at least one alkanolamine functions to provide a high pH alkaline environment for dissolving and lifting off photoresist or post-etch residues, and also functions as an electron-rich agent that attacks post-etch residues and photoresist to aid in dissolving these undesirable materials. Preferably, the pH of the cleaning composition of the present invention is greater than 9, greater than 10, about 9 to about 13, about 9.5 to about 13, about 10 to about 13, about 10 to about 12.5, or about 10 to about 12.

[0034] Suitable alkanolamine compounds include lower alkanolamines, which are primary, secondary and tertiary amines having from 1 to 10 carbon atoms. Examples of such alkanolamines include N-methylethanolamine (NMEA), monoethanolamine (MEA), diethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, cyclohexylamine diethanolamine and mixtures thereof.

[0035] In some embodiments, the alkanolamine is selected from the group consisting of methanolamine, triethanolamine (TEA), diethanolamine, N-methylethanolamine, N-methyldiethanolamine, diisopropanolamine, monoethanolamine (MEA), amino(ethoxy)ethanol (AEE), monoisopropanolamine, cyclohexylamine diethanol, and mixtures thereof. In some embodiments, the alkanolamine is selected from triethanolamine (TEA), N-methylethanolamine, monoethanolamine (MEA), amino(ethoxy)ethanol (AEE), monoisopropanolamine, and mixtures thereof. In other embodiments, the alkanolamine is selected from at least one of N-methylethanolamine, monoethanolamine (MEA), or mixtures thereof.

[0036] The amount of alkanolamine compound in the composition, for many applications, includes weight percentages within a range having beginning and ending points selected from the following number groups: 5, 7, 8, 10, 12, 15, 20, 25, 27, 30, 33, 35, 37, 40, 43, 45, 47, 50, 52, 55, 57, 60, 63, 65, 67, 70, 80, and 90. Exemplary ranges of alkanolamine compound in the compositions of the present invention may be included from about 10 wt% to about 70 wt% of the composition, particularly from about 20 wt% to 60 wt% of the composition. In some embodiments, the at least one alkanolamine compound comprises from about 10 wt% to about 65 wt%, more particularly, from about 10 to about 60 wt%, from about 10 to about 50 wt%, from about 15 to about 55 wt%, from about 25 to about 55 wt%, from about 5 to about 15 wt%, from about 25 to about 55 wt%, from about 30 to about 50 wt%, or from about 35 to about 50 wt% of the composition.

[0037] Multifunctional organic acid The composition disclosed herein comprises at least one polyfunctional organic acid. As used herein, the term "polyfunctional organic acid" refers to an acid or multi-acid having two or more carboxylic acid groups, or at least one carboxylic acid group and at least one hydroxyl group, including, but not limited to, (i) dicarboxylic acids (e.g., oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, etc.); dicarboxylic acids having aromatic moieties (e.g., phthalic acid, etc.) and combinations thereof; (ii) tricarboxylic acids (e.g., propane-1,2,3-tricarboxylic acid, citric acid, etc.), tricarboxylic acids having aromatic moieties (e.g., trimellitic acid, etc.) and combinations thereof; (iii) tetracarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA); and (iv) acids having at least one hydroxyl (-OH) group in addition to at least one carboxylic acid group (excluding phenolic acids), such as lactic acid, gluconic acid, and glycolic acid. The polyfunctional organic acid component functions primarily as a corrosion inhibitor and / or chelating agent for metals.

[0038] Preferred polyfunctional organic acids include those having at least three carboxylic acid groups, for example. Polyfunctional organic acids having at least three carboxylic acid groups are highly miscible with aprotic solvents. Examples of such acids include tricarboxylic acids (e.g. citric acid, 2-methylpropane-1,2,3-triscarboxylic acid, benzene-1,2,3-tricarboxylic acid [hemimellitic acid], propane-1,2,3-tricarboxylic acid [tricarballylic acid], 1,cis-2,3-propene tricarboxylic acid [aconitic acid] and similar), tetracarboxylic acids (e.g. butane-1,2,3,4-tetracarboxylic acid, cyclopentanetetra-1,2,3,4-carboxylic acid, benzene-1,2,4,5-tetracarboxylic acid [pyromellitic acid] and similar), pentacarboxylic acids (e.g. benzenepentacarboxylic acid) and hexacarboxylic acids (e.g. benzenehexacarboxylic acid [mellitic acid]) and similar. Citric acid, as well as other polyfunctional organic acids suitable for use in the compositions disclosed herein, functions as a chelating agent for aluminum. For example, citric acid is a tetradentate chelating agent, and chelation of citric acid with aluminum makes it an effective aluminum corrosion inhibitor.

[0039] The amount of polyfunctional organic acid (neat) in the compositions of the present disclosure will for many applications be a weight percent within a range having beginning and end points selected from the following number groups: 0.05, 0.07, 0.1, 0.3, 0.5, 0.7, 1, 1.2, 1.5, 1.7, 2, 2.3, 2.5, 2.7, 3, 3.5, 4, 4.5, 5, 10, 13, 15, 17, and 20. is considered to constitute, for example, about 0.05 wt% to about 20 wt%, about 0.05 wt% to about 15 wt%, about 0.05 wt% to about 10 wt%, about 0.1 wt% to about 1.5 wt%, about 0.5 wt% to about 3.5 wt%, about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 10 wt%, about 0.5 wt% to about 7.5 wt%, or about 1 wt% to about 5 wt%.

[0040] Corrosion Inhibitors The compositions disclosed herein include at least one phenol-type corrosion inhibitor. Phenol-type inhibitors include, for example, t-butylcatechol, catechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, or mixtures thereof. Typically, the phenol-type inhibitor acts as a corrosion inhibitor for aluminum. The at least one phenol-type inhibitor can be selected from, or can be selected from the group consisting of, t-butylcatechol, catechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol. The at least one phenol-type inhibitor in the compositions disclosed herein inhibits metal corrosion by scavenging oxygen-containing corrosion species in the medium. In alkaline solutions, oxygen reduction is the cathodic reaction, and corrosion can be controlled by reducing the oxygen content using a scavenger. In some embodiments, the phenol-type inhibitor includes catechol, gallic acid, and / or resorcinol.

[0041] For many applications, the phenolic type corrosion inhibitor, which may be at least one selected from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, will comprise a weight percent of the composition within a range having a beginning and an end point selected from 0.1, 1, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 6.5, 7, 8, 9, and 10. For example, the cleaning composition may include at least one phenolic type inhibitor in an amount of about 0.1 to about 10 wt%, about 0.1 to about 7 wt%, about 1 to about 7 wt%, about 2 to about 7 wt%, about 0.1 to about 6 wt%, or about 1 to about 5 wt% of the cleaning composition.

[0042] Auxiliary metal chelating agents (optional) An optional component that can be used in the cleaning composition of the present invention is a supplementary metal chelating agent. The chelating agent can function to improve the composition's ability to hold metals in solution and promote dissolution of metal residues. Thus, at least one phenolic corrosion inhibitor, which can be selected from t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid and resorcinol, functions as an aluminum chelating agent, while the supplementary chelating agent can function to chelate metals other than aluminum. Typical examples of the auxiliary chelating agents useful for this purpose are the following organic acids: (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylenetetraaminehexaacetic acid (TTHA) and 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), their isomers and salts. It is understood that the aforementioned chelating agents are polyfunctional organic acids, and EDTA is mentioned as an example of a useful polyfunctional organic acid and chelating agent. It should be noted that if a chelating agent is present in the cleaning composition of the present invention, it is different from one or more of the polyfunctional acids and phenol-containing inhibitors in the composition.

[0043] For many applications, the auxiliary chelating agent, if used, will be present in the composition in a weight percent of the composition within a range having beginning and ending points selected from the following number groups: 0, 0.1, 1, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 6.5, 7, 8, 9, 10, 12, 14, 16, 18, and 20. For example, the chelating agent may be present in an amount of 0 to about 5 wt%, about 0.1 to about 20 wt%, about 2 to about 10 wt%, or about 0.1 to 2 wt% of the composition.

[0044] Preferably, the compositions disclosed herein are substantially free of or free of hydroxylamine or HA derivatives.In addition, the compositions of the present invention may be substantially free of or free of one or more of the following, in any combination: abrasives, inorganic acids, inorganic bases, surfactants, oxidizing agents, peroxides, quinones, fluoride-containing compounds, chloride-containing compounds, phosphorus-containing compounds, metal-containing compounds, quaternary ammonium hydroxides, quaternary amines, amino acids, ammonium hydroxides, alkylamines, anilines or aniline derivatives, and metal salts.In some embodiments, for example, the compositions of the present invention are substantially free of or free of hydroxylamine and tetramethylammonium hydroxide.

[0045] In one embodiment of the invention, a composition useful for removing residue and photoresist from a semiconductor substrate is provided, comprising, consisting essentially of, or consisting of: about 30 to about 40 wt. % NMP or DMSO; about 40 to about 50 wt. % alkanolamine selected from the group consisting of N-methylethanolamine, monoethanolamine, and mixtures thereof; about 0.5 to about 3.5 wt. % citric acid; about 2.0 to about 4 wt. % at least one selected from, or selected from the group consisting of, catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol; and the balance being water, and is substantially free or free of hydroxylamine, with the total weight percentage of the components equaling 100 percent.

[0046] In another embodiment of the present invention, a composition useful for removing residue and / or photoresist from a semiconductor substrate is provided, comprising: about 5 to about 50 wt. % water; about 20 to about 60 wt. % water-miscible organic solvent selected from the group consisting of N-methylpyrrolidone (NMP), DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof; about 20 to about 70 wt. % alkane; and from about 0.1 to about 10 wt. % of at least one phenol-type corrosion inhibitor selected from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, and is substantially free or free of hydroxylamine, the total weight percentages of the components equaling 100 percent.

[0047] In another embodiment of the present invention, a composition useful for removing residue and / or photoresist from a semiconductor substrate is provided, comprising: about 10 to about 30 wt % or about 5 to about 15 wt % water; about 20 to about 60 wt % water-miscible organic solvent selected from or consisting of N-methylpyrrolidone (NMP), DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof; about 20 to about 50 wt % water-miscible organic solvent selected from the group consisting of; Compositions are provided that comprise, consist essentially of, or consist of at least one alkanolamine; from about 0.1 to about 10 wt. % of at least one polyfunctional organic acid; and from about 0.1 to about 5 wt. % of at least one phenolic-type corrosion inhibitor selected from, or consisting of, catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, and are substantially free or free of hydroxylamines, with the total weight percentage of the components equaling 100 percent.

[0048] In another embodiment of the present invention, a composition useful for removing residue and / or photoresist from a semiconductor substrate is provided, comprising, consisting essentially of, or consisting of about 5 to about 25 wt. % water; about 20 to about 60 wt. % water-miscible organic solvent; about 20 to about 50 wt. % at least one alkanolamine; about 0.1 to about 10 wt. % at least one multifunctional organic acid; and about 0.1 to about 5 wt. % at least one phenol-type corrosion inhibitor selected from, or consisting of, catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, and is substantially free or free of hydroxylamine, with the total weight percentage of the components equaling 100 percent.

[0049] Typically, the cleaning compositions of the present invention are prepared by mixing the components together in a container at room temperature until all solids are dissolved in the liquid medium (i.e., water, solvent or mixtures thereof).

[0050] The cleaning composition of the present invention can be used to remove undesired residues and photoresist from substrates. It is believed that the composition can be used with particularly good advantage in cleaning semiconductor substrates on which residues and / or photoresist are deposited or formed during the process for manufacturing semiconductor devices; examples of such residues include resist compositions in the form of films (both positive and negative), and etching deposits formed during dry etching, as well as chemically decomposed resist films. The use of the composition is particularly effective when the residues to be removed are resist films and / or etching deposits on semiconductor substrates having metal films exposed on the surface. Examples of substrates that can be cleaned by using the composition of the present invention without attacking the substrate itself include metal substrates, such as aluminum; titanium / tungsten; aluminum / silicon; aluminum / silicon / copper; silicon oxide; silicon nitride; aluminum nitride; and gallium / arsenide. Typically, such substrates contain residues including photoresist and / or post-etching deposits.

[0051] Examples of resist compositions that can be effectively removed by using the cleaning composition of the present invention include photoresists containing ester or ortho-naphthoquinone and a novolac type binder, and chemically amplified resists containing block polyhydroxystyrene or copolymers of polyhydroxystyrene and a photoacid generator. Examples of commercially available photoresist compositions include AZ 1518, AZ 4620 from Clariant Corporation, photoresist S1400, APEX-E from Shipley Company, Inc. TM Positive DUV, UV5 TM Positive DUV, Megaposit TM SPR TM 220 Series; Megaposit TM SPR TM3600 series; photoresists KRF (registered trademark) series, ARF (registered trademark) series from JSR Microelectronics; and Photoresists TSCR series and TDUR-P / N series from Tokyo Ohka Kogyo Co., Ltd.

[0052] The cleaning compositions disclosed herein can be used to remove post-etch and ashing residues, other organic and inorganic residues, and polymeric residues from semiconductor substrates at relatively low temperatures with little corrosive effect, e.g., low metal etch rates. The cleaning compositions of the present invention, when used in the method of the present invention, typically provide an etch rate of less than 2 Å / min for some metals, e.g., Al, AlCu, and / or W, when the cleaning composition is at a temperature of 60° C. or less, or an etch rate of less than 1 Å / min at a temperature of 60° C. or less. The cleaning compositions of the present invention, when used in the method of the present invention, typically provide an etch rate of less than 4 Å / min for some metals, e.g., AlN, when the cleaning composition contacts a substrate at 60° C. or less, or an etch rate of less than 1 Å / min at a temperature of 50° C. or less.

[0053] The cleaning composition should be applied to the surface for a period of time sufficient to achieve the desired cleaning effect. The time will vary depending on many factors, including, for example, the nature of the residue, the temperature of the cleaning composition, and the particular cleaning composition used. In general, the cleaning composition can be used by, for example, contacting the substrate at a temperature of about 25°C to about 85°C, about 45°C to about 65°C, or about 55°C to about 65°C for about 1 minute to about 1 hour, followed by one or more rinse steps (solvent and / or water) to rinse the cleaning composition from the substrate, and drying the substrate.

[0054] Thus, in another aspect, the present invention provides a method for removing residue from a substrate, the method comprising the steps of contacting the substrate with a cleaning composition as described above; rinsing the substrate with an organic solvent and then with water; and drying the substrate.

[0055] The contacting step can be performed by any suitable means, such as by immersion, by spraying, or via a single wafer process; any method that utilizes a liquid for the removal of photoresist, ashing or etching deposits and / or contaminants can be used.

[0056] Typically, the deionized water rinse step follows the intermediate organic solvent rinse and is performed by any suitable means, such as by immersion or spraying techniques, to wash the substrate with deionized water. The organic solvent rinse includes isopropyl alcohol or NMP. The water rinse can be with carbonated water. Furthermore, the prior art amine-based cleaning compositions etch silicon from the substrate. The use of the composition of the present invention minimizes the damage of silicon in such substrates.

[0057] The drying step may be carried out by any suitable means, such as by isopropyl alcohol (IPA) vapor drying, by heat, or by centripetal force.

[0058] Those skilled in the art will appreciate that the cleaning compositions of the present invention can be modified to achieve suitable cleaning without damaging the substrate so that high throughput cleaning can be maintained in the manufacturing process. For example, those skilled in the art will appreciate that variations in the amounts of some or all of the components can be made depending on the composition of the substrate being cleaned, the nature of the residue being removed, and the particular process parameters being used.

[0059] Although the invention has been described principally in connection with cleaning semiconductor substrates, the cleaning compositions of the invention can be used to clean any substrate containing organic and inorganic residues. EXAMPLES

[0060] The following examples are provided for the purpose of further illustrating the present invention and are not intended to limit the invention in any manner.

[0061] General Procedure for Preparing the Cleaning Composition All compositions of interest in this example were prepared by mixing 500 g of material in a 600 mL beaker with a Teflon coated stir bar and storing in a plastic bottle. Liquid components can be added in any order before the solid components.

[0062] Substrate Composition The substrates used in this example were Al metal lines and Al pads. The Al metal line or Al pad substrates consisted of one or more of the following layers: AlN, W, TiN, Al, TiN, Ti metallurgy, patterned and etched by reactive ion etching (RIE). The photoresist was not removed by oxygen plasma ashing. The photoresist was cleaned without an ashing step and without undesired etching of the contacted material using the compositions evaluated herein. The photoresist used in this example was MEGAPOSIT TM SPR3622, a positive photoresist from Dow.

[0063] Processing conditions Cleaning tests were performed in a beaker filled with 100 mL of the cleaning composition using a round Teflon stir bar. If necessary, the cleaning composition was heated to the desired temperature on a hot plate. Wafer segments approximately ½ inch by ½ inch in size were placed in a holder and immersed in the composition at the desired temperature for the desired time.

[0064] Upon completion, the segments were then rinsed with an intermediate solution of NMP or IPA for 3 minutes, then rinsed with DI water in an overflow bath, then dried using compressed nitrogen gas, and then analyzed for cleanliness using SEM microscopy.

[0065] Etch rate measurement procedure Blanket Al or W wafer coupons were analyzed for metal layer thickness using ResMap software from Creative Design Engineering, Inc. (Long Island City, NY). TM The thickness was measured by measuring the resistance of the layer using a Model 273 Resistance Instrument. The thickness of the metal layer of the coupon was first measured. The coupon was then immersed in the composition at the desired temperature for the desired time. After treatment, the coupon was removed from the composition, rinsed with deionized water, dried, and the thickness of the metal layer was measured again. A graph of the change in thickness as a function of immersion time was generated, and the etch rate (Angstroms / minute) was determined from the slope of the curve.

[0066] The etch rate of aluminum nitride (AlN) was evaluated by measuring the change in thickness, measured using a Filmtek Ellipsometry method. The thickness of the AlN is measured before and after immersion in the composition under the desired process conditions. A graph of the change in thickness as a function of immersion time was generated and the etch rate (Angstroms / minute) was determined from the slope of the curve.

[0067] The cleaning results were confirmed by optical microscopy and scanning electron microscopy (SEM). Resist removal was defined as "clean" if all resist was removed from the surface of the wafer coupon; "almost clean" if at least 95% of the resist was removed from the surface; and "partially clean" if approximately 80% of the resist was removed from the surface.

[0068] result The following examples describe cleaning compositions for the removal of photoresist and antireflective coatings (ARCs) from substrates for semiconductor devices. The solutions described contain DMSO, NMP, NMEA or MEA, water, citric acid and / or catechol, or other components as shown in the table below.

[0069] The effect of corrosion inhibitors on metal etch rate is shown in Table 1. The addition of citric acid and catechol improved the cleaning performance of photoresist and ARC from the substrate. Both citric acid and catechol reduced the metal etch rate with the best results when used together. Table 1. Effect of combinations of corrosion inhibitors in formulations [Table 1]

[0070] The effect of different organic solvents on the metal etching rate is shown in Table 2. Under the same processing conditions, the solvent had a slight effect on the metal etching rate. Table 2. Effect of different solvents on etching rate. [Table 2]

[0071] The effect of different polyfunctional organic acids on the metal etch rate is shown in Table 3. Compared with Comparative Example 2, different polyfunctional organic acids decreased the metal etch rate. Table 3. Effect of multifunctional organic acids on etching rate. [Table 3]

[0072] The effect of phenolic type corrosion inhibitors on metal etch rates was tested. The addition of phenolic type inhibitors decreased the metal etch rates, namely, the etch rates of AlCu and W, as shown in Table 4. Table 4. Effect of phenolic corrosion inhibitors on etch rate. [Table 4]

[0073] The formulations listed in Table 5 can effectively remove photoresist and ARC. The addition of citric acid can greatly reduce the etch rate of Al-Cu and W. Table 5. Effect of citric acid concentration [Table 5]

[0074] Example 2: Catechol as a corrosion inhibitor Table 3 shows that catechol can act as a corrosion co-inhibitor for both Al-Cu and W. Table 6. Effect of catechol concentration [Table 6]

[0075] Example 3: Optimization of corrosion inhibitors Table 7 shows that at an initial catechol concentration of 2 wt%, increasing the citric acid concentration decreases the metal etch rate for both Al-Cu and W. Table 7. Effect of citric acid concentration in the presence of catechol. [Table 7]

[0076] Example 4: Evaluation of Alkanolamines Referring to Table 8, the following results show that either MEA or NMEA is effective in the compositions disclosed herein. Example 1A showed excellent metal compatibility. Table 9 shows that the surface roughness of AlN after treatment of 1A did not change and was consistent with its very low AlN etch rate. Table 8. Effects of different alkanolamines [Table 8] Table 9. Surface roughness of blanket AlN films [Table 9]

[0077] Example 5: Optimization of water content Table 10 shows that for some embodiments, the optimized water content may range from about 10-18%. Table 10. Effect of water concentration on cleaning [Table 10]

[0078] The foregoing examples and descriptions of preferred embodiments should be taken as illustrative, rather than limiting, of the present invention as defined by the claims. As will be readily understood, various variations and combinations of the features defined above can be utilized without departing from the present invention as defined in the claims. Such variations are not to be regarded as departing from the spirit and scope of the present invention, and all such variations are intended to be included within the scope of the appended claims.

Claims

1. 1. A composition useful for removing residue and photoresist from a semiconductor substrate, comprising: about 5 to about 60 wt % water; from about 10 to about 90 wt % of at least one water-miscible organic solvent selected from pyrrolidones, sulfonyl-containing solvents, acetamides, glycol ethers, polyols, cyclic alcohols, and mixtures thereof; from about 5 to about 90 wt % of at least one alkanolamine; From about 0.05 to about 20 wt % of at least one polyfunctional organic acid; and From about 0.1 to about 10 wt % of at least one phenolic type corrosion inhibitor and being substantially free of hydroxylamine.

2. 10. The composition of claim 1 comprising from about 10 to about 60 wt % or from about 30 to about 50 wt % of said at least one water-miscible organic solvent.

3. 3. The composition of claim 1 or 2, comprising from about 10 to about 50 wt % or from about 35 to about 50 wt % of the at least one alkanolamine.

4. The composition of any one of claims 1 to 3, comprising from about 0.1 to about 20 wt % or from about 0.1 to about 5 wt % of the at least one polyfunctional organic acid.

5. The composition of any one of claims 1 to 4, comprising from about 1 to about 7 wt % of said at least one phenolic-type corrosion inhibitor.

6. The composition of any one of claims 1 to 5, comprising from about 5 to about 30 wt % or from about 5 to about 15 wt % of said water.

7. 7. The composition of any one of claims 1 to 6, wherein the water-miscible solvent is selected from N-methylpyrrolidone (NMP), sulfolane, dimethylsulfoxide (DMSO), dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), tripropylene glycol methyl ether, propylene glycol propyl ether, diethylene glycol n-butyl ether, ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, tetrahydrofurfuryl alcohol, benzyl alcohol, and mixtures thereof.

8. 8. The composition of any one of claims 1 to 7, wherein the at least one water-miscible organic solvent is selected from N-methylpyrrolidone (NMP), dimethylacetamide (DMSO), dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof.

9. 9. The composition of any one of claims 1 to 8, wherein the at least one alkanolamine is selected from N-methylethanolamine (NMEA), monoethanolamine (MEA), diethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethoxy)ethanol, triethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, cyclohexylamine diethanolamine, and mixtures thereof.

10. The composition of any one of claims 1 to 9, wherein the alkanolamine comprises N-methylethanolamine.

11. The composition of any one of claims 1 to 10, wherein the alkanolamine comprises monoethanolamine.

12. The composition of any one of claims 1 to 11, wherein the at least one phenol-type corrosion inhibitor is selected from t-butylcatechol, catechol, 2,3-dihydroxybenzoic acid, gallic acid, resorcinol, and mixtures thereof.

13. 13. The composition of any one of claims 1 to 12, wherein the at least one polyfunctional organic acid is selected from citric acid, malonic acid, malic acid, tartaric acid, oxalic acid, phthalic acid, maleic acid, (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), and mixtures thereof.

14. The composition of any one of claims 1 to 13, wherein the at least one polyfunctional organic acid comprises citric acid.

15. The composition of any one of claims 1 to 14, wherein the at least one water-miscible organic solvent comprises NMP.

16. The composition of any one of claims 1 to 15, wherein the at least one water-miscible organic solvent comprises DMSO.

17. 17. The composition of any one of claims 1 to 16, further comprising at least one chelating agent, said at least one chelating agent being different from said at least one corrosion inhibitor and said at least one multifunctional acid.

18. 18. The composition of claim 17, wherein the at least one chelating agent is present in the composition in an amount of about 0.1 to about 2 wt %.

19. 19. The composition of claim 17 or 18, wherein the at least one chelating agent is selected from (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo-)tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid (DETPA), ethylenediaminetetrapropionic acid, (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), N,N,N',N'-ethylenediaminetetra(methylenephosphonic) acid (EDTMP), triethylenetetraaminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (DHPTA), isomers or salts thereof, and mixtures thereof.

20. 20. The composition according to any one of claims 1 to 19, having a pH value of from 9 to 13 or from 10 to 12.

21. 1. A method for removing residue or photoresist from a substrate comprising at least one of aluminum copper alloy, aluminum nitride, and tungsten, comprising: A contacting step of contacting the substrate with a cleaning composition according to any one of claims 1 to 20; and rinsing said substrate with water. A method comprising:

22. 22. The method of claim 21, wherein the temperature of the cleaning composition is from about 25°C to about 85°C or from about 45°C to about 65°C during the contacting step.

23. 23. The method of claim 21 or 22, further comprising rinsing the substrate with an organic solvent prior to rinsing the substrate with water.

24. 24. The method of claim 21 or 23, wherein the substrate is a semiconductor substrate.

25. 25. The method of any one of claims 21 to 24, wherein the substrate comprises an aluminum copper alloy and the method provides an etch rate of the aluminum copper alloy of less than 2 Å / min as measured after the water rinsing step, or preferably less than 1 Å / min when the temperature of the cleaning composition during the contacting step is 60° C. or less.

26. 26. The method of any one of claims 21-25, wherein the substrate comprises tungsten and the method provides an etch rate of the tungsten of less than 2 Å / min as measured after the water rinsing step, or preferably less than 1 Å / min when the temperature of the cleaning composition during the contacting step is 60° C. or less.

27. 27. The method of any one of claims 21-26, wherein the substrate further comprises aluminum nitride, and the method provides an etch rate of the aluminum nitride measured after the water rinsing step of less than 4 Å / min when the temperature of the cleaning composition during the contacting step is 60° C. or less, or less than 1 Å / min when the temperature of the cleaning composition during the contacting step is 50° C. or less.

28. The method of any one of claims 21 to 27, further comprising the step of drying the substrate after the step of rinsing with water.

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