Cleaning composition for semiconductor substrates

Abstract

A composition and method useful for removing residues and photoresist from a semiconductor substrate, comprising about 5 to about 60 wt% water; about 10 to about 90 wt% water miscible organic solvent; about 5 to about 90 wt% at least one alkanolamine; about 0.05 to about 20 wt% at least one polyfunctional organic acid; and about 0.1 to about 10 wt% at least one phenol-type corrosion inhibitor, substantially free of hydroxylamine.

Description

Technical Field

[0001] The present invention provides a cleaning composition that can be used for various applications including, for example, removing unwanted resist films, post-etching and post-ashing residues on a semiconductor substrate. Specifically, the present invention is particularly useful for removing photoresist, etching residues and anti-reflective coatings (ARC), does not contain hydroxylamine, and exhibits 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 silicide, or dielectrics.

Background Art

[0002] The background of the present invention is described in connection with the use of the present invention in cleaning applications including the manufacture of integrated circuits. However, the use of the present invention has broader applications, as described below.

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

[0004] To ensure that only the desired portion of the film is removed, a photolithography process is used, thereby transferring a computer-designed photomask pattern onto the film surface. The mask works to identify the areas of the film to be selectively processed. This pattern is formed from a photoresist material, which is a photosensitive material that is spun onto an integrated circuit wafer during the process in thin film form and exposed to high-intensity radiation passing through the photomask. The exposed or unexposed photoresist material, depending on its composition, is typically dissolved by a developer, leaving a pattern where etching occurs in selected areas while preventing etching in other areas. For example, positive-type resists are widely used as masking materials to create patterns on the substrate that become vias, trenches, contact holes, etc., when etching occurs.

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

[0006] Furthermore, typically, such dry etching processes make it extremely difficult to remove the photoresist. For example, in complex semiconductor devices such as advanced DRAMs and logic devices with multiple layers of interconnect wiring processes, reactive ion etching (RIE) is used to create vias through the intermediate dielectric 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 a complex mixture on the substrate, which may include, for example, resputtered oxide material, polymeric material due to etching gas, and organic material due to the resist used to draw the vias.

[0007] In addition, to allow for final finishing operations following the completion of the etching process, photoresist and etching residues must be removed from the protected areas of the wafer. This can be achieved in a plasma "ashing" process using a suitable plasma ashing gas. Typically, this is done at high temperatures, for example, above 200°C. Ashing converts many organic residues into 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 vias where they may exist. As a result, ashing-treated substrates are often treated with cleaning compositions, typically called "liquid stripping compositions" or "cleaning compositions," to remove strongly adhesive residues from the substrate. It has been found that finding a suitable cleaning composition for removing these residues without adversely affecting the metal circuits, such as corrosion, dissolution, or tarnishing of the metal circuits, can be problematic. Failure to completely remove or neutralize the residues can result in breaks in the circuit wiring and an undesirable increase in electrical resistance.

[0008] Dry ashing of photoresists using plasma, which is applied after etching plasma, results in the decomposition of low-k materials. Therefore, the ashing process is not suitable for cleaning photoresists, either due to the compatibility of other layers such as the metal layer AlCu, resulting from the integration scheme, or because the process does not require an ashing process. Alternative wet chemicals 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 any of the other layers, such as the metal layer, e.g., AlCu or AlN, or the dielectric layer.

[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 its use. In this art, 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 novel or further materials present in the structure on the semiconductor substrate, such as aluminum nitride, aluminum-copper alloys, and dielectric materials. High compatibility means that the cleaning composition does not cause etching damage to these materials, or causes only limited etching damage, and therefore does not cause etching damage to structures made from these materials, or causes only limited etching damage. As the structure on the substrate shrinks, it is necessary to continuously improve the cleaning composition to improve cleaning performance while reducing etching of materials on the substrate in order to improve chip performance.

[0011] Therefore, there is a need in this field for a cleaning composition that has high compatibility requirements for aluminum-copper alloys, aluminum nitride, tungsten, aluminum oxide, and dielectrics, does not contain hydroxylamine, is non-toxic, is environmentally friendly for various final cleaning operations, including the stripping of photoresists and plasma ashing residues generated by, for example, plasma processes, and does not have the aforementioned drawbacks. [Overview of the project] [Problems that the invention aims to solve]

[0012] The present invention satisfies this requirement by providing a composition useful for removing residues and photoresists from semiconductor substrates by minimal etching of aluminum-copper alloys, aluminum nitride, and tungsten, the composition comprising, substantially, or comprising, about 5 to about 60 wt% water; about 10 to about 90 wt% at least one water-miscible organic solvent selected from pyrrolidone, sulfonyl-containing solvents, acetamide, glycol ethers, polyols, cyclic alcohols, and mixtures thereof; about 5 to about 90 wt% at least one alkanolamine; about 0.05 to about 20 wt% at least one polyfunctional organic acid; and about 0.1 to about 10 wt% at least one phenol-type corrosion inhibitor, and not containing hydroxylamine.

[0013] In one embodiment, the composition contains 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, and The material comprises: at least one water-miscible organic solvent selected from or from the group consisting of cindyl alcohols and mixtures thereof; at least one alkanolamine in about 5 to about 90 wt%; at least one polyfunctional organic acid in about 0.1 to about 20 wt%; and at least one phenol-type corrosion inhibitor in about 0.1 to about 10 wt%, such as selected from or from the group consisting of catechol, 2,3-dihydroxybenzoic acid and resorcinol, or at least one selected from gallic acid or t-butylcatechol, and does not contain 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 embodiment, the present invention relates to a method for removing a photoresist or residue from a substrate comprising one or more of aluminum, aluminum-copper alloy, tungsten, aluminum nitride, silicon oxide, and silicon, A composition useful for removing residues and photoresist from a semiconductor substrate, comprising about 5 to about 60 wt% water; selected from or from the group consisting of pyrrolidone, sulfonyl-containing solvents, acetamide, glycol ethers, polyols, cyclic alcohols, and mixtures thereof, including 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. A step of contacting a substrate with a composition that contains, substantially comprises, or is composed of, a composition that does not contain hydroxylamine, and which can be selected from a mixture or from N-methylpyrrolidone (NMP), dimethyl sulfoxide (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 polyfunctional organic acid; and about 0.1 to about 10 wt% of at least one phenol-type inhibitor, which can be selected from or from the group consisting of gallic acid, t-butylcatechol, catechol, 2,3-dihydroxybenzoic acid, and resorcinol; The process involves rinsing the substrate with water; The process of drying the substrate and This provides a method that includes [something].

[0015] The compositions of the present invention have superior cleaning properties, lower toxicity, and are more environmentally acceptable compared to compositions currently used in the semiconductor industry. Furthermore, the compositions of the present invention exhibit compatibility with various metal and dielectric materials commonly found on semiconductor substrates. [Modes for carrying out the invention]

[0016] All references cited herein, including publications, patent applications, and patents, are incorporated herein by reference to the same extent as they are individually and specifically indicated, and to the same extent as they are described herein in whole, so as to be incorporated by reference.

[0017] In the context describing the present invention (particularly in the context of the appended claims), the use of the terms “a,” “an,” and “the,” and similar demonstrative pronouns, is construed to cover both singular and plural unless otherwise indicated herein or expressly refuted by the context. The terms “comprising,” “having,” “including,” and “containing” are construed as open-ended terms (i.e., “including, but not limited to”) unless otherwise indicated herein. The descriptions of ranges of values ​​herein are intended to function simply as abbreviations for each individual value within that range, unless otherwise indicated herein, and each individual value is incorporated herein as if it were described separately herein. All methods described herein may be performed in any suitable order unless otherwise indicated herein or expressly refuted by the context. Any and all examples or illustrative words provided herein (for example, the use of “such as”) are merely intended to better illustrate the invention and, unless otherwise stated, do not limit the scope of the invention. No word herein should be construed as indicating that any element not described is essential for the practice of the invention. The use of the term “comprising” herein and in the claims encompasses the narrower terms “substantially from” and “consisting of.”

[0018] Embodiments of the present invention, including the best form known to the inventors, are described herein for carrying out the invention. Variations of these embodiments will be apparent to those skilled in the art by reading the following description. The inventors expect that those skilled in the art will appropriately use such variations, and the inventors intend that the invention will be carried out separately from those specifically described herein. Accordingly, the invention includes all modifications and equivalents of the subject matter described in the claims appended herein, as permitted by applicable law. Furthermore, any combination of the above elements in all possible variations of the invention is encompassed by the invention, unless otherwise shown herein or otherwise expressly denied by the context.

[0019] For ease of reference, “microelectronic devices” or “semiconductor substrates” refer to wafers, flat panel displays, phase-change memory devices, solar panels and other products comprising solar substrates, photocells, and micro-electromechanical systems (MEMS) manufactured for use in microelectronics, integrated circuits, 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 or may not be doped. The term “microelectronic devices” is understood to include any substrate that ultimately becomes a microelectronic device or microelectronic assembly, without any limitation on the method by which it is manufactured.

[0020] As defined herein, "low-k dielectric material" or "dielectric" corresponds to any material having a dielectric constant of less than about 3.5 that is used as a dielectric material in a stacked microelectronic device. 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 has been recognized that low-k dielectric materials can have various densities and various porosities.

[0021] As used herein, "substantially free of" is defined as less than 0.001 wt%. "Substantially free of" also includes 0.000 wt%. The term "free of" 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 the weight percent ranges of specific components of the composition include a lower limit of 0, such components may or may not be present in various specific embodiments of the composition. For example, if such components are present, they may be present at a concentration as low as about 0.001 weight percent relative to the total weight of the composition in which these components are used. The specified weight percent is relative to the total weight of the composition and is 100% in total.

[0024] The cleaning composition is required for the cleaning of Al BEOL (wiring process) of either ashed or non-ashed substrates. The key property of an effective cleaning agent is the ability to attack and dissolve post-etching and post-ashing residues without substantially attacking the underlying interconnect dielectric or metal; it is well known to those skilled in the art that the selection of corrosion inhibitors may also be key for controlling the metal etching rate. Metals that may be present include aluminum, aluminum-copper alloys, aluminum-containing metals such as aluminum nitride, aluminum oxide, titanium-containing metals such as Ti, TiN, tantalum-containing metals such as Ta, TaN, tungsten-containing metals such as tungsten, or silicides of tungsten; or other silicides. Further, a dielectric may be present thereon. Particular interest lies in 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 an amount effective to efficiently remove residues or photoresist from a substrate, such as a semiconductor substrate. In applications related to semiconductor substrates, such residues include, for example, photoresist, photoresist residues, ashing residues and etching residues, such as those caused by reactive ion etching. Further, the semiconductor substrate includes metals, silicon, silicates and / or intermediate dielectric materials, such as deposited silicon oxide, that will 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 composition of the present invention is compatible with such materials as it exhibits low metal and / or dielectric etching rates.

[0026] The cleaning composition of the present invention comprises about 5 to about 60 wt% water; pyrrolidone, e.g., N-methylpyrrolidone (NMP); sulfonyl-containing solvent, e.g., dimethyl sulfoxide (DMSO) and sulfolane; acetamide, e.g., dimethylacetamide (DMAC); glycol ether, e.g., 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; polyol, e.g., ethylene glycol, propylene glycol (PG), 1,4-butanediol and glycerol; cyclic alcohol, e.g., tetrahydrof A composition comprising, substantially comprising, or consisting of: about 10 to about 90 wt% of a water-miscible organic solvent selected from or from the group consisting of leufuryl alcohol and benzyl alcohol; and mixtures thereof; about 5 to about 90 wt% of at least one alkanolamine; about 0.05 or 0.1 to about 20 wt% of at least one polyfunctional organic acid; and about 0.1 to about 10 wt% of at least one phenol-type corrosion inhibitor which can be selected from or from the group consisting of gallic acid, t-butylcatechol, catechol, 2,3-dihydroxybenzoic acid and resorcinol, and which substantially does not contain or does not contain hydroxylamine and / or substantially does not contain or does not contain quaternary ammonium hydroxide. The compositions disclosed herein are useful, in particular, for removing residues and photoresists from semiconductor substrates during the manufacture of microelectronic devices.

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

[0028] In many applications, water is considered to constitute, for example, about 5 to about 60 wt% of the composition. Another preferred embodiment of the present invention may contain about 5 to about 40 wt% water. Yet another preferred embodiment of the present invention may contain 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 in any weight percentage range defined 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 solvent 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: pyrrolidone, sulfonyl-containing solvents, acetamide, glycol ether, polyol, cyclic alcohol, and mixtures thereof. Cyclic alcohols are alcohols having a five-membered or six-membered carbocyclic ring. The carbocyclic ring may be aromatic or aliphatic, and may consist only of carbon atoms forming the ring, or it may contain one or more heteroatoms. An example of pyrrolidone is N-methylpyrrolidone (NMP). Examples of sulfonyl-containing solvents are sulfolane and dimethyl sulfoxide (DMSO). An example of acetamide is dimethylacetamide (DMAC). Examples of glycol ethers include dipropylene glycol monomethyl ether (DPGME), diethylene glycol monomethyl ether (DEGME), butyl diglycol (BDG), 3-methoxymethylbutanol (MMB), tripylene glycol methyl ether, propylene glycol propyl ether, and diethylene glycol n-butyl ether (for example, 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 combination of 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 dimethyl sulfoxide, dimethylacetamide, dipropylene glycol monomethyl ether, n-methylpyrrolidone (NMP), 3-methoxymethylbutanol (MMB), and diethylene glycol.

[0030] In other preferred embodiments, the water-miscible organic solvent is selected from or from the group 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 or 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 substantially not contain, or omit, any of the solvents of the aforementioned classification or individual species, either alone or in any combination. For example, the cleaning compositions of the present invention may substantially not contain pyrrolidone, sulfonyl-containing solvents, acetamide, glycol ethers, polyols and / or cyclic alcohols, or may substantially not contain, or omit, ethylene glycol, propylene glycol, THFA, DGME and / or MMB, for example.

[0032] For many applications, the amount of water-miscible organic solvent in the composition may be within a range having a starting and ending point 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 approximately 10 wt% to 90 wt% of the composition; approximately 10 wt% to 60 wt%; approximately 20 wt% to 60 wt%; approximately 10 wt% to 50 wt%; approximately 10 wt% to 40 wt%; approximately 10 wt% to 30 wt%; approximately 5 wt% to 30 wt%; 5 wt% to 15 wt%; approximately 10 wt% to 20 wt%; approximately 30 wt% to 70 wt%; approximately 30 wt% to 50 wt%; or approximately 20 wt% to 50 wt%.

[0033] Alkanolamine The compositions disclosed herein comprise 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-etching residues, and also functions as an electron-rich agent to attack post-etching residues and photoresist, thereby assisting in the dissolution of these undesirable materials. Preferably, the pH of the cleaning compositions 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 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, cyclohexylaminediethanol, and mixtures thereof.

[0035] In some embodiments, the alkanolamine is selected from methanolamine, triethanolamine (TEA), diethanolamine, N-methylethanolamine, N-methyldiethanolamine, diisopropanolamine, monoethanolamine (MEA), amino(ethoxy)ethanol (AEE), monoisopropanolamine, cyclohexylaminediethanol, and mixtures thereof, or from the group comprising these. 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 compounds in the composition, in many applications, includes weight percent within a range having a starting and ending point selected from the following 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. Examples of the range of alkanolamine compounds in the composition of the present invention include about 10 wt% to about 70 wt%, and particularly about 20 wt% to 60 wt%, of the composition. In some exact settings, at least one alkanolamine compound constitutes about 10 wt% to about 65 wt%, more particularly about 10 to about 60 wt%, about 10 to about 50 wt%, about 15 to about 55 wt%, about 25 to about 55 wt%, about 5 to about 15 wt%, about 25 to about 55 wt%, about 30 to about 50 wt%, or about 35 to about 50 wt% of the composition.

[0037] Multifunctional organic acid The compositions disclosed herein comprise at least one polyfunctional organic acid. As used herein, the term “polyfunctional organic acid” means 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, and includes, but is 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, e.g., 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), e.g., lactic acid, gluconic acid, and glycolic acid. The polyfunctional organic acid components primarily function as metal corrosion inhibitors and / or chelating agents.

[0038] Preferred polyfunctional organic acids include, for example, those having at least three carboxylic acid groups. 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 [tricarbaryl acid], 1,cis-2,3-propentricarboxylic 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 [merittic acid]) and similar. Citric acid, like 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 tetraconformate chelating agent, and the chelation of citric acid with aluminum makes it an effective corrosion inhibitor for aluminum.

[0039] The amount of polyfunctional organic acid (undiluted) in the compositions of this disclosure is, for many applications, within a range having a starting and ending point selected from the following 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, by weight percentage. This can be thought to constitute, for example, approximately 0.05 wt% to 20 wt%, approximately 0.05 wt% to 15 wt%, approximately 0.05 wt% to 10 wt%, approximately 0.1 wt% to 1.5 wt%, approximately 0.5 wt% to 3.5 wt%, approximately 0.1 wt% to 5 wt%, approximately 0.1 wt% to 10 wt%, approximately 0.5 wt% to 7.5 wt%, or approximately 1 wt% to 5 wt%.

[0040] Corrosion inhibitor The compositions disclosed herein comprise at least one phenol-type corrosion inhibitor. The phenol-type inhibitors include, for example, t-butylcatechol, catechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, or mixtures thereof. Typically, the phenol-type inhibitors act as corrosion inhibitors for aluminum. The at least one phenol-type inhibitor can be selected from or 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 prevents metal corrosion by removing oxygen-containing corrosive 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 remover. In some embodiments, the phenol-type inhibitor comprises catechol, gallic acid, and / or resorcinol.

[0041] For many applications, a phenol-type corrosion inhibitor, which may be selected from or at least one selected from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, is considered to constitute a weight percentage of the composition within a range having starting and ending points 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, a cleaning composition may contain at least one phenol-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] Metal chelating agent (optional) An optional component that can be used in the cleaning composition of the present invention is an auxiliary metal chelating agent. The chelating agent can function to enhance the composition's ability to retain metals in solution and to promote the dissolution of metal residues. Thus, at least one phenol-type 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 auxiliary chelating agent can function to chelate metals other than aluminum. Typical examples of these 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. The aforementioned chelating agents are polyfunctional organic acids, and EDTA is described as an example of a useful polyfunctional organic acid and chelating agent. Note that if a chelating agent is present in the cleaning composition of the present invention, it is distinct from one or more polyfunctional acids and phenol-containing inhibitors in the composition.

[0043] For many applications, when used, auxiliary chelating agents are considered to be present in the composition in a weight percentage of the composition within a range having a starting and ending point selected from the following 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 amounts 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 do not contain hydroxylamine or HA derivatives. In addition, the compositions of the present invention may substantially not contain, or do not contain, 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 hydroxide, quaternary amines, amino acids, ammonium hydroxide, alkylamines, aniline or aniline derivatives, and metal salts. In some embodiments, for example, the compositions of the present invention are substantially free of or do not contain hydroxylamine and tetramethylammonium hydroxide.

[0045] In one embodiment of the present invention, a composition useful for removing residues and photoresist from a semiconductor substrate is provided, comprising, substantially, 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 the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid and resorcinol; and the remainder being water, substantially free or free of hydroxylamine, and the total weight percentage of the components is equal to 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 or from the group consisting of N-methylpyrrolidone (NMP), DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof; and about 20 to about 70 wt% alkanol A composition is provided comprising, substantially comprising, or comprising, hydroxylamine; at least one polyfunctional organic acid in about 0.1 to about 10 wt%; and at least one phenol-type corrosion inhibitor in about 0.1 to about 10 wt% selected from or from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, and substantially not containing, or not containing, hydroxylamine, and the total weight percentage of the components is equal to 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% of a water-miscible organic solvent selected from or from the group consisting of N-methylpyrrolidone (NMP), DMSO, dimethylacetamide (DMAC), dipropylene glycol monomethyl ether (DPGME), ethylene glycol, propylene glycol (PG), and mixtures thereof; and about 20 to about 50 wt% of a small amount of A composition is provided which comprises, substantially comprises, or comprises, at least one alkanolamine; at least one polyfunctional organic acid in about 0.1 to about 10 wt%; and at least one phenol-type corrosion inhibitor in about 0.1 to about 5 wt% selected from or from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid, and resorcinol, and which substantially does not contain or contains hydroxylamine, and whose total weight percentage of components is equal to 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, or substantially comprising, 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 polyfunctional organic acid; and about 0.1 to about 5 wt% at least one phenol-type corrosion inhibitor selected from or from the group consisting of catechol, t-butylcatechol, gallic acid, 2,3-dihydroxybenzoic acid and resorcinol, and substantially not containing or not containing hydroxylamine, with the total weight percentage of the components equal to 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 the solids are dissolved in a liquid medium (i.e., water, a solvent, or a mixture thereof).

[0050] The cleaning composition of the present invention can be used to remove undesirable residues and photoresists from a substrate. The composition is considered to have particularly good advantages in the cleaning of semiconductor substrates on which residues and / or photoresists have been deposited or formed during the manufacturing process of semiconductor devices; examples of such residues include resist compositions in the form of films (both positive and negative), etching deposits formed during dry etching, and chemically decomposed resist films. The use of the composition is particularly effective when the residue to be removed is a resist film and / or etching deposit on a semiconductor substrate having a metal film exposed on its surface. Examples of substrates that can be cleaned by using the composition of the present invention without attacking the substrate itself include metal substrates, e.g., aluminum; titanium / tungsten; aluminum / silicon; aluminum / silicon / copper; silicon oxide; silicon nitride; aluminum nitride; and gallium / arsenide. Typically, such substrates contain residues including photoresists 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 an ester or ortho-naphthoquinone and a novolac-type binder, and chemically amplified resists containing a copolymer of block polyhydroxystyrene or polyhydroxystyrene and a photoacid generator. Examples of commercially available photoresist compositions include Clariant Corporation's AZ 1518, AZ 4620, and Shipley Company, Inc.'s photoresist S1400, APEX-E TM Positive DUV, UV5 TM Positive DUV, Megaposit TM SPR TM 220 Series; Megaposit TM SPR TMThe 3600 series includes JSR Microelectronics' KRF® series and ARF® series of photoresists, as well as Tokyo Ohka Kogyo Co., Ltd.'s TSCR series and TDUR-P / N series.

[0052] The cleaning compositions disclosed herein can be used to remove post-etching and ashing residues, other organic and inorganic residues, and polymeric residues from semiconductor substrates at relatively low temperatures, with minimal corrosive effects, and, for example, at low metal etching rates. When used in the methods of the present invention, the cleaning compositions typically provide etching rates of less than 2 Å / min for some metals, such as Al, AlCu, and / or W, when the cleaning composition is at a temperature of 60°C or below, or etching rates of less than 1 Å / min at a temperature of 60°C or below. When used in the methods of the present invention, the cleaning compositions typically provide etching rates of less than 4 Å / min for some metals, such as AlN, when the cleaning composition is in contact with the substrate at a temperature of 60°C or below, or etching rates of less than 1 Å / min at a temperature of 50°C or below.

[0053] The cleaning composition should be applied to the surface for a sufficient period of time to obtain the desired cleaning effect. This time varies depending on many factors, such as the properties of the residue, the temperature of the cleaning composition, and the cleaning composition used in particular. Generally, 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 rinsing steps (solvent and / or water) to rinse the cleaning composition from the substrate, and then drying the substrate.

[0054] Accordingly, in another embodiment, the present invention provides a method for removing residue from a substrate, 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 contact process can be carried out by any suitable means, such as immersion, spraying, or via a single-wafer process; any method utilizing liquids can be used for the removal of photoresist, ashing, or etching deposits and / or contaminants.

[0056] Typically, a rinsing step with deionized water follows an intermediate rinsing with an organic solvent and is carried out by any suitable means, for example, by immersion or spraying techniques to clean the substrate with deionized water. The rinsing with an organic solvent includes isopropyl alcohol or NMP. The rinsing with water may be with carbonated water. Furthermore, prior art amine-based cleaning compositions etch silicon from the substrate. The use of the composition of the present invention minimizes silicon damage in such substrates.

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

[0058] Those skilled in the art will understand that suitable cleaning can be achieved by modifying the cleaning composition of the present invention without damaging the substrate, so as to maintain high-throughput cleaning in the manufacturing process. For example, those skilled in the art will understand that, depending on the composition of the substrate to be cleaned, the nature of the residue to be removed, and especially the process parameters used, the amounts of some or all of the components can be changed.

[0059] Although the present invention has been described in principle in relation to the cleaning of semiconductor substrates, the cleaning composition of the present invention can be used to clean any substrate containing organic and inorganic residues. [Examples]

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

[0061] General procedure for preparing cleaning compositions All compositions intended for this embodiment were prepared by mixing 500 g of materials in a 600 mL beaker using a Teflon®-coated stirring rod, and then storing the mixture in a plastic bottle. Liquid components can be added in any order before the solid components.

[0062] composition of the base material The substrates used in this embodiment were Al metal wires and Al pads. The Al metal wire or Al pad substrate consisted of one or more of the following layers, patterned and etched by reactive ion etching (RIE): AlN, W, TiN, Al, TiN, and Ti metallurgy. The photoresist was not removed by oxygen plasma ashing. Without using an ashing process, the photoresist was cleaned using the compositions evaluated herein without undesirable etching of the contacting material. The photoresist used in this embodiment was MEGAPOSIT TM SPR3622 was a positive photoresist from Dow.

[0063] Processing conditions A cleaning test was performed in a beaker filled with 100 mL of cleaning composition using a round Teflon® stirring rod. If necessary, the cleaning composition was heated to the desired temperature on a hot plate. A wafer segment of approximately 1 / 2 inch × 1 / 2 inch size was placed in a holder and immersed in the composition at the desired temperature for the desired time.

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

[0065] Etching rate measurement procedure For blanket Al or W wafer coupons, regarding the thickness of the metal layer, see ResMap by Creative Design Engineering, Inc. (Long Island City, NY) TM The thickness was measured by measuring the resistance of the layers using a Model 273 resistor. First, the thickness of the metal layer of the coupon was measured. Then, the coupon was immersed in the composition at a desired temperature for a desired time. After the 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 created, and the etching rate (angstroms / min) was determined from the slope of the curve.

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

[0067] The cleaning results were confirmed using an optical microscope and a scanning electron microscope (SEM). Resist removal was defined as "clean" if all resist was removed from the wafer coupon surface; "mostly 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 example describes a cleaning composition for removing photoresist and anti-reflective coating (ARC) from substrates for semiconductor devices. The solution described contains DMSO, NMP, NMEA or MEA, water, citric acid and / or catechol, or other components, as shown in the table below.

[0069] Table 1 shows the effect of corrosion inhibitors on metal etching rate. 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 etching rate best when used together. Table 1. Effects of combinations of corrosion inhibitors in the formulation. [Table 1]

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

[0071] Table 3 shows the effect of different polyfunctional organic acids on the metal etching rate. Compared to Comparative Example 2, different polyfunctional organic acids reduced the metal etching rate. Table 3. Effect of polyfunctional organic acids on etching rate [Table 3]

[0072] The effect of phenol-type corrosion inhibitors on metal etching rates was tested. As shown in Table 4, the addition of phenol-type inhibitors reduced the metal etching rates, specifically those of AlCu and W. Table 4. Effect of phenol-type corrosion inhibitors on etching rate [Table 4]

[0073] The formulations listed in Table 5 can effectively remove photoresist and ARC. The addition of citric acid can significantly reduce the etching rates of Al-Cu and W. Table 5. Effects of citric acid concentration [Table 5]

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

[0075] Example 3: Optimization of corrosion inhibitor Table 7 shows that, at an initial catechol concentration of 2 wt%, increasing the citrate concentration reduces the metal etching rates for both Al-Cu and W. Table 7. Effect of citrate concentration in the presence of catechol [Table 7]

[0076] Example 4: Evaluation of alkanolamines Referring to Table 8, the following results indicate 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 remained unchanged after treatment of 1A and was consistent with its very low AlN etching rate. Table 8. Effects of Different Alkanolamines [Table 8] Table 9. Surface roughness of AlN blanket film [Table 9]

[0077] Example 5: Optimization of water content Table 10 shows that for several embodiments, the optimized water content may be in the range of approximately 10–18%. Table 10. Effect of water concentration on washing [Table 10]

[0078] The examples and descriptions of the preferred embodiments set forth above should be taken as illustrative, not limiting, the invention as defined by the claims. For ease of understanding, various variations and combinations of the features defined above can be used without departing from the invention as defined by the claims. Such variations are not considered to depart from the spirit and scope of the invention, and all such variations are intended to be included within the appended claims.

Claims

1. A composition useful for removing residues and photoresist from a semiconductor substrate, 5-60 wt% water; 10 to 80 wt% of at least one water-miscible organic solvent selected from pyrrolidone, sulfonyl-containing solvents, acetamides, polyols, cyclic alcohols, and mixtures thereof; 35–50 wt% of at least one alkanolamine; 0.05 to 20 wt% of at least one polyfunctional organic acid; and 0.1 to 10 wt% of at least one corrosion inhibitor A composition comprising, wherein the corrosion inhibitor is selected from phenol-type corrosion inhibitors, the composition does not contain glycol ether, the composition contains less than 0.001% by mass of hydroxylamine, and the composition contains less than 0.001% by mass of fluoride-containing compounds (excluding compositions containing hydroxides).

2. The composition according to claim 1, comprising 10 to 60 wt% of at least one water-miscible organic solvent.

3. The composition according to claim 1 or 2, comprising 0.1 to 20 wt% of the at least one polyfunctional organic acid.

4. The composition according to any one of claims 1 to 3, comprising 1 to 7 wt% of the at least one phenol-type corrosion inhibitor.

5. A composition according to any one of claims 1 to 4, comprising 5 to 30 wt% of the water.

6. The composition according to any one of claims 1 to 5, wherein the water-miscible organic solvent is selected from N-methylpyrrolidone (NMP), sulfolane, dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), 3-methoxymethylbutanol (MMB), ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, tetrahydrofurfuryl alcohol, benzyl alcohol, and mixtures thereof.

7. The composition according to any one of claims 1 to 6, wherein the at least one water-miscible organic solvent is selected from N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAC), ethylene glycol, propylene glycol (PG), and mixtures thereof.

8. The composition according to any one of claims 1 to 7, 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, cyclohexylaminediethanol, and mixtures thereof.

9. The composition according to any one of claims 1 to 8, wherein the alkanolamine comprises N-methylethanolamine.

10. The composition according to any one of claims 1 to 9, wherein the alkanolamine comprises monoethanolamine.

11. The composition according to any one of claims 1 to 10, 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.

12. The composition according to any one of claims 1 to 11, 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.

13. The composition according to any one of claims 1 to 12, wherein the at least one polyfunctional organic acid comprises citric acid.

14. The composition according to any one of claims 1 to 13, wherein the at least one water-miscible organic solvent comprises NMP.

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

16. The composition according to any one of claims 1 to 15, further comprising at least one chelating agent, wherein the at least one chelating agent is different from the at least one corrosion inhibitor and the at least one polyfunctional acid.

17. The composition according to claim 16, wherein the at least one chelating agent is present in the composition in an amount of 0.1 to 2 wt%.

18. The composition according to claim 16 or 17, 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.

19. A composition according to any one of claims 1 to 18, having a pH value of 9 to 13.

20. A method for removing residue or photoresist from a substrate containing at least one of aluminum-copper alloy, aluminum nitride, and tungsten, A contact step of bringing the substrate into contact with the cleaning composition according to any one of claims 1 to 19; and The process of rinsing the substrate with water. Methods that include...

21. The method according to claim 20, wherein the temperature of the cleaning composition is 25°C to 85°C during the contact step.

22. The method according to claim 20 or 21, further comprising the step of rinsing the substrate with an organic solvent before the step of rinsing the substrate with water.

23. The method according to claim 20 or 22, wherein the substrate is a semiconductor substrate.

24. The method according to any one of claims 20 to 23, wherein the substrate comprises an aluminum-copper alloy, and the method provides an etching rate of the aluminum-copper alloy of less than 2 Å / min when measured after the rinsing step with water, when the temperature of the cleaning composition during the contact step is 60°C or lower.

25. The method according to any one of claims 20 to 24, wherein the substrate comprises tungsten, and the method provides an etching rate of the tungsten of less than 2 Å / min when measured after the rinsing step with water, when the temperature of the cleaning composition during the contact step is 60°C or less.

26. The method according to any one of claims 20 to 25, wherein the substrate further comprises aluminum nitride, and the method provides an etching rate of the aluminum nitride measured after the rinsing step of water, which is less than 4 Å / min when the temperature of the cleaning composition during the contact step is 60°C or less, or less than 1 Å / min when the temperature of the cleaning composition during the contact step is 50°C or less.

27. The method according to any one of claims 20 to 26, further comprising the step of drying the substrate after the step of rinsing with water.

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