Cleaning formulation for removing residue on semiconductor substrates

Abstract

The present invention relates to a cleaning composition comprising 1) at least one redox agent; 2) at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers; 3) at least one metal containing additive; and 4) water.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 431,620, filed December 8, 2016, and U.S. Provisional Application No. 62 / 404,852, filed October 6, 2016, both of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention relates to a novel cleaning composition for semiconductor substrates and a method for cleaning semiconductor substrates. More specifically, this invention relates to a cleaning composition for use on semiconductor substrates after plasma etching of a metal layer or dielectric material layer deposited on the substrate, and to removing residues remaining on the substrate after most of the photoresist has been removed by plasma ashing. Background Technology

[0004] In the fabrication of integrated circuit devices, photoresist serves as an intermediate mask, used to transfer the original mask pattern of a reticle onto a wafer substrate through a series of photolithography and plasma etching steps. One of the fundamental steps in the integrated circuit device manufacturing process is the removal of the patterned photoresist film from the wafer substrate. Typically, this step is performed using one of two methods.

[0005] One method involves a wet stripping step in which a photoresist-coated substrate is contacted with a photoresist stripping agent solution primarily composed of organic solvents and amines. However, the stripping agent solution cannot completely and reliably remove the photoresist film, especially if the photoresist film has been exposed to ultraviolet radiation and plasma treatment during manufacturing. Some photoresist films become highly cross-linked and more difficult to dissolve in the stripping agent solution through this treatment. Furthermore, the chemicals used in this conventional wet stripping method are sometimes ineffective in removing inorganic or organometallic residues formed during etching of metal or oxide layers with halogen-containing gas plasma.

[0006] Another method for removing photoresist involves exposing the photoresist-coated wafer to oxygen-based plasma to burn the photoresist off the substrate in a process known as plasma ashing. However, plasma ashing is not entirely effective for removing these plasma etching byproducts. Instead, removal of these byproducts is typically accomplished by subsequently exposing the treated metal and dielectric films to a cleaning solution.

[0007] Metallic substrates are generally susceptible to corrosion. For example, substrates such as aluminum, copper, aluminum-copper alloys, tungsten nitride, tungsten (W), cobalt (Co), titanium oxide, other metals, and metal nitrides are easily corroded, and dielectrics [ILD, ULK] can be etched using conventional cleaning chemicals. Furthermore, as device geometries shrink, the tolerance for corrosion among integrated circuit device manufacturers is becoming increasingly smaller.

[0008] At the same time, because residues become more difficult to remove and corrosion needs to be controlled to a lower level, cleaning solutions need to be safe to use and environmentally friendly.

[0009] Therefore, the cleaning solution must effectively remove residues from plasma etching and plasma ashing, and must also be non-corrosive to all exposed substrate materials. Summary of the Invention

[0010] This invention relates to a non-corrosive cleaning composition that can be used as an intermediate step in a multi-step manufacturing process to remove residues (e.g., residues from plasma etching and / or plasma ashing) from a semiconductor substrate. Such residues include organic compounds, such as residual photoresist; organometallic compounds; metal oxides, such as aluminum oxide (AlOx), titanium oxide (TiOx), zirconium oxide (ZrOx), tantalum oxide (TaOx), and hafnium oxide (HfOx) (which are formed as reaction byproducts from exposed metals); metals, such as aluminum (Al), aluminum / copper alloys, copper (Cu), titanium (Ti), tantalum (Ta), tungsten (W), and cobalt (Co); metal nitrides, such as aluminum nitride (AlN), aluminum oxynitride (AlOxNy), titanium nitride (TiN), tantalum nitride (TaN), tungsten nitride (WN), and alloys thereof; and a range of relatively insoluble mixtures of other materials. The cleaning compositions described herein have the advantage of being able to clean a wide range of residues and are generally non-corrosive to exposed substrate materials (e.g., exposed metals such as aluminum, aluminum / copper alloys, copper, titanium, tantalum, tungsten, and cobalt), metal nitrides such as titanium, tantalum, and tungsten nitrides, and their alloys).

[0011] On one hand, the present invention is characterized by a cleaning composition containing

[0012] 1) At least one oxidizing or reducing agent;

[0013] 2) At least one organic solvent, selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters and water-soluble ethers;

[0014] 3) At least one metal-containing additive; and

[0015] 4) Water.

[0016] The present invention is further characterized by a method for cleaning residues from a semiconductor substrate. This method involves contacting a semiconductor substrate containing etch residues and / or ashing residues with the cleaning composition described herein. For example, the method may include the following steps:

[0017] (A) Provides a semiconductor substrate containing etch residues and / or ashing residues;

[0018] (B) Contact the semiconductor substrate with the cleaning composition described herein;

[0019] (C) Rinse the semiconductor substrate with a suitable rinsing solvent; and

[0020] (D) Optionally, the semiconductor substrate may be dried by any means of removing the rinsing solvent without compromising the integrity of the semiconductor substrate. Detailed Implementation

[0021] As defined herein, unless otherwise stated, all percentages expressed shall be understood as weight percentages relative to the total weight of the cleaning composition. Unless otherwise stated, ambient temperature is defined as about 16 degrees Celsius to about 27 degrees Celsius (°C), such as 25°C.

[0022] The terms "layer" and "film" are used interchangeably.

[0023] As defined herein, a "water-soluble" substance (e.g., a water-soluble alcohol, ketone, ester, or ether) means a substance that has a solubility of at least 5% by weight in water at 25°C.

[0024] One embodiment of the present invention relates to a non-corrosive cleaning composition comprising:

[0025] 1) At least one oxidizing or reducing agent;

[0026] 2) At least one organic solvent, selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters and water-soluble ethers;

[0027] 3) At least one metal-containing additive; and

[0028] 4) Water.

[0029] The compositions of the present invention contain at least one redox agent, which is believed to aid in the dissolution of residues on semiconductor surfaces, such as photoresist residues, metal residues, and metal oxide residues. As used herein, the term "redox agent" refers to a compound that can induce oxidation and / or reduction during semiconductor cleaning. A suitable example of a redox agent is hydroxylamine. In some embodiments, the redox agent or cleaning composition described herein does not include peroxides (e.g., hydrogen peroxide).

[0030] In some embodiments, the compositions of the present invention comprise at least about 0.5% by weight (e.g., at least about 1% by weight, at least about 2% by weight, at least about 3% by weight, or at least about 5% by weight) and / or up to about 20% by weight (e.g., up to about 17% by weight, up to about 15% by weight, up to about 12% by weight, or up to about 10% by weight) of an oxidizing agent.

[0031] The compositions of the present invention contain at least one (e.g., two, three, four or more) organic solvents selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters and water-soluble ethers (e.g., glycol diethers).

[0032] Water-soluble alcohols include, but are not limited to, alkyldiols (including, but not limited to, alkylene diols), glycols, alkoxyl alcohols (including, but not limited to, glycol monoethers), saturated aliphatic monohydroxyl alcohols, unsaturated non-aromatic monohydroxyl alcohols, and low molecular weight alcohols containing cyclic structures.

[0033] Examples of water-soluble alkyldiols include, but are not limited to, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycols.

[0034] Examples of water-soluble alkylene glycols include, but are not limited to, ethylene glycol, propylene glycol, hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

[0035] Examples of water-soluble alkoxyl alcohols include, but are not limited to, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and water-soluble diol monoethers.

[0036] Examples of water-soluble glycol monoethers include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and ethylene glycol monobenzyl ether and diethylene glycol monobenzyl ether.

[0037] Examples of water-soluble saturated aliphatic monohydroxy alcohols include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, tert-pentanol, and 1-hexanol.

[0038] Examples of water-soluble unsaturated non-aromatic monohydroxy alcohols include, but are not limited to, allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol and 4-penten-2-ol.

[0039] Examples of water-soluble low molecular weight alcohols containing cyclic structures include, but are not limited to, tetrahydrofuran methanol, furan methanol, and 1,3-cyclopentanediol.

[0040] Examples of water-soluble ketones include, but are not limited to, acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 2,5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone.

[0041] Examples of water-soluble esters include, but are not limited to, ethyl acetate, glycol monoesters such as ethylene glycol monoacetate, diethylene glycol monoacetate, and glycol monoether monoesters such as propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoethyl ether acetate.

[0042] In some embodiments, the cleaning compositions of the present invention comprise at least about 60% by weight (e.g., at least about 65% by weight, at least about 70% by weight, or at least about 75% by weight) and / or up to about 95% by weight (e.g., up to about 90% by weight, up to about 85% by weight, or up to about 80% by weight) of at least one organic solvent.

[0043] The cleaning composition of the present invention further includes water. Preferably, the water is deionized and ultrapure, free of organic contaminants, and has a minimum resistance of about 4 to about 17 megohms. More preferably, the resistance of the water is at least 17 megohms.

[0044] In some embodiments, the compositions of the present invention comprise at least about 5% by weight (e.g., at least about 8% by weight, at least about 12% by weight, or at least about 16% by weight) and / or up to about 28% by weight (e.g., up to about 24% by weight, up to about 20% by weight, or up to about 18% by weight) of water.

[0045] The metal-containing additives considered for use in the cleaning compositions of the present invention contain a metal selected from Group 2A, Group 3B, Group 4B, Group 5B, and lanthanides. In some embodiments, the metal is Ca, Ba, Ti, Hf, Sr, La, Ce, W, V, Nb, or Ta. In some embodiments, the metal is selected from Group 4B metals (such as Ti or Hf).

[0046] The metal-containing additive may be in the form of a metal halide, metal hydroxide, metal boride, metal alkoxide, metal oxide, or a metal-containing ammonium salt. In some embodiments, the metal-containing additive is an ammonium salt. This ammonium salt may be a salt having the formula (I): (NH4)mMXn(I); wherein m is 1, 2, 3, or 4; n is 1, 2, 3, 4, 5, or 6; M is a metal ion (such as ions of Group 2A, Group 3B, Group 4B, Group 5B, or lanthanides); and X is a halide ion (e.g., F, Cl, Br, or I). In some embodiments, the metal-containing additive is ammonium hexafluorotitanate. Examples of metal-containing additives may include tungsten boride, Ca(OH)2, BaCl2, SrCl2, LaCl3, CeCl3, (NH4)2TiF6, BaTiO3, Ti(OEt)4, Ti(OCH(CH3)2)4, HfO2, V2O5, Nb2O5, or TaF3.

[0047] In some embodiments, the metal-containing additive may be in an amount of at least about 0.001% by weight (e.g., at least about 0.002% by weight, at least about 0.004% by weight, at least about 0.006% by weight, at least about 0.008% by weight, or at least about 0.01% by weight) and / or at most about 0.5% by weight (e.g., at most about 0.4% by weight, at most about 0.3% by weight, at most about 0.2% by weight, at most about 0.1% by weight, at most about 0.08% by weight, at most about 0.06% by weight, at most about 0.04% by weight, at most about 0.02% by weight, or at most about 0.01% by weight). While not bound by theory, it is believed that the presence of the metal-containing additive in the cleaning composition in the amounts detailed above can reduce the corrosive effect of the composition, i.e., reduce the etching rate of the cleaning composition on exposed substrate materials (e.g., exposed metals or dielectric materials) that are not intended to be removed during the cleaning process.

[0048] The cleaning compositions of the present invention optionally contain at least one cleaning additive to improve their cleaning ability (e.g., removal of etching or ashing residues) and / or reduce their corrosive effect. In some embodiments, the cleaning additive may be a sulfur-containing additive or an amino acid. In some embodiments, the cleaning composition may contain both a sulfur-containing additive and an amino acid.

[0049] The sulfur-containing additives considered for use in the cleaning compositions of the present invention are not particularly limited. In some embodiments, the sulfur-containing additives are those with a thiol group (i.e., SH) or a thioether group (e.g., SR, where R is C1-C). 10The molecule contains an alkyl group. In some embodiments, the sulfur-containing additive may be an alcohol, acid, amine, or heterocyclic compound containing a thiol or thioether group. Examples of sulfur-containing additives include, but are not limited to, 3-amino-5-mercapto-1H-1,2,4-triazole, β-mercaptoethanol, 3-amino-5-methylthio-1H-1,2,4-triazole, 1-phenyl-1H-tetrazole-5-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-mercaptopyridine, 3-mercaptopropionic acid, etc. In some embodiments, sulfur-containing additives may exclude sulfur-containing organic acids.

[0050] In some embodiments, the sulfur-containing additive may be in an amount of at least about 0.01% by weight (e.g., at least about 0.02% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, or at least about 0.08% by weight) and / or at most about 0.15% by weight (e.g., at most about 0.14% by weight, at most about 0.12% by weight, at most about 0.1% by weight, at most about 0.08% by weight, or at most about 0.07% by weight) of the composition. While not intended to be theoretically limiting, it is believed that the presence of the sulfur-containing additive in the cleaning composition in the amounts detailed above may improve the cleaning ability of the composition for removing post-etching and / or post-ashing residues and / or reduce the etching rate of the cleaning composition on exposed substrate materials (e.g., exposed metals or dielectric materials) that are not intended to be removed during the cleaning process.

[0051] In some embodiments, the cleaning additive may include at least one amino acid. Examples of suitable amino acids include glycine. The amino acid may be a natural amino acid or a non-natural amino acid (e.g., a synthetic amino acid). The amino acid may be a D- or L-amino acid.

[0052] In some embodiments, the amino acids may be in an amount of at least about 0.01% by weight (e.g., at least about 0.02% by weight, at least about 0.04% by weight, at least about 0.05% by weight, at least about 0.06% by weight, or at least about 0.08% by weight) and / or at most about 0.15% by weight (e.g., at most about 0.14% by weight, at most about 0.12% by weight, at most about 0.1% by weight, at most about 0.08% by weight, or at most about 0.07% by weight). While not intended to be theoretically restrictive, it is believed that the presence of the amino acids detailed above in the cleaning composition may improve the cleaning ability of the composition for removing post-etching and / or post-ashing residues and / or reduce the etching rate of the cleaning composition on exposed substrate materials (e.g., exposed metals or dielectric materials) that are not intended to be removed during the cleaning process.

[0053] In some embodiments, the cleaning compositions of the present invention may contain one or more organic acids. The organic acids may be used in the cleaning compositions with or without the aforementioned cleaning additives (e.g., sulfur-containing additives or amino acids). Organic acids considered for use in the cleaning compositions of the present invention include carboxylic acids and sulfonic acids. Exemplary carboxylic acids considered for use in the compositions of the present invention include, but are not limited to, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, α-hydroxy and β-hydroxy acids of monocarboxylic acids, α-hydroxy or β-hydroxy acids of dicarboxylic acids, or α-hydroxy and β-hydroxy acids of tricarboxylic acids. In some embodiments, this at least one carboxylic acid includes citric acid, maleic acid, fumaric acid, lactic acid, glycolic acid, oxalic acid, tartaric acid, succinic acid, or benzoic acid. Examples of sulfonic acids include, but are not limited to, methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroethanesulfonic acid, perfluoroethanesulfonic acid, perfluoro(ethoxyethane)sulfonic acid, perfluoro(methoxyethane)sulfonic acid, dodecyl sulfonic acid, perfluorododecyl sulfonic acid, butyric acid, perfluorobutyric acid, propanesulfonic acid, perfluoropropanesulfonic acid, octyl sulfonic acid, perfluorooctyl sulfonic acid, methanedisulfonic acid, 2-methylpropanesulfonic acid, cyclohexanesulfonic acid, camphor sulfonic acid, perfluorohexanesulfonic acid, ethanedisulfonic acid, and benzene. Methanesulfonic acid, hydroxybenzenesulfonic acid, naphthylmethanesulfonic acid, and norbornenesulfonic acid, benzenesulfonic acid, chlorobenzenesulfonic acid, bromobenzenesulfonic acid, fluorobenzenesulfonic acid, hydroxybenzenesulfonic acid, nitrobenzenesulfonic acid, 2-hydroxy-5-sulfobenzoic acid, benzenedisulfonic acid, toluenesulfonic acid (e.g., p-toluenesulfonic acid), methylchlorobenzenesulfonic acid, dodecylbenzenesulfonic acid, butylbenzenesulfonic acid, cyclohexylbenzenesulfonic acid, picric acid, dichlorobenzenesulfonic acid, dibromobenzenesulfonic acid, and 2,4,5-trichlorobenzenesulfonic acid.

[0054] In some embodiments, the organic acid may be in an amount of at least about 0.1% by weight (e.g., at least about 0.12% by weight, at least about 0.14% by weight, at least about 0.16% by weight, at least about 0.18% by weight, or at least about 0.2% by weight) and / or at most about 0.5% by weight (e.g., at most about 0.4% by weight, at most about 0.3% by weight, at most about 0.2% by weight, at most about 0.18% by weight, or at most about 0.16% by weight). While not bound by theory, it is believed that the organic acid can act as a chelating agent in cleaning compositions to facilitate the removal of residues after etching and / or ashing.

[0055] The cleaning composition of the present invention optionally contains at least one conductivity enhancer. Suitable conductivity enhancers include quaternary ammonium hydroxides, quaternary ammonium salts, and imidazole salts. For example, suitable conductivity enhancers may be tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrabutylammonium chloride, benzyltrimethylammonium hydroxide, or 1-butyl-3-methylimidazolium methanesulfonate.

[0056] In some embodiments, the conductivity promoter may be at least about 1% (e.g., at least about 2 wt%, at least about 3 wt%, at least about 4 wt%, at least about 5 wt%, or at least about 6 wt%) to at most about 10 wt% (e.g., at most about 9 wt%, at most about 8 wt%, at most about 7 wt%, at most about 6 wt%, or at most about 5 wt%) of the composition. While not intended to be theoretically sound, it is believed that the conductivity promoter can reduce Co loss or corrosion during cleaning steps and can act as a Co corrosion inhibitor.

[0057] The cleaning compositions of the present invention optionally contain at least one pH adjuster (e.g., an acid or a base) to control the pH at about 7 to about 11. In some embodiments, the compositions of the present invention may have a pH of at least about 7 (e.g., at least about 7.5, at least about 8, or at least about 8.5) to at most about 11 (e.g., at most about 10.5, at most about 10, at most about 9.5, at most about 9). While not intended to be theoretically restrictive, it is believed that cleaning compositions with a pH higher than 11 reduce the cleaning of plasma etching residues to a level that is not completely cleanable, and that a pH lower than 7 increases the etching rate of certain metals or dielectric materials to an undesirable level. The effective pH will vary depending on the type and amount of the components used in the compositions described herein.

[0058] If applicable, the amount of pH adjuster required can vary because the concentrations of other components, particularly hydroxylamine and organic acids, will vary in different formulations, and the amount of pH adjuster required is a function of the molecular weight of the specific pH adjuster used. Typically, the concentration of the pH adjuster ranges from about 0.1% by weight to about 3% by weight of the cleaning composition. In some embodiments, the cleaning composition of the present invention contains at least about 0.1% by weight (e.g., at least about 0.5% by weight, at least about 1% by weight, or at least about 1.5% by weight) and / or at most about 3% by weight (e.g., at most about 2.5% by weight, at most about 2% by weight, or at most about 1.5% by weight) of a pH adjuster.

[0059] Typically, pH adjusters are free of any metal ions (except for trace metal ion impurities). Suitable metal-free pH adjusters include ammonium hydroxide, quaternary ammonium hydroxides, monoamines (including alkanolamines), imines (such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]-5-nonene), and guanidine salts (such as guanidine carbonates).

[0060] Suitable examples of quaternary ammonium hydroxides include, but are not limited to, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, dimethyldiethylammonium hydroxide, choline, tetraethanolammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and benzyltributylammonium hydroxide.

[0061] Suitable examples of monoamines include, but are not limited to, triethylamine, tributylamine, tripentylamine, ethanolamine, diethanolamine, diethylamine, butylamine, dibutylamine, and benzylamine.

[0062] Furthermore, in some embodiments, the cleaning compositions of the present invention may contain additives as optional components, such as additional pH adjusters, corrosion inhibitors (e.g., substituted or unsubstituted benzotriazoles), surfactants, additional organic solvents, biocides, and defoamers.

[0063] Examples of suitable defoamers include polysiloxane defoamers (e.g., polydimethylsiloxane), polyethylene glycol methyl ether polymers, ethylene oxide / propylene oxide copolymers, and glycidyl ether-terminated acetylation glycol ethoxides (such as those described in U.S. Patent No. 6,717,019, which is incorporated herein by reference).

[0064] In some embodiments, the cleaning compositions of the present invention may specifically exclude one or more (or more than one, in any combination) additive components. This component is selected from the group consisting of: oxygen scavengers; quaternary ammonium hydroxides; amines; alkali metal and alkaline earth metal bases (such as NaOH, KOH, LiOH, magnesium hydroxide, and calcium hydroxide); surfactants other than defoamers; fluorinated compounds; oxidizing agents (e.g., peroxides, hydrogen peroxide, ferric nitrate, potassium iodate, potassium permanganate, nitric acid, ammonium chlorite, ammonium chlorate, ammonium iodate, ammonium perborate, ammonium perchlorate, ammonium periodate, ammonium persulfate, tetramethylammonium chlorite, tetramethylammonium iodate, tetramethylammonium perborate, tetramethylammonium perchlorate, tetramethylammonium periodate, tetramethylammonium persulfate, urea peroxide, and peracetic acid); abrasives; silicates; hydroxycarboxylic acids; amino-deficient carboxylic acids and polycarboxylic acids; nonazole corrosion inhibitors; guanidine; guanidine salts; inorganic acids (e.g., sulfonic acid, sulfuric acid, sulfurous acid, nitrous acid, nitric acid, phosphoric acid, and phosphoric acid); pyrrolidone; polyvinylpyrrolidone; metal halides; formula W z MX y The metal halide, wherein W is selected from H, alkali metals or alkaline earth metals, and metal-ion-free hydroxide base moiety, M is a metal selected from the group consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ru and Sb, y is 4 to 6, and z is 1, 2 or 3; and corrosion inhibitors other than the corrosion inhibitors described in this invention.

[0065] In some embodiments, the cleaning composition of the present invention is not specifically designed to remove most of the photoresist film from a semiconductor substrate. Instead, the cleaning composition of the present invention may be designed to remove all residues remaining after most of the photoresist has been removed by a dry or wet stripping method. Therefore, in some embodiments, the cleaning method of the present invention is preferably used after a dry or wet photoresist stripping method. This photoresist stripping step is typically performed after a patterning transfer step, such as an etching or implantation step, or before patterning transfer to correct mask errors. The chemical composition of the residue depends on the processes preceding the cleaning step or the individual processes.

[0066] Any suitable dry stripping method can be used to remove most of the photoresist from a semiconductor substrate. Examples of suitable dry stripping methods include oxygen-based plasma ashing, such as fluorine / oxygen plasma or N2 / H2 plasma; ozone phase treatment; fluorine plasma treatment; thermal H2 gas treatment (such as that described in U.S. Patent No. 5,691,117, which is incorporated herein by reference in its entirety), etc. Furthermore, any conventional organic wet stripping solution known to those skilled in the art can be used to remove most of the photoresist from a semiconductor substrate.

[0067] A preferred stripping method used in conjunction with the cleaning method of the present invention is a dry stripping method. Preferably, this dry stripping method is an oxygen-based plasma ashing method. This method removes most of the photoresist from the semiconductor substrate by applying an active oxygen atmosphere at high temperature (typically 250°C) and vacuum conditions (i.e., 1 torr). Organic materials are oxidized and removed by the process gas. However, this method cannot remove inorganic or organometallic contaminants from the semiconductor substrate. Typically, subsequent cleaning of the semiconductor substrate with the cleaning composition of the present invention is required to remove such residues.

[0068] In some embodiments, a method for cleaning residues from a semiconductor substrate is provided. This method may, for example, involve contacting the semiconductor substrate containing etched residues and / or ashing residues with the cleaning composition described herein. The method may further include rinsing the semiconductor substrate with a rinsing solvent after this contact step and / or drying the semiconductor substrate after the rinsing step. In some embodiments, the semiconductor substrate may further comprise a material (e.g., exposed material) or a layer of material, wherein the material is selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.

[0069] In some embodiments, the cleaning method includes the following steps:

[0070] (A) Providing a semiconductor substrate containing etched and / or ashing residues;

[0071] (B) Contact the semiconductor substrate with the cleaning composition described herein;

[0072] (C) Rinse the semiconductor substrate with a suitable rinsing solvent; and

[0073] (D) Optionally, the semiconductor substrate may be dried by any means of removing the rinsing solvent without compromising the integrity of the semiconductor substrate.

[0074] In some embodiments, the cleaning method further includes forming a semiconductor device (e.g., an integrated circuit device, such as a semiconductor wafer) from the semiconductor substrate obtained by the above method. The semiconductor substrate to be cleaned in the method may contain organic residues and organometallic residues, as well as a series of metal oxides to be removed. The semiconductor substrate is typically composed of silicon, silicon-germanium, III-V compounds such as GaAs, or combinations thereof. The semiconductor substrate may additionally contain exposed integrated circuit structures, such as interconnect features (e.g., metal lines and dielectric materials). Metals and metal alloys used for interconnect features include, but are not limited to, aluminum, copper-aluminum alloys, copper, titanium, tantalum, cobalt, and silicon, titanium nitride, tantalum nitride, tungsten, and alloys thereof. The semiconductor substrate may also contain interlayer dielectrics, layers of silicon oxide, silicon nitride, silicon carbide, titanium oxide, and carbon-doped silicon oxide.

[0075] The semiconductor substrate may be brought into contact with the cleaning composition by any suitable method, such as placing the cleaning composition in a tank and immersing and / or submerging the semiconductor substrate in the cleaning composition, spraying the cleaning composition onto the semiconductor substrate, flowing the cleaning composition onto the semiconductor substrate, or any combination thereof. Preferably, the semiconductor substrate is immersed in the cleaning composition.

[0076] The cleaning composition of the present invention can be used effectively at temperatures up to about 90°C (e.g., from about 25°C to about 80°C, from about 30°C to about 60°C, or from about 40°C to about 60°C).

[0077] Similarly, cleaning time can vary widely depending on the specific cleaning method used and the temperature. When cleaning with an immersion batch method, a suitable time range is, for example, up to about 60 minutes (e.g., about 1 minute to about 60 minutes, about 3 minutes to about 20 minutes, or about 4 minutes to about 15 minutes).

[0078] The cleaning time range for a single wafer process can be from about 10 seconds to about 5 minutes (e.g., from about 15 seconds to about 4 minutes, from about 15 seconds to about 3 minutes, or from about 20 seconds to about 2 minutes).

[0079] To further enhance the cleaning ability of the cleaning composition of the present invention, mechanical agitation methods can be used. Examples of suitable agitation methods include circulating the cleaning composition on the substrate during the cleaning method, flowing or spraying the cleaning composition onto the substrate, and ultrasonic or megasonic agitation. The orientation of the semiconductor substrate relative to the ground can be any angle. Horizontal or vertical orientation is preferred.

[0080] The cleaning compositions of the present invention can be used with conventional cleaning tools known to those skilled in the art. A significant advantage of the compositions of the present invention is that they contain, wholly or partially, relatively non-toxic, non-corrosive, and non-reactive components, and therefore, the compositions are stable over a wide range of temperatures and processing times. The compositions of the present invention are chemically compatible with virtually all materials used in constructing existing and recommended semiconductor wafer cleaning processing tools for batch and individual wafer cleaning.

[0081] After cleaning, the semiconductor substrate may be rinsed with a suitable rinsing solvent for approximately 5 seconds to approximately 5 minutes, with or without agitation. Examples of suitable rinsing solvents include, but are not limited to, deionized (DI) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether acetate. Alternatively, an aqueous rinsing solution with a pH > 8 (such as a dilute aqueous solution of ammonium hydroxide) may be used. Preferred examples of rinsing solvents include, but are not limited to, dilute aqueous solution of ammonium hydroxide, deionized water, methanol, ethanol, and isopropanol. More preferred rinsing solvents are dilute aqueous solution of ammonium hydroxide, deionized water, and isopropanol. The most preferred rinsing solvents are dilute aqueous solution of ammonium hydroxide and deionized water. The solvent may be applied using a method similar to that used for applying the cleaning composition described herein. The cleaning composition may have been removed from the semiconductor substrate before the rinsing step begins, or it may still be in contact with the semiconductor substrate at the start of the rinsing step. Preferably, the temperature for the rinsing step is 16°C to 27°C.

[0082] Optionally, the semiconductor substrate is dried after the rinsing step. Any suitable drying method known in the art can be used. Examples of suitable drying methods include rotary drying, passing a drying gas over the semiconductor substrate, or heating the semiconductor substrate with a heating device such as a hot plate or infrared lamp, Marangoni drying, Rotagoni drying, IPA drying, or any combination thereof. The drying time depends on the specific method used, but is typically in the range of 30 seconds to several minutes.

[0083] In some embodiments, a method for fabricating an integrated device using the cleaning composition described herein may include the following steps. First, a photoresist layer is applied to a semiconductor substrate. The resulting semiconductor substrate is then subjected to a patterning transfer step, such as etching or implantation, to form an integrated circuit. Most of the photoresist is then removed by a dry or wet stripping method (e.g., oxygen plasma ashing). Residue remaining on the semiconductor substrate is then removed using the cleaning composition described herein in the manner described above. The semiconductor substrate may then be processed to form one or more additional circuits on the substrate, or may be processed to form a semiconductor wafer by, for example, assembly (e.g., dicing and bonding) and encapsulation (e.g., wafer sealing).

[0084] All publicly available information cited in this article (e.g., patents, patent application publications and documents) is incorporated herein in its entirety for reference.

[0085] Example

[0086] The invention is illustrated in more detail with reference to the following examples, which are for illustrative purposes and should not be construed as limiting the scope of the invention. Unless otherwise stated, any percentages listed are by weight (wt%). Unless otherwise noted, controlled stirring during testing was performed at 300 rpm using a 1-inch stir bar.

[0087] General Procedure 1

[0088] Formulation blending

[0089] The composition of this invention is prepared by mixing an organic solvent and ultrapure deionized water (DIW) under stirring. After obtaining a homogeneous solution, the remaining components are added. All components used are commercially available and of high purity.

[0090] General Procedure 2

[0091] Cleanliness assessment using beaker test

[0092] Using a multilayer substrate of photoresist / TiOx / SiN / Co / ILD (ILD = interlayer dielectric) or photoresist / TiOx / SiN / W / ILD that has been photolithographically patterned, etched in a plasma metal etchant, and subsequently ashed by oxygen plasma to completely remove the upper photoresist layer, the above-described cleaning composition is used to clean the PER (post-etching residue) from the substrate.

[0093] The test piece is secured using 4” long plastic locking tweezers, and then suspended in a 500 mL glass beaker containing approximately 200 mL of the cleaning composition of the present invention. Before immersing the test piece in the cleaning composition, the composition is preheated to the desired test condition temperature (typically 40°C or 60°C, as mentioned) with controlled stirring. The cleaning test is then performed by placing the test piece secured with the plastic locking tweezers into the heated composition with the PER layer side of the test piece facing the stirring rod. The test piece is allowed to stand in the cleaning composition for a period of time (typically 2 to 5 minutes) while the composition is maintained at the test temperature with controlled stirring. When the desired cleaning time is complete, the test piece is quickly removed from the cleaning composition and placed in… A 500 mL plastic beaker containing approximately 400 mL of deionized water at ambient temperature (~17°C) was gently stirred. The test piece was left in the beaker of deionized water for approximately 30 seconds, then quickly removed and rinsed under a stream of deionized water at ambient temperature for approximately 30 seconds. The test piece was immediately exposed to a stream of nitrogen from a handheld nitrogen gun to blow away any droplets from the surface and further dry the surface completely. After the final nitrogen drying step, the test piece was removed from the plastic tweezers holder and placed in a covered plastic container, device side up, for a short storage period of no more than approximately 2 hours. Scanning electron microscopy (SEM) images of key features on the cleaned test piece surface were then acquired.

[0094] General Procedure 3

[0095] Material compatibility assessment using beaker tests

[0096] Co-coated silicon substrates, W-coated silicon substrates, TiOx-coated SiO2-coated silicon substrates, SiN-coated silicon substrates, ILD-coated silicon substrates, SiC-coated silicon substrates, and W alloy-coated silicon substrates were cut into approximately 1-inch × 1-inch rectangular test pieces for material compatibility testing. First, the thickness or sheet resistance of the metal film (Co, W) test pieces was measured using a Woollam M-2000X with a 4-point probe CDE Resmap 27, and the thickness or sheet resistance of the dielectric film (TiOx, SiN, and ILD) test pieces was measured using an Elisometry. Then, the test pieces were mounted on 4” long plastic locking tweezers and treated for 10 minutes using the cleaning procedure described in General Procedure 2, with the side containing the Co, W, W alloy, TiOx, SiN, SiC, or ILD layer facing the stirring rod.

[0097] After the final nitrogen drying step, the test piece is removed from the plastic tweezers holder and placed in a covered plastic container. Then, using a Woollam M-2000X with a 4-point probe CDE Resmap 273, post-thickness or sheet resistance is collected on the surface of the processed metal film (Co, W, and W alloy) test piece, and using an Elipsometry to collect post-thickness or sheet resistance on the surface of the processed dielectric film (TiOx, SiN, SiC, and ILD) test piece.

[0098] Formulation Examples FE-1-FE-7

[0099] Table 1 includes formulations FE-1 to FE-7 (containing sulfur-containing additives) prepared by general procedure 1.

[0100] Table 1

[0101]

[0102] DEGBE = diethylene glycol butyl ether; Hex glycol = hexanediol; MSA = methanesulfonic acid

[0103] Example 1-3

[0104] Compatibility of cleaning agents with exposed metals or dielectrics

[0105] The cleaning capabilities of formulations FE-4, FE-6, and FE-7 were tested at 65°C for 4 minutes according to general procedure 2, and their material compatibility was tested at 65°C for 4 minutes according to general procedure 3. The etching rates (ER) (Å / min) of the cleaning compositions for Co, W, W alloys, TiOx, SiN, SiC, and ILD are shown in Table 2.

[0106] Table 2

[0107]

[0108] "NA" indicates that data is unavailable.

[0109] The data in Table 2 show that the formulations of the present invention (i.e., FE-4, FE-6 and FE-7) clean the etching residues and do not significantly etch semiconductor materials commonly found in semiconductor devices (such as Co, W, TiOx, SiN, SiC, TEOS and ILD).

[0110] Formulation Examples FE-8-FE-26 and CFE-1

[0111] Table 3 includes formulations FE-8 to FE-26 prepared by general procedure 1 (which do not include any sulfur-containing additives or any acids).

[0112] Table 3

[0113]

[0114] Examples 4-22 and Comparative Example 1

[0115] Compatibility of cleaning agents with exposed metals

[0116] The material compatibility of formulations FE-8 to FE-26 and CFE-1 was tested at 65°C for 4 minutes according to general procedure 3. The etching rates (ER) (Å / min) of the cleaning formulations for W alloys, TiOx, Co and W are shown in Table 4.

[0117] Table 4

[0118] Ex. W alloy TiOx Co W CFE-1 4.5 1.5 4.0 0.2 FE-8 2.0 0.1 0.8 0.0 FE-9 2.8 0.2 0.2 0.0 FE-10 2.6 0.3 8.6 0.0 FE-11 4.9 0.3 0.6 0.2 FE-12 5.5 4.4 0.4 0.2 FE-13 2.3 0.8 0.2 0.2 FE-14 0.8 0.5 0.8 0.1 FE-15 0.4 0.9 0.7 0.2 FE-16 0.4 0.9 0.7 0.1 FE-17 0.9 0.9 0.6 0.2 FE-18 1.9 0.1 0.6 0.0 FE-19 1.7 0.1 0.7 0.0 FE-20 1.4 0.2 0.6 0.0 FE-21 0.8 0.8 0.4 0.1 FE-22 0.2 0.9 0.4 0.0 FE-23 0.2 0.5 0.2 0.1 FE-24 0.6 1.7 0.1 0.6 FE-25 0.5 0.0 0.1 0.3 FE-26 1.0 0.7 0.3 0.2

[0119] The data in Table 4 show that, compared with cleaning agents without any metal-containing additives, the cleaning agents of the present invention (i.e., FE-8 to FE-26) significantly reduce corrosion or etching of at least one of the metals commonly found in semiconductor devices (such as W, W alloys, Co, or TiOx).

[0120] Formulation Examples FE-27-FE-32

[0121] Table 5 includes formulations FE-27 to FE-32 (which include the amino acid glycine) prepared by general procedure 1.

[0122] Table 5

[0123] Ex. bitterness self-indulgence DEGBE <![CDATA[(NH4)2TiF6]]> sweet acid water FE-27 9％ 65.77％ 9.2％ 0.0025％ 0.03％ 16％ FE-28 9％ 64.17％ 10.8％ 0.0025％ 0.03％ 16％ FE-29 9％ 64.97％ 10％ 0.0023％ 0.03％ 16％ FE-30 9％ 64.97％ 10％ 0.0027％ 0.03％ 16％ FE-31 9％ 64.97％ 10％ 0.0025％ 0.0276％ 16％ FE-32 9％ 64.97％ 10％ 0.0025％ 0.0324％ 16％

[0124] Examples 23-28

[0125] Compatibility of cleaning agents with exposed metals

[0126] The material compatibility of formulations FE-27 to FE-32 was tested at 65°C for 4 minutes according to standard procedure 3. The etching rates (ER) (Å / min) of the cleaning formulations on W alloys, Co, AlOx and TiOx are shown in Table 6.

[0127] Table 6

[0128] Ex. W alloy Co AlOx TiOx FE-27 1.7±0.8 1.2±0.3 3.1±0.1 3.1±0.0 FE-28 2.4±0.7 1.1±0.2 2.7±0.1 2.3±0.1 FE-29 1.7±0.6 1.4±0.1 2.2±0.1 2.5±0.0 FE-30 1.0±0.3 1.0±0.1 2.8±0.1 2.6±0.0 FE-31 3.7±0.5 1.2±0.1 2.5±0.1 2.6±0.1 FE-32 3.0±0.2 1.1±0.1 2.6±0.1 2.3±0.1

[0129] The data in Table 6 show that certain cleaning agents of the present invention (i.e., FE-27 to FE-32) exhibit relatively low corrosion or etching of metals commonly found in semiconductor devices (such as W alloys, Co, AlOx, or TiOx), and this low corrosion is not significantly altered by changes in the amount of solvent, metal-containing additives (i.e., NH4TiF6), and amino acids (i.e., glycine).

[0130] Formulation Examples FE-33-FE-40

[0131] Table 7 includes formulations FE-33 to FE-40 (which include the amino acid glycine) prepared by general procedure 1.

[0132] Table 7

[0133] Ex. bitterness self-indulgence DEGBE <![CDATA[(NH4)2TiF6]]> sweet acid water FE-33 9％ 62％ 10％ 0.0025％ 0.03％ 18.9820％ FE-34 9％ 63％ 10％ 0.0025％ 0.03％ 17.9820％ FE-35 9％ 64％ 10％ 0.0025％ 0.03％ 16.9820％ FE-36 9％ 65％ 10％ 0.0025％ 0.03％ 15.9820％ FE-37 9％ 66％ 10％ 0.0025％ 0.03％ 14.9820％ FE-38 9％ 67％ 10％ 0.0025％ 0.03％ 13.9820％ FE-39 9％ 68％ 10％ 0.0025％ 0.03％ 12.9820％ FE-40 9％ 69％ 10％ 0.0025％ 0.03％ 11.9820％

[0134] Examples 29-36

[0135] Compatibility of cleaning agents with exposed metals

[0136] The material compatibility of formulations FE-33 to FE-40 was tested at 65°C for 4 minutes according to standard procedure 3. The etching rates (ER) (Å / min) of the cleaning formulations on W alloys, Co, AlOx and TiOx are shown in Table 8.

[0137] Table 8

[0138] Ex. W alloy Co AlOx TiOx FE-33 6.7±0.1 1.4±0.3 2.8±0.0 3.4±0.2 FE-34 2.5±0.4 0.9±0.1 2.1±0.0 2.5±0.1 FE-35 3.2±0.3 1.2±0.2 2.2±0.3 2.7±0.2 FE-36 2.8±0.2 1.0±0.2 2.3±0.3 2.4±0.0 FE-37 3.3±0.4 0.8±0.01 2.83±0.02 2.29±0.03 FE-38 2.5±0.1 0.73±0.01 2.64±0.03 2.23±0.02 FE-39 2.73±0.3 0.63±0.01 2.16±0.03 2.02±0.03 FE-40 2.7±0.1 0.63±0.01 2.0±0.1 1.94±0.02

[0139] The data in Table 8 show that certain cleaning formulations of the present invention (i.e., FE-33 to FE-44) exhibit relatively low corrosion or etching of metals commonly found in semiconductor devices (such as W alloys, Co, AlOx, or TiOx), and this low corrosion is not significantly altered by changes in the amount of solvent and water in the formulation.

[0140] Formulation Examples FE-41-FE-52

[0141] Table 9 includes formulations FE-41 to FE-52 prepared by general procedure 1 (except for FE-41, all of which include conductivity enhancers).

[0142] Table 9

[0143]

[0144] TMAH: Tetramethylammonium hydroxide; TEAH: Tetraethylammonium hydroxide;

[0145] TBAH: Tetrabutylammonium hydroxide; TBACl: Tetrabutylammonium chloride;

[0146] BzTAH: Benzyltrimethylammonium hydroxide; BMIMS: 1-Butyl-3-methyl-imidazolium methanesulfonate

[0147] The conductivity of formulations FE-41 to FE-52 was measured using a conductivity meter. The results are summarized in Table 10 below.

[0148] Table 10

[0149] Ex. Electricity rate (μS / cm) FE-41 16 FE-42 767 FE-43 720 FE-44 755 FE-45 2331 FE-46 677 FE-47 610 FE-48 1030 FE-49 1407 FE-50 673 FE-51 1245 FE-52 709

[0150] As shown in Table 10, formulations FE-42 to FE-52 (which include conductivity enhancers) all exhibit significantly higher conductivity than formulation FE-41 (which does not include conductivity enhancers). While not wishing to be bound by theory, it is believed that increasing the conductivity of the cleaning formulation can result in reduced Co loss during the cleaning process. Therefore, it is believed that formulations FE-42 to FE-52 will have reduced Co loss compared to formulation FE-41.

[0151] While the present invention has been described in detail with reference to certain embodiments thereof, it should be understood that modifications and alterations are within the spirit and scope of the description and claims.

Claims

1. A cleaning composition comprising: 1) At least one oxidizing or reducing agent, said at least one oxidizing or reducing agent being from 0.5% to 20% by weight of the composition; 2) At least one organic solvent, selected from the group consisting of water-soluble alcohols, water-soluble ketones, water-soluble esters, and water-soluble ethers, wherein the at least one organic solvent comprises 60% to 95% by weight of the composition; 3) at least one metal-containing additive, said at least one metal-containing additive being present in the composition at a concentration of 0.001% to 0.3% by weight; and 4) Water, wherein the water comprises 5% to 28% by weight of the composition; The at least one metal-containing additive includes tungsten boride, Ca(OH)2, BaCl2, SrCl2, LaCl3, CeCl3, BaTiO3, Ti(OEt)4, Ti(OCH(CH3)2)4, HfO2, V2O5, Nb2O5, or TaF3; Wherein, the composition does not include formula W z MX y The metal halide, wherein W is selected from H, alkali metals or alkaline earth metals and the base portion of hydroxides without metal ions, M is a metal selected from the group consisting of Si, Ge, Sn, Pt, P, B, Au, Ir, Os, Cr, Ti, Zr, Rh, Ru and Sb, X is a halide ion selected from F, Cl, Br or I, y is 4 to 6, and z is 1, 2 or 3.

2. The composition of claim 1, wherein, The composition has a pH of 7 to 11.

3. The composition of claim 1, wherein, The at least one oxidizing agent includes hydroxylamine.

4. The composition of claim 1, wherein, The at least one oxidizing or reducing agent is 5% to 20% by weight of the composition.

5. The composition of claim 1, wherein, The at least one organic solvent comprises two organic solvents.

6. The composition of claim 5, wherein, The two organic solvents are each independently selected from the group consisting of alkylene glycols and alkylene glycol ethers.

7. The composition of claim 1, wherein, The at least one organic solvent is present in the composition at a concentration of 65% to 95% by weight.

8. The composition of claim 1, wherein, The at least one metal-containing additive is present in the composition at a concentration of 0.001% to 0.25% by weight.

9. The composition of claim 1, wherein, The water content is from 8% to 28% by weight of the composition.

10. The composition of claim 1, further comprising a pH adjuster.

11. The composition of claim 10, wherein, The pH adjuster is 1,8-diazabicyclo[5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-nonene.

12. The composition of claim 1, further comprising at least one cleaning additive.

13. The composition of claim 12, wherein, The at least one cleaning additive is a sulfur-containing additive.

14. The composition of claim 13, wherein, The sulfur-containing additives include thiols or thioethers.

15. The composition of claim 14, wherein, The sulfur-containing additives include 3-amino-5-mercapto-1H-1,2,4-triazole, β-mercaptoethanol, 3-amino-5-methylthio-1H-1,2,4-triazole, 1-phenyl-1H-tetrazole-5-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol, 2-mercaptopyridine, or 3-mercaptopropionic acid.

16. The composition of claim 13, wherein, The sulfur-containing additive is present in the composition at a concentration of 0.01% to 0.15% by weight.

17. The composition of claim 12, wherein, The at least one cleaning additive includes amino acids.

18. The composition of claim 17, wherein, The amino acid in question is glycine.

19. The composition of claim 17, wherein, The amino acid is present in the composition at a concentration of 0.01% to 0.15% by weight.

20. The composition of claim 1, further comprising at least one organic acid.

21. The composition of claim 20, wherein, The at least one organic acid includes carboxylic acids or sulfonic acids.

22. The composition of claim 20, wherein, The at least one organic acid is present in the composition at a concentration of 0.1% to 0.5% by weight.

23. The composition of claim 1 further comprises at least one conductivity enhancer selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium salts and imidazole salts.

24. The composition of claim 23, wherein, The conductivity enhancer is tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, tetrabutylammonium chloride, benzyltrimethylammonium hydroxide, or 1-butyl-3-methyl-imidazolium-methanesulfonate.

25. The composition of claim 23, wherein, The at least one conductivity enhancer is present in the composition at a concentration of 1% to 10% by weight.

26. The composition of claim 11, wherein, The pH adjuster is 0.1% to 3% of the weight of the cleaning composition.

27. A method comprising: The semiconductor substrate containing etching residues or ashing residues is brought into contact with the cleaning composition as described in any one of claims 1 to 26.

28. The method of claim 27, wherein, The semiconductor substrate further includes a layer comprising a material selected from the group consisting of Cu, Co, W, AlOx, AlN, AlOxNy, Ti, TiN, Ta, TaN, TiOx, ZrOx, HfOx, and TaOx.

29. The method of claim 27, further comprising rinsing the semiconductor substrate with a rinsing solvent after the contact step.

30. The method of claim 29, further comprising drying the semiconductor substrate after the rinsing step.

31. The method of claim 27, further comprising forming a semiconductor device from the semiconductor substrate.

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